N-heterocyclic carbene functionalized transition metal dichalcogenides

Abstract

This invention relates to N-heterocyclic carbene functionalized transition metal dichalcogenides. This invention also relates to methods of making N-heterocyclic carbene functionalized transition metal dichalcogenides. This invention also relates to articles of manufacture comprising N-heterocyclic carbene functionalized transition metal dichalcogenides.

Description

N-HETEROCYCLIC CARBENE FUNCTIONALIZED TRANSITION METAL DICHALCOGENIDES CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 63 / 601,649 filed November 21, 2023, and U.S. Provisional Patent Application No.63 / 682,851 filed August 14, 2024, both of which are incorporated herein by reference in their entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] This invention was made with government support under Grant Nos. FA9550-20- 1-0349 and FA9550-23-1-0581 awarded by the U.S. Air Force Office of Scientific Research. The government has certain rights in the invention. FIELD OF THE INVENTION

[0003] This invention relates to N-heterocyclic carbene functionalized transition metal dichalcogenides. This invention also relates to methods of making N-heterocyclic carbene functionalized transition metal dichalcogenides. This invention also relates to articles of manufacture comprising N-heterocyclic carbene functionalized transition metal dichalcogenides. BACKGROUND

[0004] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. The following description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.

[0005] Efforts have been directed toward the functionalization of mono-to-few-layered transition metal dichalcogenides (TMDs). According to the literature, two approaches have been used to address this challenge, each employing distinctive categories of reagents: thiol-based 4886-5650-6109.1 Page 1 of 224094876-000020WOPTorganic adsorbates and electron-donating molecules. However, both of these previously reported approaches currently suffer from limitations. In the thiol-based strategy, organic molecules containing thiol (-SH) or disulfide (-S-S-) groups are used to establish a sulfur-chalcogenide bridge with TMDs. This bonding interaction is, however, fragile.

[0006] The current electron-donating strategy, while an improvement over the existing thiol-based strategy, still suffers from several limitations. Using the current electron-donating strategy, it has been observed that excessive intercalation can induce phase transformations within the TMDs. These phase transformations include a shift from the semiconducting state to the metallic state, rendering the functionalized TMDs impractical and unsuitable for use in several intended applications, specifically those where semiconducting properties and / or characteristics are needed.

[0007] Therefore, there is an ongoing need for new and improved functionalized transition metal dichalcogenides and methods of making them that overcome these limitations. The embodiments of the present invention address these needs. SUMMARY OF THE INVENTION

[0008] In various embodiments, the present invention provides a N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N-heterocyclic carbene.

[0009] In some embodiments, the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II),substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.4886-5650-6109.1Page 2 of 224 094876-000020WOPT

[0010] In some embodiments, the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A), substituted alkyl, optionally substituted heteroalkyl, optionallysubstituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R3aand R4aare not both absent, and wherein R5aand R6aare not both absent; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0011] In some embodiments, the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 3 of 224 094876-000020WOPTFormula (II-B), , 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0012] In some embodiments, the at least one N-heterocyclic carbene has a structure of Formula (IV): Formula (IV)4886-5650-6109.1Page 4 of 224 094876-000020WOPTwherein: Z1ais C; Z2ais C; R10ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12aand R13aare not both absent, and wherein R14aand R15aare not both absent; and between Z1aand Z2aindicates a bond that may be a single bond or a double bond; or R12aand R14a, or R12aand R15a, or R13aand R14a, or R13aand R15amay be taken together to form a ring, wherein the ring is optionally substituted.

[0013] In some embodiments, the at least one N-heterocyclic carbene is4886-5650-6109.1Page 5 of 224 094876-000020WOPT.

[0014] In some embodiments, the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen. In some embodiments, Mais a Group 6 transition metal. In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the at least one transition metal dichalcogenide is MoS2or WS2.

[0015] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one N- heterocyclic carbene forms a self-assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0016] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated4886-5650-6109.1Page 6 of 224 094876-000020WOPTsurface comprises at least one exfoliated basal plane, and wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0017] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0018] In some embodiments, the at least one N-heterocyclic carbene precursor has a structure of Formula (I):Formula (I), wherein: A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1is an optionally substituted linker.

[0019] In various embodiments, the present invention provides an article of manufacture comprising at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of the present invention. In some embodiments, the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material. In some embodiments, the article of manufacture is a semiconductor or has semiconducting properties.4886-5650-6109.1Page 7 of 224 094876-000020WOPTBRIEF DESCRIPTION OF THE DRAWINGS

[0020] Exemplary embodiments are illustrated in referenced figures. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.

[0021] FIG. 1A – FIG. 1B depicts in accordance with various embodiments of the invention, extinction spectra of redox exfoliated MoS2colloidal (FIG.1A) and the corresponding 2ndderivative transformations in the A-exciton transition regions (FIG.1B).

[0022] FIG. 2A – FIG. 2B depicts in accordance with various embodiments of the invention, the AFM image of redox exfoliated MoS2dispersion deposited on SiO2 / Si substrate (FIG.2A) and the corresponding height profiles of selected nanosheets (FIG.2B).

[0023] FIG. 3 depicts in accordance with various embodiments of the invention, XRD patterns of thin film NHC15OH[OMs]-functionalized MoS2where NHC = N-heterocyclic carbene. The functionalized samples are labeled as x-NHC-MoS2where x represents the NHC:MoS2molar ratio.

[0024] FIG. 4A – FIG. 4B depicts in accordance with various embodiments of the invention, the 2ndderivatives of exfoliated MoS2entire extinction spectra (FIG. 4A) and the A- exciton positions obtained by centrifuge cascade of exfoliated MoS2(FIG.4B).

[0025] FIG. 5 depicts in accordance with various embodiments of the invention, AFM height distribution of redox exfoliated MoS2, deposited onto SiO2 / Si wafer, subjected to statistical analysis. The counted population is N = 311.

[0026] FIG. 6 depicts in accordance with various embodiments of the invention, XRD patterns of bulk MoS2and thin film exfoliated MoS2.

[0027] FIG. 7 depicts in accordance with various embodiments of the invention, XRD pattern of white powder NHC15OH[OMs].

[0028] FIG.8 depicts in accordance with various embodiments of the invention, ATR-IR spectra of thin film of studied materials deposited onto optical slides.

[0029] FIG. 9 depicts in accordance with various embodiments of the invention, Zeta potential of redox exfoliated MoS2and anticipated NHC-functionalized MoS2colloidal.

[0030] FIG. 10A – FIG. 10B depicts in accordance with various embodiments of the invention, the extinction spectra of exfoliated MoS2suspension collected at different centrifuge rates (FIG.10A) and the 2ndderivative transformation of the extinction spectra (FIG.10B).4886-5650-6109.1Page 8 of 224 094876-000020WOPT

[0031] FIG. 11 depicts in accordance with various embodiments of the invention, XRD pattern of bulk, exfoliated, and functionalized MoS2.

[0032] FIG. 12 depicts in accordance with various embodiments of the invention, Zeta potentials of redox-exfoliated MoS2and sonication-induced exfoliated MoS2colloidal.

[0033] FIG. 13 depicts various embodiments of the invention, Raman E12gand A1gvibrational modes of redox-exfoliated MoS2and NHC-functionalized MoS2.

[0034] FIG. 14 depicts various embodiments of the invention, the hetero-superlattice structure formed by the restacking of multiple monolayers of TMDs is achieved through NHC functionalization. This approach is adaptable to different types of TMDs, with MoS2and WS2provided here as examples.

[0035] FIG. 15 depicts in accordance with various embodiments of the invention, 2D Nanolayered MoS2Exfoliation, redox exfoliation of 2D nanolayered MoS2. Jawaid, A.; Che, J.; Drummy, L. F.; Bultman, J.; Waite, A.; Hsiao, M.-S.; Vaia, R. A. Redox Exfoliation of Layered Transition Metal Dichalcogenides. ACS Nano 2017, 11, 635-646; Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater.2020, 32, 6550-6565.

[0036] FIG. 16 depicts in accordance with various embodiments of the invention, basal plane functionalization, proposed SAM formation and self-restacking.

[0037] FIG. 17 depicts in accordance with various embodiments of the invention, basal- plane functionalized 2D MoS2, XRD patterns of functionalized 2D MoS2.

[0038] FIG. 18A – FIG. 18D depicts in accordance with various embodiments of the invention, (FIG. 18A) Normalized extinction spectra of redox-exfoliated MoS2, (FIG. 18B) the corresponding 2ndderivatives of A excitons, (FIG. 18C) the relationship between A-excitonic wavelengths and the employed centrifuge rates, and (FIG.18D) Zeta potentials of redox-exfoliated MoS2and sonication-induced exfoliated MoS2colloidal.

[0039] FIG. 19A – FIG. 19H depicts in accordance with various embodiments of the invention, (FIG.19A) AFM height retrace image, (FIG.19B) the corresponding height profiles of selected nanosheets, and (FIG.19C) AFM height distribution of redox-exfoliated MoS2; counted population is N = 311 nanosheets. (FIG. 19D) XRD patterns and (FIG. 19E- FIG. 19H) TEM images of redox-exfoliated MoS2.4886-5650-6109.1Page 9 of 224 094876-000020WOPT

[0040] FIG. 20A – FIG. 20D depicts in accordance with various embodiments of the invention, (FIG.20A) XRD patterns, (FIG.20B) ATIR spectra, (FIG.20C) Zeta potential of NHC- functionalized MoS2, labeled as x-NHC / MoS2where x represents the NHC:MoS2molar ratio, and (FIG.20D) the proposed interaction scheme.

[0041] FIG. 21A – FIG. 21D depicts in accordance with various embodiments of the invention, XPS spectra of redox-exfoliated MoS2and 15-NHC / MoS2.

[0042] FIG. 22A – FIG. 22B depicts in accordance with various embodiments of the invention, two intercalated structures arise from the restacking of exfoliated few- to monolayered TMDs.

[0043] FIG. 23A – FIG. 23N depicts in accordance with various embodiments of the invention, (FIG.23A) Normalized extinction spectra, (FIG.23B, FIG.23D) the corresponding 2ndderivatives in the A-B-excitonic regions and A excitons in energy (eV), (FIG.23C) A-D excitonic wavelengths, (FIG. 23E – FIG. 23H) SEM images, and (FIG. 23I – FIG. 23N) statistical size distribution of redox-exfoliated MoS2at four different collected fractions.

[0044] FIG. 24A – FIG. 24F depicts in accordance with various embodiments of the invention, (FIG. 24A, FIG. 24D, FIG. 24E) Raman E12gand A1gvibration modes of redox- exfoliated MoS2and 15-NHC / MoS2; the label 15-NHC / MoS2Px denotes data collected at different points within the same sample. (FIG. 24B) Si transverse optical vibration mode as an internal reference, (FIG.24C) the corresponding E12gand A1gpeak positions, and (FIG.24F) FMHWs of E12gand A1gpeaks.

[0045] FIG. 25A – FIG. 25D depicts in accordance with various embodiments of the invention, (FIG.25A) XRD patterns of 15-NHC / MoS2Fx, where Fx represents different redox- exfoliated MoS2fractions, which are categorized as: F1 at 2000-2500 rpm, F2 at 2500-3000 rpm, F3 at 3000-4000 rpm, and F4 at >4000 rpm. (FIG.25B) XRD patterns of 15-NHC / MoS2Fx, which are redispersed in fresh a-ACN by sonication. (FIG. 25C) Normalized extinction spectra of redispersed 15-NHC / MoS2Fx in image b and (FIG. 25D) the corresponding 2ndderivatives of extinction spectra in image c.

[0046] FIG. 26A – FIG. 26B depicts in accordance with various embodiments of the invention, (FIG.26A) Hybridization-induced by the perpendicular pzorbitals within the aromatic π-configuration and the out-of-plane chalcogen pzand metal dz2 orbitals. (FIG. 26B) Hybridization-induced by the donation of in-plane lone pair electrons from the N-heterocyclic ring4886-5650-6109.1Page 10 of 224 094876-000020WOPTto the metal dz2 orbitals. Atom color code: purple, metal; yellow, chalcogen; blue, nitrogen; grey, carbon.

[0047] FIG. 27 depicts in accordance with various embodiments of the invention, Molecular structure of NHC15OH[OMs].

[0048] FIG. 28A – FIG. 28D depicts in accordance with various embodiments of the invention, thin film fabrication by liquid-liquid thin film self-assembly technique.

[0049] FIG.29 depicts in accordance with various embodiments of the invention, size and thickness selection of exfoliated TMD nanosheets by centrifuge cascade technique.

[0050] FIG. 30A – FIG. 30B depicts in accordance with various embodiments of the invention, The 2ndderivatives of extinction spectra of redox-exfoliated MoS2(FIG.30A) and WS2(FIG.30B).

[0051] FIG. 31A – FIG. 31D depicts in accordance with various embodiments of the invention, (FIG.31A) Normalized extinction spectra, (FIG.31B, FIG.31D) the corresponding 2ndderivatives of A and B excitons and A-excitonic transition in energy (eV), and (FIG.31C) A-D excitonic wavelengths of redox-exfoliated WS2colloidal at different centrifuge rates.

[0052] FIG. 32A – FIG. 32E depicts in accordance with various embodiments of the invention, (FIG. 32A) AFM height retrace, (FIG. 32B) the corresponding height profiles of selected nanosheets, (FIG.32C) amplitude retrace images, (FIG.32D) XRD patterns, and (FIG. 32E) SEM image of redox-exfoliated MoS2thin film rendering flat-lying nanosheets.

[0053] FIG. 33A – FIG. 33B depicts in accordance with various embodiments of the invention, AFM height retrace (FIG. 33A) and amplitude retrace images (FIG. 33B) of redox- exfoliated MoS2.

[0054] FIG. 34A – FIG. 34E depicts in accordance with various embodiments of the invention, (FIG.34A – FIG.34D) AFM images and the (FIG.34E) corresponding height profiles of selected redox-exfoliated WS2nanosheets.

[0055] FIG. 35A – FIG. 35D depicts in accordance with various embodiments of the invention, (FIG. 35A) AFM image, (FIG. 35B) the corresponding height profiles of selected nanosheets, and (FIG.35C) AFM height distribution of redox-exfoliated WS2, counted population is N = 149 nanosheets. (FIG.35D) XRD patterns of bulk and redox-exfoliated WS2.

[0056] FIG. 36 depicts in accordance with various embodiments of the invention, XRD patterns of powder NHC15OH[OMs].4886-5650-6109.1Page 11 of 224 094876-000020WOPT

[0057] FIG. 37A – FIG. 37D depicts in accordance with various embodiments of the invention, XPS spectra of redox-exfoliated WS2and 15-NHC / WS2.

[0058] FIG. 38 depicts in accordance with various embodiments of the invention, XRD patterns of 15-NHC / MoS2samples at different sonicating-restacking cycles, labeled as 15-NHC- / MoS2xS where x represents sonicating-restacking cycles.

[0059] FIG. 39A – FIG. 39B depicts in accordance with various embodiments of the invention, XRD patterns of 15-NHC / MoS2and 15-NHC / WS2, labeled as x-NHC / TMDs where x represents NHC:TMDs molar ratio (FIG. 39A), and cartoon of two intercalated structures (FIG. 39B).

[0060] FIG. 40A – FIG. 40D depicts in accordance with various embodiments of the invention, (FIG. 40A, FIG. 40B) XPS low binding energy regions, (FIG. 40C) schematic illustration of charge transfer process from NHC15OH[OMs] to MoS2and (FIG. 40D) energy mismatch between Fermi level (EF) and valence band (EVB) of redox-exfoliated MoS2and 15- NHC / MoS2.

[0061] FIG. 41A – FIG. 41B depicts in accordance with various embodiments of the invention, XPS low binding energy regions of redox-exfoliated WS2and 15-NHC / WS2.

[0062] FIG. 42A – FIG. 42F depicts in accordance with various embodiments of the invention, (FIG. 42A, FIG. 42D, FIG. 42E) Raman E12gand A1gvibration modes of redox- exfoliated WS2and 15-NHC / WS2samples; the label 15-NHC / WS2Px denotes the same deposited sample collected at different points. (FIG.42B) Si optical transverse vibration mode as an internal reference, (FIG.42C) the corresponding E12gand A1gpeak positions, and (FIG.42F) FMHWs of E12gand A1gpeaks.

[0063] FIG. 43A – FIG. 43B depicts in accordance with various embodiments of the invention, The corresponding separation of E12g– A1gfrom FIG.24A – FIG.24F (FIG.43A) and FIG.42A – FIG.42F (FIG.43B).

[0064] FIG. 44A – FIG. 44B depicts in accordance with various embodiments of the invention, XRD patterns of 15-NHC / MoS2F4, where F4 represents for the redox-exfoliated MoS2fractions collected at centrifuge rate >4000 rpm, and the corresponding sonication-induced redispersed 15-NHC / MoS2F4 RS in a-ACN or DCM. Emerging (006*) and (008*) reflections, at 20.5 and 27.4 (2θ), respectively, are observed while trace amounts of crystallized NHC15OH[OMs] adsorbates are detected at an angle 21.3 (2θ) (see FIG.36).4886-5650-6109.1Page 12 of 224 094876-000020WOPT

[0065] FIG. 45A – FIG. 45D depicts in accordance with various embodiments of the invention, (FIG.45A) Absorption spectra of Mo6+complexes and (FIG.45B) extracted calibration fitting. (FIG.45C) Extinction spectra of redox-exfoliated MoS2and (FIG.45D) extracted titration fitting.

[0066] FIG. 46A – FIG. 46D depicts in accordance with various embodiments of the invention, (FIG.46A) Absorption spectra of W6+complexes and (FIG.46B) extracted calibration fitting. (FIG.46C) Extinction spectra of redox-exfoliated WS2and (FIG.46D) extracted titration fitting.

[0067] FIG.47 depicts in accordance with various embodiments of the invention, Image of deposited mono- to few-layered MoS2nanosheets on 300 nm SiO2 / Si substrate under the optical microscope equipped within AFM instrument.

[0068] FIG. 48A - FIG. 48B depicts in accordance with various embodiments of the invention, Functionalization of MoS2.

[0069] FIG. 49A – FIG. 49B depicts in accordance with various embodiments of the invention, (FIG. 49A) Photoluminescence of 15-NHC / MoS2Fx, where Fx represents different redox-exfoliated MoS2fractions, which are categorized as: F1 at 2000-2500 rpm, F2 at 2500-3000 rpm, F3 at 3000-4000 rpm, and F4 at >4000 rpm. (FIG.49B) Constructed band gap diagrams of MoS2and NHC-functionalized MoS2.

[0070] FIG. 50A – FIG. 50B depicts in accordance with various embodiments of the invention, extracted titration fitting at the local minimum ε345of MoS2fraction F1 (FIG.50A) and F4 (FIG.50B).

[0071] FIG. 51A – FIG. 51L depicts in accordance with various embodiments of the invention, (FIG.51A, FIG.51D) Raman E12gand A1gvibration modes of redox-exfoliated MoS2Fx and 15-NHC / MoS2Fx, where Fx represents different redox-exfoliated MoS2fractions, which are categorized as: F1 at 2000-2500 rpm, F2 at 2500-3000 rpm, F3 at 3000-4000 rpm, and F4 at >4000 rpm. (FIG. 51B, FIG.51C, FIG.51E, FIG.51F) Raman E12gand A1gvibration modes of individual redox-exfoliated MoS2fraction and their corresponding 15-NHC / MoS2counterpart. (FIG. 51G, FIG. 51J) The corresponding E12gand A1gpeak positions, (FIG. 51H, FIG. 51K) FMHWs of E12gand A1gpeaks, and (FIG.51I) the intensity ratio of E12g / A1g. (FIG.51L) Si optical transverse vibration mode as an internal reference.4886-5650-6109.1Page 13 of 224 094876-000020WOPT

[0072] FIG. 52A – FIG. 52D depicts in accordance with various embodiments of the invention, photoluminescence of individual MoS2Fx and their corresponding 15-NHC / MoS2Fx, where Fx represents different redox-exfoliated MoS2fractions, which are categorized as: F1 at 2000-2500 rpm (FIG.52A), F2 at 2500-3000 rpm (FIG.52B), F3 at 3000-4000 rpm (FIG.52C), and F4 at >4000 rpm (FIG.52D).

[0073] FIG.53 depicts in accordance with various embodiments of the present invention, benzimidazolium salts as the N-heterocyclic carbene precursors. In various embodiments, A and B are each independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl. In some embodiments, A and B are each independently alkyl. In some embodiments, A and B are each independently ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In various embodiments, C and D are each independently H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl. In various embodiments, X- is a counterion. In some embodiments, X- is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6.

[0074] FIG. 54A – FIG. 54B depicts in accordance with various embodiments of the invention, XRD patterns of the NHC-functionalized MoS2(FIG.54B), and (FIG.54A) shows the chemical structure of the NHC precursor used to prepare the NHC-functionalized MoS2. DETAILED DESCRIPTION OF THE INVENTION

[0075] All references cited herein are incorporated by reference in their entirety as though fully set forth. Unless defined otherwise, technical, and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0076] One skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which could be used in the practice of the present invention. Other features and advantages of the invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, various features of embodiments of the invention. Indeed, the present invention is in no4886-5650-6109.1Page 14 of 224 094876-000020WOPTway limited to the methods and materials described. For purposes of the present invention, the following terms are defined below. For convenience, certain terms employed herein, in the specification, examples and appended claims are collected here.

[0077] Unless stated otherwise, or implicit from context, the following terms and phrases include the meanings provided below. Unless explicitly stated otherwise, or apparent from context, the terms and phrases below do not exclude the meaning that the term or phrase has acquired in the art to which it pertains. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It should be understood that this invention is not limited to the particular methodology, protocols, and reagents, etc., described herein and as such can vary. The definitions and terminology used herein are provided to aid in describing particular embodiments, and are not intended to limit the claimed invention, because the scope of the invention is limited only by the claims.

[0078] As used herein the term “comprising” or “comprises” is used in reference to compositions, methods, systems, articles of manufacture, apparatus, and respective component(s) thereof, that are useful to an embodiment, yet open to the inclusion of unspecified elements, whether useful or not. It will be understood by those within the art that, in general, terms used herein are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). Although the open- ended term “comprising,” as a synonym of terms such as including, containing, or having, is used herein to describe and claim the invention, the present invention, or embodiments thereof, may alternatively be described using alternative terms such as “consisting of” or “consisting essentially of.”

[0079] Unless stated otherwise, the terms “a” and “an” and “the” and similar references used in the context of describing a particular embodiment of the application (especially in the context of claims) can be construed to cover both the singular and the plural. The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or4886-5650-6109.1Page 15 of 224 094876-000020WOPTotherwise clearly contradicted by context. The use of any and all examples, or exemplary language (for example, “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the application and does not pose a limitation on the scope of the application otherwise claimed. The abbreviation, “e.g.” is derived from the Latin exempli gratia, and is used herein to indicate a non-limiting example. Thus, the abbreviation “e.g.” is synonymous with the term “for example.” No language in the specification should be construed as indicating any non- claimed element essential to the practice of the application.

[0080] “Optional" or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.

[0081] In some embodiments, the numbers expressing quantities of reagents, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0082] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.4886-5650-6109.1Page 16 of 224 094876-000020WOPT

[0083] As used herein the term “electron donating group” is well-known in the art and generally refers to a functional group or atom that pushes electron density away from itself, towards other portions of the molecule, e.g., through resonance and / or inductive effects. Non- limiting examples of electron-donating groups include ORc, NRcRd, alkyl groups, wherein Rcand Rdare each independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cyclyl, or optionally substituted heterocyclyl.

[0084] As used herein the term “electron withdrawing group” is well-known in the art and generally refers to a functional group or atom that pulls electron density towards itself, away from other portions of the molecule, e.g., through resonance and / or inductive effects. Non-limiting examples of electron-withdrawing groups include NO2, F, Cl, Br, I, CF3, CN, CO2Ra, C(=O)NRaRb, C(=O)Ra, SO2Ra, SO2ORa, SO2NRaRb, PO3RaRb, or NO, wherein Raand Rbare each independently H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cyclyl, or optionally substituted heterocyclyl.

[0085] As used herein, the term “alkyl” means a straight or branched, saturated aliphatic group having a chain of carbon atoms. Cxalkyl and Cx-Cyalkyl are typically used where X and Y indicate the number of carbon atoms in the chain. For example, C1-C6alkyl includes alkyls that have a chain of between 1 and 6 carbons (e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and the like). Alkyl represented along with another group (e.g., as in arylalkyl) means a straight or branched, saturated alkyl divalent group having the number of atoms indicated or when no atoms are indicated means a bond, e.g., (C6-C10)aryl(C0- C3)alkyl includes phenyl, benzyl, phenethyl, 1-phenylethyl 3-phenylpropyl, and the like. The backbone of the alkyl can be optionally inserted with one or more heteroatoms, such as N, O, or S.

[0086] In preferred embodiments, a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone (e.g., C1-C30 for straight chains, C3-C30 for branched chains), and more preferably 20 or fewer. Likewise, preferred cycloalkyls have from 3-10 carbon atoms in their ring structure, and more preferably have 5, 6 or 7 carbons in the ring structure. The term “alkyl” (or “lower alkyl”) as used throughout the specification, examples, and claims is intended to include both “unsubstituted alkyls” and “substituted alkyls”, the latter of which refers to alkyl moieties4886-5650-6109.1Page 17 of 224 094876-000020WOPThaving one or more substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone.

[0087] Unless the number of carbons is otherwise specified, “lower alkyl” as used herein means an alkyl group, as defined above, but having from one to ten carbons, more preferably from one to six carbon atoms in its backbone structure. Likewise, “lower alkenyl” and “lower alkynyl” have similar chain lengths. Throughout the application, preferred alkyl groups are lower alkyls. In preferred embodiments, a substituent designated herein as alkyl is a lower alkyl.

[0088] Non-limiting examples of substituents of a substituted alkyl can include halogen, hydroxy, nitro, thiols, amino, azido, imino, amido, phosphoryl (including phosphonate and phosphinate), sulfonyl (including sulfate, sulfonamido, sulfamoyl and sulfonate), and silyl groups, as well as ethers, alkylthios, carbonyls (including ketones, aldehydes, carboxylates, and esters),- CF3, -CN and the like.

[0089] As used herein, the term “alkenyl” refers to unsaturated straight-chain, branched- chain or cyclic hydrocarbon group having at least one carbon-carbon double bond. Cxalkenyl and Cx-Cyalkenyl are typically used where X and Y indicate the number of carbon atoms in the chain. For example, C2-C6alkenyl includes alkenyls that have a chain of between 2 and 6 carbons and at least one double bond, e.g., vinyl, allyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2- methylallyl, 1-hexenyl, 2-hexenyl, 3- hexenyl, and the like). Alkenyl represented along with another group (e.g., as in arylalkenyl) means a straight or branched, alkenyl divalent group having the number of atoms indicated. The backbone of the alkenyl can be optionally inserted with one or more heteroatoms, such as N, O, or S.

[0090] As used herein, the term “alkynyl” refers to unsaturated hydrocarbon groups having at least one carbon-carbon triple bond. Cxalkynyl and Cx-Cyalkynyl are typically used where X and Y indicate the number of carbon atoms in the chain. For example, C2-C6alkynyl includes alkynyls that have a chain of between 2 and 6 carbons and at least one triple bond, e.g., ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, isopentynyl, 1,3-hexa-diyn-yl, n-hexynyl, 3-pentynyl, 1- hexen-3-ynyl and the like. Alkynyl represented along with another group (e.g., as in arylalkynyl) means a straight or branched, alkynyl divalent group having the number of atoms indicated. The backbone of the alkynyl can be optionally inserted with one or more heteroatoms, such as N, O, or S.4886-5650-6109.1Page 18 of 224 094876-000020WOPT

[0091] The terms “alkylene,” “alkenylene,” and “alkynylene” refer to divalent alkyl, alkenyl, and alkynyl” groups. Prefixes Cxand Cx-Cyare typically used where X and Y indicate the number of carbon atoms in the chain. For example, C1-C6alkylene includes methylene, (— CH2—), ethylene (—CH2CH2—), trimethylene (—CH2CH2CH2—), tetramethylene (— CH2CH2CH2CH2—), 2-methyltetramethylene (—CH2CH(CH3)CH2CH2—), pentamethylene (— CH2CH2CH2CH2CH2—) and the like).

[0092] As used herein, the term “alkylidene” means a straight or branched unsaturated, aliphatic, divalent group having a general formula =CRaRb. Non-limiting examples of Raand Rbare each independently hydrogen, alkyl, substituted alkyl, alkenyl, or substituted alkenyl. Cxalkylidene and Cx-Cyalkylidene are typically used where X and Y indicate the number of carbon atoms in the chain. For example, C2-C6alkylidene includes methylidene (=CH2), ethylidene (=CHCH3), isopropylidene (=C(CH3)2), propylidene (=CHCH2CH3), allylidene (=CH— CH=CH2), and the like).

[0093] The term “heteroalkyl”, as used herein, refers to straight or branched chain, or cyclic carbon-containing groups, or combinations thereof, containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P, Se, B, and S, wherein the phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. Heteroalkyls can be substituted as defined above for alkyl groups.

[0094] As used herein, the term “halogen” or “halo” refers to an atom selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). The term “halogen radioisotope” or “halo radioisotope” refers to a radionuclide of an atom selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0095] In some embodiments, “iodo” refers to the iodine atom (I) when it is used in the context of a halo functional group or halogen functional group or as a halo substituent or halogen substituent.

[0096] In some embodiments, “bromo” refers to the bromine atom (Br) when it is used in the context of a halo functional group or halogen functional group or as a halo substituent or halogen substituent.

[0097] In some embodiments, “chloro” refers to the chlorine atom (Cl) when it is used in the context of a halo functional group or halogen functional group or as a halo substituent or halogen substituent.4886-5650-6109.1Page 19 of 224 094876-000020WOPT

[0098] In some embodiments, “fluoro” refers to the fluorine atom (F) when it is used in the context of a halo functional group or halogen functional group or as a halo substituent or halogen substituent.

[0099] A “halogen-substituted moiety” or “halo-substituted moiety”, as an isolated group or part of a larger group, means an aliphatic, alicyclic, or aromatic moiety, as described herein, substituted by one or more “halo” atoms, as such terms are defined in this application. For example, halo-substituted alkyl includes haloalkyl, dihaloalkyl, trihaloalkyl, perhaloalkyl and the like (e.g., halosubstituted (C1-C3)alkyl includes chloromethyl, dichloromethyl, difluoromethyl, trifluoromethyl (-CF3), 2,2,2-trifluoroethyl, perfluoroethyl, 2,2,2-trifluoro-l,l-dichloroethyl, and the like).

[0100] The term “aryl” refers to monocyclic, bicyclic, or tricyclic fused aromatic ring system. Cxaryl and Cx-Cyaryl are typically used where X and Y indicate the number of carbon atoms in the ring system. For example, C6-C12aryl includes aryls that have 6 to 12 carbon atoms in the ring system. Exemplary aryl groups include, but are not limited to, pyridinyl, pyrimidinyl, furanyl, thienyl, imidazolyl, thiazolyl, pyrazolyl, pyridazinyl, pyrazinyl, triazinyl, tetrazolyl, indolyl, benzyl, phenyl, naphthyl, anthracenyl, azulenyl, fluorenyl, indanyl, indenyl, naphthyl, phenyl, tetrahydronaphthyl, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3 b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3- oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl,4886-5650-6109.1Page 20 of 224 094876-000020WOPTtetrazolyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4- thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl, and the like. In some embodiments, 1, 2, 3, or 4 hydrogen atoms of each ring can be substituted by a substituent.

[0101] The term “heteroaryl” refers to an aromatic 5-8 membered monocyclic, 8-12 membered fused bicyclic, or 11-14 membered fused tricyclic ring system having 1-3 heteroatoms if monocyclic, 1-6 heteroatoms if bicyclic, or 1-9 heteroatoms if tricyclic, said heteroatoms selected from O, N, or S (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S if monocyclic, bicyclic, or tricyclic, respectively. Cxheteroaryl and Cx-Cyheteroaryl are typically used where X and Y indicate the number of carbon atoms in the ring system. For example, C4-C9heteroaryl includes heteroaryls that have 4 to 9 carbon atoms in the ring system. Heteroaryls include, but are not limited to, those derived from benzo[b]furan, benzo[b] thiophene, benzimidazole, imidazo[4,5-c]pyridine, quinazoline, thieno[2,3-c]pyridine, thieno[3,2-b]pyridine, thieno[2, 3-b]pyridine, indolizine, imidazo[l,2a]pyridine, quinoline, isoquinoline, phthalazine, quinoxaline, naphthyridine, quinolizine, indole, isoindole, indazole, indoline, benzoxazole, benzopyrazole, benzothiazole, imidazo[l,5-a]pyridine, pyrazolo[l,5-a]pyridine, imidazo[l,2- a]pyrimidine, imidazo[l,2-c]pyrimidine, imidazo[l,5-a]pyrimidine, imidazo[l,5-c]pyrimidine, pyrrolo[2,3-b]pyridine, pyrrolo[2,3cjpyridine, pyrrolo[3,2-c]pyridine, pyrrolo[3,2-b]pyridine, pyrrolo[2,3-d]pyrimidine, pyrrolo[3,2-d]pyrimidine, pyrrolo [2,3-b]pyrazine, pyrazolo[l,5- a]pyridine, pyrrolo[l,2-b]pyridazine, pyrrolo[l,2-c]pyrimidine, pyrrolo[l,2-a]pyrimidine, pyrrolo[l,2-a]pyrazine, triazo[l,5-a]pyridine, pteridine, purine, carbazole, acridine, phenazine, phenothiazene, phenoxazine, l,2-dihydropyrrolo[3,2,l-hi]indole, indolizine, pyrido[l,2-a]indole, 2(lH)-pyridinone, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3- oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl,4886-5650-6109.1Page 21 of 224 094876-000020WOPToxepanyl, oxetanyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H- quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl. Some exemplary heteroaryl groups include, but are not limited to, pyridyl, furyl or furanyl, imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, pyridazinyl, pyrazinyl, quinolinyl, indolyl, thiazolyl, naphthyridinyl, 2-amino-4-oxo-3,4-dihydropteridin-6-yl, tetrahydroisoquinolinyl, and the like. In some embodiments, 1, 2, 3, or 4 hydrogen atoms of each ring may be substituted by a substituent.

[0102] The term “cyclyl” or “cycloalkyl” refers to saturated and partially unsaturated cyclic hydrocarbon groups having 3 to 12 carbons, for example, 3 to 8 carbons, and, for example, 3 to 6 carbons. Cxcyclyl and Cx-Cycycyl are typically used where X and Y indicate the number of carbon atoms in the ring system. For example, C3-C8cyclyl includes cyclyls that have 3 to 8 carbon atoms in the ring system. The cycloalkyl group additionally can be optionally substituted, e.g., with 1, 2, 3, or 4 substituents. C3-C10cyclyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, 2,5-cyclohexadienyl, cycloheptyl, cyclooctyl, bicyclo[2.2.2]octyl, adamantan-l-yl, decahydronaphthyl, oxocyclohexyl, dioxocyclohexyl, thiocyclohexyl, 2- oxobicyclo [2.2.1]hept-l-yl, and the like.

[0103] Aryl and heteroaryls can be optionally substituted with one or more substituents at one or more positions, for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphate, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, a heterocyclyl, an aromatic or heteroaromatic moiety, -CF3, -CN, or the like.

[0104] The term “heterocyclyl” refers to a nonaromatic 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring system having 1-3 heteroatoms if monocyclic, 1-6 heteroatoms if bicyclic, or 1-9 heteroatoms if tricyclic, said heteroatoms selected4886-5650-6109.1Page 22 of 224 094876-000020WOPTfrom O, N, or S (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S if monocyclic, bicyclic, or tricyclic, respectively). Cxheterocyclyl and Cx-Cyheterocyclyl are typically used where X and Y indicate the number of carbon atoms in the ring system. For example, C4-C9heterocyclyl includes heterocyclyls that have 4-9 carbon atoms in the ring system. In some embodiments, 1, 2 or 3 hydrogen atoms of each ring can be substituted by a substituent. Exemplary heterocyclyl groups include, but are not limited to piperazinyl, pyrrolidinyl, dioxanyl, morpholinyl, tetrahydrofuranyl, piperidyl, 4-morpholyl, 4-piperazinyl, pyrrolidinyl, perhydropyrrolizinyl, 1,4- diazaperhydroepinyl, 1,3-dioxanyl, 1,4-dioxanyland the like.

[0105] The terms “bicyclic” and “tricyclic” refer to fused, bridged, or joined by single bond polycyclic ring assemblies.

[0106] The term “cyclylalkylene” means a divalent aryl, heteroaryl, cyclyl, or heterocyclyl.

[0107] As used herein, the term “fused ring” refers to a ring that is bonded to another ring to form a compound having a bicyclic structure when the ring atoms that are common to both rings are directly bound to each other. Non-exclusive examples of common fused rings include decalin, naphthalene, anthracene, phenanthrene, indole, furan, benzofuran, quinoline, and the like. Compounds having fused ring systems can be saturated, partially saturated, cyclyl, heterocyclyl, aromatics, heteroaromatics, and the like.

[0108] As used herein, the term “carbonyl” means the group —C(O)—. It is noted that the carbonyl group can be further substituted with a variety of substituents to form different carbonyl groups including acids, acid halides, amides, esters, ketones, and the like.

[0109] The term “carboxy” means the group —C(O)O—. It is noted that compounds described herein containing carboxy moieties can include protected derivatives thereof, i.e., where the oxygen is substituted with a protecting group. Suitable protecting groups for carboxy moieties include benzyl, tert-butyl, and the like. The term "carboxyl" means –COOH.

[0110] The term “cyano” means the group —CN.

[0111] The term, “heteroatom” refers to an atom that is not a carbon atom. Particular examples of heteroatoms include, but are not limited to nitrogen, oxygen, sulfur and halogens. A “heteroatom moiety” includes a moiety where the atom by which the moiety is attached is not a carbon. Examples of heteroatom moieties include —N=, —NRN—, —N+(O-)=, —O—, —S— or —S(O)2—, —OS(O)2—, and —SS—, wherein RNis H or a further substituent.4886-5650-6109.1Page 23 of 224 094876-000020WOPT

[0112] The term “hydroxy” means the group —OH.

[0113] The term “imine derivative” means a derivative comprising the moiety —C(NR)— , wherein R comprises a hydrogen or carbon atom alpha to the nitrogen.

[0114] The term “nitro” means the group —NO2.

[0115] An “oxaaliphatic,” “oxaalicyclic”, or “oxaaromatic” mean an aliphatic, alicyclic, or aromatic, as defined herein, except where one or more oxygen atoms (—O—) are positioned between carbon atoms of the aliphatic, alicyclic, or aromatic respectively.

[0116] An “oxoaliphatic,” “oxoalicyclic”, or “oxoaromatic” means an aliphatic, alicyclic, or aromatic, as defined herein, substituted with a carbonyl group. The carbonyl group can be an aldehyde, ketone, ester, amide, acid, or acid halide.

[0117] As used herein, the term “aromatic” means a moiety wherein the constituent atoms make up an unsaturated ring system, all atoms in the ring system are sp2hybridized and the total number of pi electrons is equal to 4n+2. An aromatic ring can be such that the ring atoms are only carbon atoms (e.g., aryl) or can include carbon and non-carbon atoms (e.g., heteroaryl).

[0118] As used herein, the term “substituted” refers to independent replacement of one or more (typically 1, 2, 3, 4, or 5) of the hydrogen atoms on the substituted moiety with substituents independently selected from the group of substituents listed below in the definition for “substituents” or otherwise specified. In general, a non-hydrogen substituent can be any substituent that can be bound to an atom of the given moiety that is specified to be substituted. Examples of substituents include, but are not limited to, acyl, acylamino, acyloxy, aldehyde, alicyclic, aliphatic, alkanesulfonamido, alkanesulfonyl, alkaryl, alkenyl, alkoxy, alkoxycarbonyl, alkyl, alkylamino, alkylcarbanoyl, alkylene, alkylidene, alkylthios, alkynyl, amide, amido, amino, aminoalkyl, aralkyl, aralkylsulfonamido, arenesulfonamido, arenesulfonyl, aromatic, aryl, arylamino, arylcarbanoyl, aryloxy, azido, carbamoyl, carbonyl, carbonyls including ketones, carboxy, carboxylates, CF3, cyano (CN), cycloalkyl, cycloalkylene, ester, ether, haloalkyl, halogen, halogen, heteroaryl, heterocyclyl, hydroxy, hydroxyalkyl, imino, iminoketone, ketone, mercapto, nitro, oxaalkyl, oxo, oxoalkyl, phosphoryl (including phosphonate and phosphinate), silyl groups, sulfonamido, sulfonyl (including sulfate, sulfamoyl and sulfonate), thiols, and ureido moieties, each of which may optionally also be substituted or unsubstituted. In some cases, two substituents, together with the carbon(s) to which they are attached to, can form a ring.4886-5650-6109.1Page 24 of 224 094876-000020WOPT

[0119] Substituents may be protected as necessary and any of the protecting groups commonly used in the art may be employed. Non-limiting examples of protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999).

[0120] The terms “alkoxyl” or “alkoxy” as used herein refers to an alkyl group, as defined above, having an oxygen atom attached thereto. Representative alkoxyl groups include methoxy, ethoxy, propyloxy, tert-butoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, and the like. An “ether” is two hydrocarbons covalently linked by an oxygen. Accordingly, the substituent of an alkyl that renders that alkyl an ether is or resembles an alkoxyl, such as can be represented by one of -O-alkyl, -O-alkenyl, and -O-alkynyl. Aroxy can be represented by –O-aryl or O- heteroaryl, wherein aryl and heteroaryl are as defined below. The alkoxy and aroxy groups can be substituted as described above for alkyl.

[0121] The term “aralkyl”, as used herein, refers to an alkyl group substituted with an aryl group (e.g., an aromatic or heteroaromatic group).

[0122] The term “alkylthio” refers to an alkyl group, as defined above, having a sulfur atom attached thereto. In preferred embodiments, the “alkylthio” moiety is represented by one of -S-alkyl, -S-alkenyl, and -S-alkynyl. Representative alkylthio groups include methylthio, ethylthio, and the like. The term “alkylthio” also encompasses cycloalkyl groups, alkene and cycloalkene groups, and alkyne groups. “Arylthio” refers to aryl or heteroaryl groups.

[0123] The term “sulfinyl” means the group —SO—. It is noted that the sulfinyl group can be further substituted with a variety of substituents to form different sulfinyl groups including sulfinic acids, sulfinamides, sulfinyl esters, sulfoxides, and the like.

[0124] The term “sulfonyl” means the group —SO2—. It is noted that the sulfonyl group can be further substituted with a variety of substituents to form different sulfonyl groups including sulfonic acids (-SO3H), sulfonamides, sulfonate esters, sulfones, and the like.

[0125] The term “thiocarbonyl” means the group —C(S)—. It is noted that the thiocarbonyl group can be further substituted with a variety of substituents to form different thiocarbonyl groups including thioacids, thioamides, thioesters, thioketones, and the like.

[0126] As used herein, the term “amino” means -NH2. The term “alkylamino” means a nitrogen moiety having at least one straight or branched unsaturated aliphatic, cyclyl, or heterocyclyl groups attached to the nitrogen. For example, representative amino groups include4886-5650-6109.1Page 25 of 224 094876-000020WOPT—NH2, —NHCH3, —N(CH3)2, —NH(C1-C10alkyl), —N(C1-C10alkyl)2, and the like. The term “alkylamino” includes “alkenylamino,” “alkynylamino,” “cyclylamino,” and “heterocyclylamino.” The term “arylamino” means a nitrogen moiety having at least one aryl group attached to the nitrogen. For example —NHaryl, and —N(aryl)2. The term “heteroarylamino” means a nitrogen moiety having at least one heteroaryl group attached to the nitrogen. For example —NHheteroaryl, and —N(heteroaryl)2. Optionally, two substituents together with the nitrogen can also form a ring. Unless indicated otherwise, the compounds described herein containing amino moieties can include protected derivatives thereof. Suitable protecting groups for amino moieties include acetyl, tert-butoxycarbonyl, benzyloxycarbonyl, and the like.

[0127] The term “aminoalkyl” means an alkyl, alkenyl, and alkynyl as defined above, except where one or more substituted or unsubstituted nitrogen atoms (—N—) are positioned between carbon atoms of the alkyl, alkenyl, or alkynyl . For example, an (C2-C6) aminoalkyl refers to a chain comprising between 2 and 6 carbons and one or more nitrogen atoms positioned between the carbon atoms.

[0128] The term "alkoxyalkoxy" means –O-(alkyl)-O-(alkyl), such as –OCH2CH2OCH3, and the like.

[0129] The term “alkoxycarbonyl" means –C(O)O-(alkyl), such as –C(=O)OCH3, – C(=O)OCH2CH3, and the like.

[0130] The term “alkoxyalkyl" means -(alkyl)-O-(alkyl), such as -- CH2OCH3, – CH2OCH2CH3, and the like.

[0131] The term “aryloxy" means –O-(aryl), such as –O-phenyl, –O-pyridinyl, and the like.

[0132] The term “arylalkyl" means -(alkyl)-(aryl), such as benzyl (i.e., –CH2phenyl), – CH2-pyrindinyl, and the like.

[0133] The term “arylalkyloxy" means –O-(alkyl)-(aryl), such as –O-benzyl, –O–CH2- pyridinyl, and the like.

[0134] The term “cycloalkyloxy" means –O-(cycloalkyl), such as –O-cyclohexyl, and the like.

[0135] The term “cycloalkylalkyloxy" means –O-(alkyl)-(cycloalkyl, such as – OCH2cyclohexyl, and the like.4886-5650-6109.1Page 26 of 224 094876-000020WOPT

[0136] The term “aminoalkoxy" means –O-(alkyl)-NH2, such as –OCH2NH2, – OCH2CH2NH2, and the like.

[0137] The term “mono- or di-alkylamino" means –NH(alkyl) or –N(alkyl)(alkyl), respectively, such as –NHCH3, –N(CH3)2, and the like.

[0138] The term "mono- or di-alkylaminoalkoxy" means –O-(alkyl)-NH(alkyl) or –O- (alkyl)-N(alkyl)(alkyl), respectively, such as –OCH2NHCH3, –OCH2CH2N(CH3)2, and the like.

[0139] The term “arylamino" means –NH(aryl), such as –NH-phenyl, –NH-pyridinyl, and the like.

[0140] The term “arylalkylamino" means –NH-(alkyl)-(aryl), such as –NH-benzyl, – NHCH2-pyridinyl, and the like.

[0141] The term “alkylamino" means –NH(alkyl), such as –NHCH3, –NHCH2CH3, and the like.

[0142] The term “cycloalkylamino" means –NH-(cycloalkyl), such as –NH-cyclohexyl, and the like.

[0143] The term “cycloalkylalkylamino" –NH-(alkyl)-(cycloalkyl), such as –NHCH2- cyclohexyl, and the like.

[0144] It is noted in regard to all of the definitions provided herein that the definitions should be interpreted as being open ended in the sense that further substituents beyond those specified may be included. Hence, a C1alkyl indicates that there is one carbon atom but does not indicate what are the substituents on the carbon atom. Hence, a C1alkyl comprises methyl (i.e., — CH3) as well as —CRaRbRcwhere Ra, Rb, and Rccan each independently be hydrogen or any other substituent where the atom alpha to the carbon is a heteroatom or cyano. Hence, CF3, CH2OH and CH2CN are all C1alkyls.

[0145] Unless otherwise stated, structures depicted herein are meant to include compounds which differ only in the presence of one or more isotopically enriched atoms. For example, compounds having the present structure except for the replacement of a hydrogen atom by a deuterium or tritium, or the replacement of a carbon atom by a13C- or14C-enriched carbon are within the scope of the invention.

[0146] In various embodiments, compounds of the present invention as disclosed herein may be synthesized using any synthetic method available to one of skill in the art. Non-limiting4886-5650-6109.1Page 27 of 224 094876-000020WOPTexamples of synthetic methods used to prepare various embodiments of compounds of the present invention are disclosed in the Examples section herein.

[0147] Transition metal dichalcogenides (TMDs) adopt a general chemical formula MX2, where M represents a transition metal of group 4 to 10 within the periodic table and X signifies a chalcogen. TMDs exhibit diverse intrinsic properties, encompassing insulating, semiconducting, semi-metallic and metallic attributes. These materials primarily crystallize in a two-dimensional (2D) layered structure, akin to graphite. Each layer consists of a layer of hexagonally packed metal atoms sandwiched between two layers of chalcogen atoms. Based on the atomic packing order, the TMD crystal structures are divided into two main polymorphs: 1T and 2H, where the front number delineates the number of layers per unit cell and the followed letter presents for octahedral or trigonal prismatic coordination respectively. At mono- to few-layered scale, TMDs retain their bulk properties while manifesting additional characteristics and versatile chemical reactivity. Among the TMDs family, particular attention is directed towards group VI TMDs, because of their stability and semiconducting features, which demonstrate band gaps around 1–2 eV, being highly attractive for potential applications. Importantly, at few- to mono-layered architecture, these materials exhibit a gradual shift from indirect to direct band gap transition, rendering them valuable in the realm of electronic and optoelectronic applications. The change of this band structure is owing to the quantum confinement effect and the consequent change in the overlap of chalcogen pzorbitals between the 2D TMDs layers. As a result of this special feature, exfoliated 2D TMDs are attractive for photodetectors over a wide range of wavelengths that can be selected by finely tuning the number of layers. Also, they can serve as light-absorbing materials in thin-film solar cells with a direct band gap spanning the visible region.

[0148] Consequently, scalable exfoliation methods to produce high-quality few- to mono- layered TMDs have been intensively investigated. Among these, the most efficient approach is exfoliating natural TMDs through intercalation chemistry, typically employing Li-based reagents. However, current research efforts have revealed a crucial limitation. It has been observed that excessive intercalation, beyond a certain threshold, induces phase transformation within the TMDs. In order to mitigate this issue, an alternative method - direct liquid phase exfoliation (LPE) – harnesses the intricate relation between the miss-match surface energies of TMDs and solvents, defined within the context of Hansen solubility framework. Nevertheless, this method encounters a fundamental limitation in terms of its solvent selection, primarily realizing on solvents such as4886-5650-6109.1Page 28 of 224 094876-000020WOPTN-methyl-pyrrolidone (NMP), leading to persistence of organic residues on the TMDs’ surface. Furthermore, the LPE process necessitates extended sonication periods, which tend to fragment TMDs nanosheets into relatively smaller flakes.

[0149] Hence, to avoid phase transformation, achieve high-quality mono- to few-layered nanosheets and maintain efficient exfoliation, mild redox chemistry was recently proposed in the literature and could afford large amounts of exfoliated TMDs with tunable layer thicknesses. In various embodiments, we envision exfoliating large-scale 2D nanolayered TMDs and using them as starting materials to further tune the electronic, optical, or interfacial properties for targeted goals based on the strategies discussed below.

[0150] Despite the TMDs’ attractiveness at mono- to few-layered architectures, the full extent of their potential applications is limited by the inherent band gap structures of TMDs. Efforts have been directed toward engineering TMDs’ band gap window. Common doping methods to modify TMDs’ surface and charge density, such as ion implantation, are ineffective at mono- to few-layered scale due to local defect generation and physical damage, which are detrimental to electronic applications. Currently, two predominant approaches have been used to address this challenge, each employing distinctive categories of reagents: thiol-based organic adsorbates and electron-donating molecules. In the thiol-based strategy, organic molecules containing thiol (-SH) or disulfide (-S-S-) groups are used to establish a sulfur-chalcogenide bridge with TMDs. This bonding interaction is, however, fragile.

[0151] More recent studies have revealed that TMDs can catalyze the formation of a disulfide bridge between two thiol molecules, indicating that the organic molecules tend to be physiosorbed rather than chemically bound to the surface of the TMDs. Furthermore, the affinity between transition metals and chalcogenide elements induces a pre-step modification that includes the creation of defects, such as the absence of chalcogenide atoms. These defects are poised for healing through the interaction between the transition metals and the thiol groups. Recently, a novel non-thiol-based strategy has been employed, utilizing the Michael addition reaction for the selective attack of chalcogenide nucleophiles upon the double bonds in maleimide-based adsorbates. However, this strategic approach requires the presence of maleimide ring, which severely limits the tunability of the electronic properties.

[0152] With the electron-donating strategy reported in the literature, a limited library of molecules (Lewis bases) serve as electron donors, imparting their electrons to the anti-bonding4886-5650-6109.1Page 29 of 224 094876-000020WOPTorbitals of the transition metals of TMDs. This process leads to compression of the TMD nanosheets and intercalation of the donor molecules between the van der Waals layers of the TMDs, giving rise to an intercalated structure with an expanded interlayer spacing. This particular approach demonstrates at least two advantages over the thiol-based method. First, the electron- donating molecules form strong chemical interactions via the donating electrons, leading to more robust bond formation. Second, the degree of intercalation can be controlled by finely modulating the ratio of precursor materials, which directly influences the electronic properties of the final intercalated products. Despite these advantages, as mentioned above, excessive intercalation, using strong electron donors, induces phase transformations within the TMDs. These phase transformations include a shift from the semiconducting to the metallic state, rendering impractical and unsuitable characteristics in several intended applications, specifically those within the semiconductor realm. Hence, the need for new and improved functionalized TMDs and methods for making them.

[0153] Taking into account the limitations of previously reported work, herein in various embodiments of the present invention we successfully developed an entirely new strategy based on the use of N-heterocyclic carbenes (NHCs) – a gentle electron donating reagent – to intercalate and functionalize the basal plane of mono- to few-layered TMDs. Unexpectedly, the resulting NHC-functionalized TMDs did not experience any undesirable phase transformations. In particular, the N-heterocyclic carbene functionalized TMDs of the present invention do not undergo the undesired phase transformation from the semiconducting state to the metallic state. This is crucial for semiconducting Group VI TMDs. In various non-limiting embodiments MoS2was selected as a representative example for illustrating N-heterocyclic carbene functionalized TMDs of the present invention. The step-by-step redox exfoliation method used and the corresponding evidence of exfoliated MoS2are described herein. Finally, concerning basal plane functionalized TMDs, the results are demonstrated herein.

[0154] Redox Exfoliation of Mono- to Few-layered MoS2 Nanosheets

[0155] The ultraviolet-visible spectroscopy (UV-vis) data, shown in FIG. 1A – FIG.1B, depicts the extinction (ε) spectra of exfoliated MoS2colloidal obtained from the redox exfoliation process. The spectrum combines the aspects of both absorbance (α) and size-dependent scattering (σ) backgrounds; hence, pertinent information can be extracted for approximate estimation of the thicknesses and lateral sizes of exfoliated MoS2nanosheets. Previous literature reports observed4886-5650-6109.1Page 30 of 224 094876-000020WOPTand reported this phenomenon, particularly as it relates to the evolving thicknesses and lateral sizes of those nanosheets. Importantly, the experimental set of data in these previous literature reports helped to interpolate the significance of a local minimum at 345 nm as an independent metric, free from the influence of scattering effects. This feature, then, can serve as a reference point for normalization in comparative analysis. Based on these previous literature reports, our data, in FIG. 1A, delineates the normalized extinction spectra of exfoliated MoS2nanosheets. This data was collected from exfoliated MoS2at different centrifuge rates subsequent to the redox exfoliation process. It is worth highlighting that increasing centrifuge rate results in thinner and smaller nanosheets, which emphasizes the discussed phenomenon in the region from 700 to 800 nm. In the spectral range from 700 to 350 nm, the exciton peaks of MoS2were designated as A, B, C, D from right to left respectively. Among these excitons, A presents the transition from the K-point (the highest energy point) in the valence band to the conduction band, which demonstrates the band gap of material. Consequently, the position of the A exciton can be employed to infer the thicknesses of MoS2nanosheets. This previously reported approach is feasible owing to 2D TMDs layer-dependent characteristics, which has been thoroughly examined and documented in the literature. Nevertheless, within the range below 700 nm, the dominance of scattering background necessitates the conversion of the original extinction spectrum into its second derivative. This mathematical transformation is recommended in the literature as an essential data processing step to reduce the peak shifts caused by the broad background. The second derivative transformation of A exciton is presented in FIG.1B with x-axis converted to energy scale. At a high centrifuge rate of 2500 rpm (740 G), the resultant exfoliated MoS2nanosheets exhibit their minimum thicknesses with an approximate A-exciton transition of 1.85 eV (λA= 671 nm). In contrast, the thicker ones are observed when A-excitons transition energy fall below 1.85 eV at lower centrifuge rates. The full second derivate transformation (FIG.4A – FIG.4B) and relationship between A- exciton transition energy at different centrifuge rates are shown herein. Compared to the fitted models and corresponding reported equations, the resultant exfoliated MoS2nanosheets exhibit thicknesses varying from 4 –7 layers. However, it is important to emphasize that UV-vis extinction spectrum only provide an approximate estimation about thicknesses of predominant populations of nanosheets. Furthermore, as mentioned, scattering backgrounds play a key role in understanding thicknesses-related aspects. Additionally, the inherent nature of redox exfoliation, which leads to the absorption of POMs on the surface of 2D TMDs nanosheets, might contribute4886-5650-6109.1Page 31 of 224 094876-000020WOPTto the peak shifts. This effect might be pronounced when POMs species exhibit comparable sizes, at least 1nm in height. Hence, as a complementary data, statistical analysis based on height retrace from AFM was conducted (FIG.5).

[0156] The height profiles of redox exfoliated MoS2dispersion are presented in FIG.2A – FIG.2B. Herein, it is important to note that the actual thickness of a single layer of TMDs is not identical to the theoretical one, owing to factors such as solvent effects and the presence of adsorbed POMs absorbed on the nanosheets’ surface. To address this issue, an internal reference, known as “step height”, is employed. This solution is based on the observation that incomplete exfoliation results in staircase-like height profile. As illustrated in our data, a step height of approximate 2.0 to 2.5 nm was found and attributed to the thickness of a single layer. This observation is also in agreement with the published studies employing redox exfoliation methods. Finally, to provide further evidence of successful exfoliation of MoS2, XRD measurements were carried out for a comparative analysis between bulk MoS2,and thin film exfoliated materials (FIG. 6). As a consequence of mono- to few-layer architecture, the [hk0] and [h0l] reflections experience disappearance or substantial attenuation. This phenomenon is due to the loss of intralayer order within the material. Only

[0002] reflection, attributed to the interlayer thickness, persists after the restacking process.

[0157] NHCs-Functionalized MoS2 Nanosheets

[0158] Based on our experiments we observed the interaction between NHC15OH[OMs] adsorbates (molecular structure of NHC15OH[OMs] is provided in the Examples herein) and the exfoliated MoS2colloidal. Following the complete dissolution of the NHC15OH[OMs] in dichloromethane (DCM), exfoliated MoS2in anhydrous acetonitrile (ACN) was introduced, and the system was allowed to stand undisturbed in 24 h. Typically, depending on the molar ratio between the NHCs and the exfoliated MoS2, abrupt compression resulting precipitation could be directly observed within a matter of minutes. The resultant black powder was centrifuged and washed by DCM three times to remove unreacted NHCs. Subsequently, the washed powder was deposited as thin film on a glass slide (details provided in the Examples section herein) and subjected to X-ray powder diffraction (XRD). FIG. 3 illustrates the XRD patterns of thin film NHC15OH[OMs]-functionalized MoS2. Interestingly, diffraction patterns of the novel material reveal two distinct and prominent peaks at 7.98 and 24.25 (2θ), which can be attributed to the molecular intercalation occurring between MoS2layers. Without being bound by theory, we4886-5650-6109.1Page 32 of 224 094876-000020WOPTpropose these two newly emerged peaks corresponding to the [002’] and [004’] reflections of the novel phase with an expanded thickness of 11.1 ^ compared to 6.1 ^ observed in bulk MoS2. In accordance with prior published literature, intercalation chemistry of 2D TMDs within groups IV and V have been investigated. This is primarily due to their metallic characteristics, which facilitate acceptance of electrons from donating reagents, but limited studies regarding the intercalation of group VI. A common employed strategy involves the pre-step exfoliation of semiconducting group VI TMDs, accomplished by Li-based reagents, which induce a phase transition to metallic state. From another perspective, solvent or partial hydrated species intercalation have been previously documented in the literature as well. Nevertheless, recovery of initial layer thickness can be accomplished by simple drying at solvent boiling temperature. However, it is noted that our samples were washed out and dried properly (details provided in Examples section herein). Furthermore, provided powder XRD pattern of NHC15OH[OMs] (FIG. 7) shows clearly different features compared to the functionalized materials.

[0159] In various embodiments of the present invention, NHC molecules adopting longer chain length, extending up to 15 carbon atoms, led to interlayer expansion of 2.5 ^ on each side of the TMDs’ single layer.

[0160] In previous reports NHC15OH[OMs] shows an approximate sub-layer height of NHC molecules forming self-assembly monolayers (SAMs) at 11 2 ^, even when the SAMs sub-layer was not densely packed. In another recent literature study, STM evidence was presented that revealed that the height of the carbene ring was at 235 pm, which was comparable to our calculations from our experimental data. Hence, without being bound by theory, we hypothesized that the NHC adsorbates, NHC precursors, and / or N-heterocyclic carbenes (NHCs) might not stand perpendicular to the plane, but rather lie nearly flat at a tilted angle. Also, as illustrated in the XRD patterns, it is evident that the intercalation process remains incomplete, even at high NHC:MoS2molar ratio, as indicated by the persistence of bulky MoS2reflection peaks. It can be potentially due to the bulky and cumbersome structure of the carbene head group. To further offer supplement about the intercalation triggered by the carbene, attenuated total reflectance infrared spectroscopy (ATR-IR) was conducted on thin film samples deposited onto optical glass slides (FIG.8). Finally, the zeta potential of the anticipated NHC-functionalized MoS2was measured and compared to that of exfoliated MoS2, providing a preliminary assessment of the surficial characteristics (FIG. 9). Since the zeta potential measurement provides surficial charge, redox4886-5650-6109.1Page 33 of 224 094876-000020WOPTexfoliated MoS2shows a negative surface charge of -29.2 1 mV, which is in great agreement with reported observations due to the adsorption of negative charge POMs species. Upon interaction with NHC adsorbates, NHC precursors, and / or N-heterocyclic carbenes (NHCs), the POMs are desorbed and replaced by N-heterocyclic carbenes (NHCs), which results in an increase in surface charge.

[0161] In various embodiments of the present invention described herein, the successful exfoliation of MoS2have been demonstrated, obtaining the recent redox exfoliation method. The interaction between the various NHC molecules (e.g., NHC adsorbates, NHC precursors, N- heterocyclic carbenes (NHCs)), and the representative 2D TMDs (MoS2) are described herein in various embodiments of the present invention. Without being bound by theory, according to the experimental data provided herein molecular intercalation between the van der Waals layers of MoS2was illustrated.

[0162] Transition metal dichalcogenides (TMDs) adopt a general chemical formula denoted as MX2, where M represents a transition metal of group 4 to 10 within the periodic table, and X corresponds to a chalcogen. TMDs exhibit diverse intrinsic properties that include insulating, semiconducting, semi-metallic and metallic. These materials primarily crystallize in a 2D layered structure akin to graphite. At mono- to few-layered scale, TMDs retain their inherent bulk properties while manifesting additional characteristics and versatile chemical reactivity. Among the TMD family, particular attention is directed toward group VI TMDs, because of their stability and semiconducting features. At mono-layered architectures, these materials exhibit a direct band gap transition, rendering them valuable in the realm of electronic and optoelectronic applications. Nevertheless, without being bound by theory, the full extent of their potential applications is limited by the inherent band gap structures of TMDs. Consequently, the work described herein in various embodiments of the present invention overcomes this limitation by demonstrating an entirely unique functionalization method that allows fine-tuning of the electronic properties, optical properties, band gap structures, and surficial characteristics of TMDs to broaden their applications across new and diverse technological domains.

[0163] In various embodiments of the present invention described herein we demonstrate, for the first time, the effective functionalization of the basal plane of 2D mono-to-few-layered TMDs employing NHCs (N-heterocyclic carbenes) and / or N-heterocyclic carbene precursors and / or NHC adsorbates. This pioneering and novel approach yields N-heterocyclic carbene4886-5650-6109.1Page 34 of 224 094876-000020WOPTfunctionalized TMD superstructures with immense potential not only within the semiconductor industry, but also as nano-building blocks for electronics, optoelectronics, and semiconductor nano-micro-fabrication engineering. This transformative and novel invention marks a crucial advancement in the utilization of TMDs and their functionalized derivatives, expanding promising applications and paving the way for innovative advancements in nano-micro technology.

[0164] In various embodiments, the present invention provides an entirely new strategy based on the use of N-heterocyclic carbenes (NHCs) and / or N-heterocyclic carbene precursors and / or N-heterocyclic carbene adsorbates to intercalate and functionalize the basal plane of mono- to-few-layered TMDs. Unexpectedly, the resulting N-heterocyclic carbene functionalized TMDs do not undergo undesirable phase transformations. In particular, the N-heterocyclic carbene functionalized TMDs of the present invention do not undergo the undesired phase transformation from the semiconducting state to the metallic state. This is a crucial feature for semiconducting Group VI TMDs. Furthermore, in various embodiments, the electronic characteristics and band gap structures of the N-heterocyclic carbene functionalized TMDs of the present invention can be systematically engineered through structural variation of the N-heterocyclic carbene headgroups. In addition, in various embodiments the resulting superstructure of functionalized and restacked N-heterocyclic carbene functionalized TMDs, characterized by their expanded space, holds promise for applications in molecular encapsulation, information encoding technology, and as fundamental building blocks for nano-micro architecture engineering in the semiconductor industry and beyond.

[0165] In various embodiments the present invention provides a novel approach for the functionalization of the basal plane of two-dimensional (2D) transition metal dichalcogenides (TMDs) by employing a gentle electron-donating agent based on N-heterocyclic carbenes (NHCs). In various embodiments, the process of the present invention involves the exfoliation of bulk TMDs to yield mono-to-few-layered TMD nanosheets that are subsequently exposed to NHC adsorbates (i.e., NHC precursors), which interact with the TMDs. The NHC molecules (e.g., NHC adsorbates, NHC precursors, NHCs) form self-assembled monolayers (SAMs) on the TMDs, which leads to compression of the nanosheets and their subsequent self-restacking. The resulting NHC-functionalized TMDs exhibit a final superstructure comprised of NHC-intercalated layers. Surprisingly and unexpectedly, this novel and innovative functionalization method described herein in various embodiments of the present invention preserves the inherent structures and4886-5650-6109.1Page 35 of 224 094876-000020WOPTphases of the TMDs, a critical factor for group VI TMDs that exclusively exhibit semiconducting characteristics in their natural 2H polymorph. In various embodiments, the present invention possesses the capability to fabricate advanced and unprecedented 2D assembled materials with potential applications, for example, in energy storage, sensing, and semiconductor electronics and optoelectronics.

[0166] Surface functionalization of 2D nanolayered transition metal dichalcogenides for tunable electronic and optical properties. Two-dimensional (2D) transition metal (VI) dichalcogenides (TMDs) exhibit attractive layer-dependent characteristics. Among these characteristics, direct band gap transitions spanning the visible spectrum as the thicknesses decreases to the monolayer level is a special feature that offers advantages in various device applications such as photodetectors and solar cells. In this work, 2D nanolayered TMDs were exfoliated via a facile mild redox wet chemistry method. The corresponding exfoliated products were prepared and collected as a function of the specific layer thickness and the lateral size of the 2D nanosheets. The basal planes of mono to few-layered 2D TMDs were then functionalized with organic molecules or metal complexes to form covalent bonds designed to tune the optical and electronic properties of the TMDs. Characterization by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy revealed the layer-dependent absorption spectra of the unfunctionalized exfoliated and functionalized exfoliated materials. Surface morphology details and particle size measurements were obtained by transmission electron microscopy (TEM). Finally, X-ray photoelectron spectroscopy (XPS) was used to evaluate the covalent functionalization of the TMDs.

[0167] Two-dimensional transition metal dichalcogenides (2D TMDs) display compelling electronic and optoelectronic attributes, holding promise for microelectronic applications. Nonetheless, in contrast to their monolayer counterparts, thicker-layered TMDs manifest an indirect band gap, limiting their utility across various optoelectronic applications. This research attempts to achieve a methodology for large-scale fabrication of mono- to few-layer 2D TMDs through the process of redox exfoliation, followed by subsequent functionalization with organic adsorbates. By systematically investigating the impact of adsorbates’ structures on exfoliated MoS2, we seek to deliberately modulate the physical and chemical properties of 2D TMDs for optoelectronic devices.4886-5650-6109.1Page 36 of 224 094876-000020WOPT

[0168] A core objective of this research is to establish an effective approach for the functionalization of 2D MoS2. Initially, the study focuses on using redox exfoliation to produce high-quality 2D nanolayered MoS2. The exfoliation process achieves an impressive yield of up to 8% with primarily mono to few-layer MoS2structure (< 5 layers). Additionally, the bulk portion can be recycled for subsequent exfoliation cycles. Afterwards, the research introduces the utilization of self-assembled monolayers (SAMs) comprised of organic molecules on the basal plane of exfoliated MoS2. This demonstrates the potential of functionalized MoS2as fundamental building blocks for the engineering of advanced nano-architectures within TMDs domain.

[0169] In various embodiments of the present invention, bulk MoS2has been effectively exfoliated using a convenient wet-chemistry method. In various embodiments of the present invention, the redox exfoliation affords substantial quantities of exfoliated materials, achieving a yield exceeding 8% per cycle. In various embodiments of the present invention, UV-vis extinction spectra validate the presence of mono to few-layered MoS2with prominent thicknesses ranging down to 4 layers. In various embodiments of the present invention, XRD pattern provides evidence of successful functionalization on the basal plane of MoS2.In various embodiments of the present invention, a novel strategy to functionalize 2D TMDs is introduced.

[0170] Herein, we introduce a novel, mild electron-donating approach that enables functionalization of the basal plane of two-dimensional (2D) few- to monolayered transition metal dichalcogenides (TMDs) using N-Heterocyclic Carbenes (NHCs). This strategy employs benzimidazolium methanesulfonates, a representative bench stable NHC adsorbate, to functionalize semiconducting TMDs through a one-step synthesis conducted under ambient conditions at room temperature. Without being bound by theory, the functionalization is hypothesized to be driven by hybridization-induced process, which concurrently leads to restacking and entrapment of bilayer self-assembled monolayers (SAMs) of NHCs between the TMD monolayers, thereby forming superlattice structures. The resultant superlattice materials are signified by expanded van der Waals (vdW) interlayer gaps of 11.1 and 13.0 Å, which are tunable by controlling the sizes and thicknesses of TMD nanosheets. In addition to structural modifications, NHCs induce an n-doping effect, supported by alterations in both intrinsic in-plane and out-of-plane vibrations of TMDs. Finally, the experimental observations demonstrate that the bulky structures of NHCs can be incorporated into the interlayer gaps of TMDs while preserving their intrinsic semiconducting properties. Notably, the functionalized superlattice materials4886-5650-6109.1Page 37 of 224 094876-000020WOPTpreserve the semiconducting properties typical of monolayers, as evidenced by their detectable photoluminescence.

[0171] Two-dimensional transition metal dichalcogenides (2D TMDs) display compelling electronic and optoelectronic attributes at the monolayer architecture (1L). However, the ability to modulate these inherent characteristics is constrained by the electronic structures and morphological limitations inherent to 1L TMDs. To address these challenges, the work described herein aims to achieve large-scale, high-quality production of few- to monolayered 2D TMDs, followed by subsequent functionalization with custom-designed organic adsorbates.

[0172] Layered TMDs are emerging class of 2D materials with their attractive thickness- dependent optical and electrical properties (Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L.-J.; Loh, K. P.; Zhang, H. The Chemistry of Two-Dimensional Layered Transition Metal Dichalcogenide Nanosheets. Nat. Chem.2013, 5, 263–275). Akin to graphite, TMDs primarily crystallize in a 2D layered structure, wherein their composition covers transition metals from group 4 to 10 while the chalcogen atoms signify S, Se, or Te. With a vast compositional library, TMDs exhibit diverse intrinsic properties, encompassing insulating, semi-conducting, semi-metallic and metallic attributes. Notably, group VI TMDs (MoS2, MoSe2, WS2, WSe2) have garnered significant attention, thanks to their stability and semiconducting characteristics, featuring optical band gaps around 1-2 eV. These properties render this group of TMDs become highly promising for various applications. At few- to monolayered architecture, these materials undergo a gradual transition from indirect to direct band gap, thereby enhancing their utilities in the realm of electronic and optoelectronic domains, such as 2D field-effect transistors (2D FETs) (Sebastian, A.; Pendurthi, R.; Choudhury, T. H.; Redwing, J. M.; Das, S. Benchmarking Monolayer MoS2and WS2Field- Effect Transistors. Nat. Commun. 2021, 12, 693), memristors (Xu, R.; Jang, H.; Lee, M.-H.; Amanov, D.; Cho, Y.; Kim, H.; Park, S.; Shin, H.; Ham, D. Vertical MoS2Double-Layer Memristor with Electrochemical Metallization as an Atomic-Scale Synapse with Switching Thresholds Approaching 100 Mv. Nano Lett. 2019, 19, 2411–2417), photodetectors (Lopez- Sanchez, O.; Lembke, D.; Kayci, M.; Radenovic, A.; Kis, A. Ultrasensitive Photodetectors Based on Monolayer MoS2. Nat. Nanotechnol. 2013, 8, 497–501), solar cell (Tsai, M.-L.; Su, S.-H.; Chang, J.-K.; Tsai, D.-S.; Chen, C.-H.; Wu, C.-I.; Li, L.-J.; Chen, L.-J.; He, J.-H. Monolayer MoS2Heterojunction Solar Cells. ACS Nano 2014, 8, 8317–8322). However, beyond the proof of concept from laboratory to device, several challenges have been addressed, concerning the4886-5650-6109.1Page 38 of 224 094876-000020WOPTlimitations of exfoliation methods (Velický, M.; Donnelly, G. E.; Hendren, W. R.; McFarland, S.; Scullion, D.; DeBenedetti, W. J. I.; Correa, G. C.; Han, Y.; Wain, A. J.; Hines, M. A.; Muller, D. A.; Novoselov, K. S.; Abruña, H. D.; Bowman, R. M.; Santos, E. J. G.; Huang, F. Mechanism of Gold-Assisted Exfoliation of Centimeter-Sized Transition-Metal Dichalcogenide Monolayers. ACS Nano 2018, 12, 10463–10472; Rangnekar, S. V.; Sangwan, V. K.; Jin, M.; Khalaj, M.; Szydłowska, B. M.; Dasgupta, A.; Kuo, L.; Kurtz, H. E.; Marks, T. J.; Hersam, M. C. Electroluminescence from Megasonically Solution-Processed MoS2Nanosheet Films. ACS Nano 2023, 17, 17516–17526; Yang, R.; Mei, L.; Zhang, Q.; Fan, Y.; Shin, H. S.; Voiry, D.; Zeng, Z. High-Yield Production of Mono- or Few-Layer Transition Metal Dichalcogenide Nanosheets by an Electrochemical Lithium Ion Intercalation-Based Exfoliation Method. Nat. Protoc.2022, 17, 358–377 and technical fabrication issues such as metal / semiconductor contact, and resistance (Chhowalla, M.; Jena, D.; Zhang, H. Two-Dimensional Semiconductors for Transistors. Nat. Rev. Mater.2016, 1, 1–15). Other echoing challenges are the inherent TMDs' electronic properties and band gap windows, which are primarily tunable through custom-designed thicknesses or elemental doping (Splendiani, A.; Sun, L.; Zhang, Y.; Li, T.; Kim, J.; Chim, C.-Y.; Galli, G.; Wang, F. Emerging Photoluminescence in Monolayer MoS2. Nano Lett.2010, 10, 1271–1275; Robertson, A. W.; Lin, Y.-C.; Wang, S.; Sawada, H.; Allen, C. S.; Chen, Q.; Lee, S.; Lee, G.-D.; Lee, J.; Han, S.; Yoon, E.; Kirkland, A. I.; Kim, H.; Suenaga, K.; Warner, J. H. Atomic Structure and Spectroscopy of Single Metal (Cr, V) Substitutional Dopants in Monolayer MoS2. ACS Nano 2016, 10, 10227–10236). The two strategies have their own limitations; specifically, defects formation resulting from conventional doping methods at the atomically thin structure introduces additional energy levels and sites for electron-hole trapping. As a matter of fact, great efforts have been made to modify the electronic and optical properties of these group VI monolayered TMDs without causing significant damage to the crystal structure while preserving their inherent semiconducting features. A feasible approach that promotes simplicity and scalability is "chemical doping" or "chemical functionalization", achieved by regulating the properties of introduced chemical species. It should be noted that these terms encompass not only robust covalent bond formation but also physiosorbed interactions, leading to unparallel outcomes.

[0173] From the covalent approach, the impact is straightforward. Despite that, natural semiconducting group VI TMDs (denoted as 2H or 1H at monolayer) exhibit chemical inertness due to the orientation of chalcogen pzorbitals and metals dz2 orbitals. These orbitals construct the4886-5650-6109.1Page 39 of 224 094876-000020WOPTantibonding orbitals and contribute to the minimum conduction band, effectively passivating the basal plane of TMD monolayers (Chang, C.-H.; Fan, X.; Lin, S.-H.; Kuo, J.-L. Orbital Analysis of Electronic Structure and Phonon Dispersion in MoS2, MoSe2, WS2, and WSe2Monolayers under Strain. Phys. Rev. B 2013, 88, 195420). Consequently, the range of available strategies is limited. Most studies have demonstrated the effectiveness of defects-healing approach using thiol- organic molecules; however, this strategy is constrained by the concentration of defects (Makarova, M.; Okawa, Y.; Aono, M. Selective Adsorption of Thiol Molecules at Sulfur Vacancies on MoS2(0001), Followed by Vacancy Repair via S–C Dissociation. J. Phys. Chem. C 2012, 116, 22411–22416; Bertolazzi, S.; Bonacchi, S.; Nan, G.; Pershin, A.; Beljonne, D.; Samorì, P. Engineering Chemically Active Defects in Monolayer MoS2Transistors via Ion-Beam Irradiation and Their Healing via Vapor Deposition of Alkanethiols. Adv. Mater. 2017, 29, 1606760; Ippolito, S.; Urban, F.; Zheng, W.; Mazzarisi, O.; Valentini, C.; Kelly, A. G.; Gali, S. M.; Bonn, M.; Beljonne, D.; Corberi, F.; Coleman, J. N.; Wang, H. I.; Samorì, P. Unveiling Charge-Transport Mechanisms in Electronic Devices Based on Defect-Engineered MoS2Covalent Networks. Adv. Mater. 2023, 35, 2211157). A minor branch, employing the thiol-functional groups to directly interact with the basal plane of TMDs, showed negligible effects owing to the weak S-S bonds, giving to the formation of physiosorbed dithiol molecules (Chen, X.; Berner, N. C.; Backes, C.; Duesberg, G. S.; McDonald, A. R. Functionalization of Two-Dimensional MoS2: On the Reaction Between MoS2and Organic Thiols. Angew. Chem. Int. Ed.2016, 55, 5803–5808). Recently, a mild covalent functionalization approach based on electrophilic maleimides through Michael addition reaction has been proposed (Vera-Hidalgo, M.; Giovanelli, E.; Navío, C.; Pérez, E. M. Mild Covalent Functionalization of Transition Metal Dichalcogenides with Maleimides: A “Click” Reaction for 2H-MoS2and WS2. J. Am. Chem. Soc.2019, 141, 3767–3771). The method offers a direct covalent toolbox; however, the extent of functionalization achieved was overestimated due to subsequent polymerization (Quirós-Ovies, R.; Vázquez Sulleiro, M.; Vera- Hidalgo, M.; Prieto, J.; Gómez, I. J.; Sebastián, V.; Santamaría, J.; Pérez, E. M. Controlled Covalent Functionalization of 2 H-MoS2with Molecular or Polymeric Adlayers. Chem. – Eur. J. 2020, 26, 6629–6634; Vázquez Sulleiro, M.; Quirós-Ovies, R.; Vera-Hidalgo, M.; Gómez, I. J.; Sebastián, V.; Santamaría, J.; Pérez, E. M. Covalent Cross-Linking of 2H-MoS2Nanosheets. Chem. – Eur. J.2021, 27, 2993–2996). To overcome the inertness of semiconducting TMDs, a pre-activation step was proposed that converts the thermodynamically favorable 1H phase to4886-5650-6109.1Page 40 of 224 094876-000020WOPTmetastable 1T phase (Eda, G.; Fujita, T.; Yamaguchi, H.; Voiry, D.; Chen, M.; Chhowalla, M. Coherent Atomic and Electronic Heterostructures of Single-Layer MoS2. ACS Nano 2012, 6, 7311–7317; Fan, X.; Xu, P.; Zhou, D.; Sun, Y.; Li, Y. C.; Nguyen, M. A. T.; Terrones, M.; Mallouk, T. E. Fast and Efficient Preparation of Exfoliated 2H MoS2Nanosheets by Sonication- Assisted Lithium Intercalation and Infrared Laser-Induced 1T to 2H Phase Reversion. Nano Lett. 2015, 15, 5956–5960). The metastable 1T phase, characterized by its high electron density, is metallic and acts as a nucleophile, enabling it to react with electrophilic species such as organohalides (Voiry, D.; Goswami, A.; Kappera, R.; Silva, C. de C. C. e; Kaplan, D.; Fujita, T.; Chen, M.; Asefa, T.; Chhowalla, M. Covalent Functionalization of Monolayered Transition Metal Dichalcogenides by Phase Engineering. Nat. Chem.2015, 7, 45–49; Ries, L.; Petit, E.; Michel, T.; Diogo, C. C.; Gervais, C.; Salameh, C.; Bechelany, M.; Balme, S.; Miele, P.; Onofrio, N.; Voiry, D. Enhanced Sieving from Exfoliated MoS2Membranes via Covalent Functionalization. Nat. Mater.2019, 18, 1112–1117) or radical-initiated species such as diazonium salts (Knirsch, K. C.; Berner, N. C.; Nerl, H. C.; Cucinotta, C. S.; Gholamvand, Z.; McEvoy, N.; Wang, Z.; Abramovic, I.; Vecera, P.; Halik, M.; Sanvito, S.; Duesberg, G. S.; Nicolosi, V.; Hauke, F.; Hirsch, A.; Coleman, J. N.; Backes, C. Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts. ACS Nano 2015, 9, 6018–6030), and alkyl azide (Tuci, G.; Mosconi, D.; Rossin, A.; Luconi, L.; Agnoli, S.; Righetto, M.; Pham-Huu, C.; Ba, H.; Cicchi, S.; Granozzi, G.; Giambastiani, G. Surface Engineering of Chemically Exfoliated MoS2in a “Click”: How To Generate Versatile Multifunctional Transition Metal Dichalcogenides-Based Platforms. Chem. Mater. 2018, 30, 8257–8269). Though, phase transformation diminishes the semiconducting characteristics, while an additional phase reconversion, typically involving heat, generates defects and chemical transformation.

[0174] Without being bound by theory, we hypothesize that instead of complete conversion to metallic phase, a milder reductant could donate a sufficient number of electrons into the antibonding orbitals of semiconducting TMDs without inducing phase transformation. This approach would potentially allow for subsequent covalent functionalization. To test our hypothesis, we chose NHCs, owing to their mild electron donating feature (Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An Overview of N-Heterocyclic Carbenes. Nature 2014, 510, 485–496). Surprisingly, experimental observations exceeded our initial hypotheses. Upon interaction with group VI TMDs, NHCs possess the capability to remain on the basal plane of 2D4886-5650-6109.1Page 41 of 224 094876-000020WOPTmonolayered TMD nanosheets and subsequently drive a restacking phenomenon, giving to the entrapment of NHCs between the single layers of TMDs. This interaction is surprising since the bulky NHCs head groups are not expected to achieve an intercalation state within group VI TMD hosts. Moreover, the inertness of group VI TMDs limits the intercalation possibilities, which was previously believed to be exclusively driven by dual-charged host-guest systems (Heising, J.; Kanatzidis, M. G. Exfoliated and Restacked MoS2and WS2:  Ionic or Neutral Species? Encapsulation and Ordering of Hard Electropositive Cations. J. Am. Chem. Soc.1999, 121, 11720– 11732). As such, the previously reported strategies involved the use of small metallic cations or dual process of restacking and guest entrapment in chemically exfoliated few- to monolayered TMDs (Divigalpitiya, W. M. R.; Frindt, R. F.; Morrison, S. R. Inclusion Systems of Organic Molecules in Restacked Single-Layer Molybdenum Disulfide. Science 1989, 246, 369–371; Tagaya, H.; Hashimoto, T.; Karasu, M.; Izumi, T.; Chiba, K. Inclusion of Substituted Ferrocenes and Aromatic Compounds into MoS2Layers as New Intercalation Compounds. Chem. Lett.1991, 20, 2113–2116. Chem. Lett. 1991, 20, 2113–2116; Bissessur, R.; Heising, J.; Hirpo, W. Toward Pillared Layered Metal Sulfides. Intercalation of the Chalcogenide Clusters Co6Q8(PR3)6 (Q = S, Se, and Te and R = Alkyl) into MoS2. Chem. Mater.1996, 8, 318–320; Brenner, J.; Marshall, C. L.; Ellis, L.; Tomczyk, N.; Heising, J.; Kanatzidis, M. Microstructural Characterization of Highly HDS-Active Co6S8-Pillared Molybdenum Sulfides. Chem. Mater. 1998, 10, 1244–1257; Kosidowski, L.; Powell, A. V. Naphthalene Intercalation into Molybdenum Disulfide. Chem. Commun. 1998, 2201–2202). In either case, excessive electrons were injected into the host framework, inducing a metallic phase transformation. In our work described herein, the original exfoliated TMDs, and the resultant intercalated materials preserve the semiconducting characteristics. To our knowledge, such an observation has not been reported.

[0175] Herein, we present the first experimental functionalization of 2D few-to- monolayered MoS2and WS2using NHCs, in the form of benzimidazolium salts. The adopted molecule, labeled as NHC15OH[OMs] is shown in FIG. 27). The bulk MoS2and WS2were initially exfoliated to obtain few- to monolayered nanosheets using the redox exfoliation methods (Jawaid, A.; Che, J.; Drummy, L. F.; Bultman, J.; Waite, A.; Hsiao, M.-S.; Vaia, R. A. Redox Exfoliation of Layered Transition Metal Dichalcogenides. ACS Nano 2017, 11, 635–646; Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater. 2020, 32, 6550–6565). Herein, we demonstrate that the NHCs4886-5650-6109.1Page 42 of 224 094876-000020WOPTinteract with the basal plane of exfoliated 2D MoS2and WS2nanosheets, replacing the surface- adsorbed redox products and consequently altering the surface Zeta potential. Without being bound by theory, the interaction nature between NHCs and exfoliated TMDs is hypothesized to involve orbital hybridization, leading to a restacking phenomenon. As a result, the NHC molecules become entrapped within the interlayer gaps of the TMDs, thereby forming superlattice structures signified by interlayer expansion. The molecular entrapment and interlayer expansion are characterized by X-ray powder diffraction (XRD), attenuated total reflectance infrared spectroscopy (ATIR), and X-ray photoelectron spectroscopy (XPS). The implications of intercalated NHCs are further elaborated upon using Raman spectroscopy, with complementary insights drawn from observations made via photoluminescence (PL), XPS, atomic force microscopy (AFM), scanning electron microscopy (SEM), in conjunction with centrifuge cascade and thin film fabrication methodologies.

[0176] Redox Exfoliation of Few- to Monolayered TMD Nanosheets

[0177] Exfoliation of pre-treated bulk MoS2and WS2was carried out, following the reported procedures, with minor adjustments (Jawaid, A.; Che, J.; Drummy, L. F.; Bultman, J.; Waite, A.; Hsiao, M.-S.; Vaia, R. A. Redox Exfoliation of Layered Transition Metal Dichalcogenides. ACS Nano 2017, 11, 635–646; Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater. 2020, 32, 6550–6565). (see Experimental section herein). After thorough removal of the adsorbed polyoxometalates macroanions (POMs), a centrifuge screening process was employed to isolate thin-layered nanosheets. The ultraviolet-visible spectroscopy (UV-vis) data, shown in FIG.18A, depicts the extinction (ε) spectra of exfoliated MoS2colloidal fractions at four different centrifuge rates. The spectra combine the aspects of both absorbance (α) and size-dependent scattering (σ) background; hence, pertinent information can be extracted for approximate estimation of the thicknesses and lateral sizes of exfoliated MoS2nanosheets. A comprehensive study was conducted, highlighting the significance of evolving thicknesses and lateral sizes of liquid-phase- exfoliated nanosheets (Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; Hanlon, D.; Scheuschner, N.; Maultzsch, J.; Houben, L.; Duesberg, G. S.; Donegan, J. F.; Nicolosi, V.; Coleman, J. N. Edge and Confinement Effects Allow in Situ Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun. 2014, 5, 4576; Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon,4886-5650-6109.1Page 43 of 224 094876-000020WOPTD.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater. 2017, 29, 243–255). An important feature is the local minimum at 345 nm, extrapolated from statistical data set as an independent metric, free from the influence of scattering effects. This feature serves as a reference point for normalization in comparative analysis. Based on these aforementioned reports, our data, in FIG. 18A, delineates the normalized extinction spectra of exfoliated MoS2. It is worth highlighting that increasing centrifuge rate results in thinner and smaller nanosheets, (Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; Hanlon, D.; Scheuschner, N.; Maultzsch, J.; Houben, L.; Duesberg, G. S.; Donegan, J. F.; Nicolosi, V.; Coleman, J. N. Edge and Confinement Effects Allow in Situ Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun.2014, 5, 4576; Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon, D.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater.2017, 29, 243–255) which emphasizes the discussed phenomenon in the region from 700 to 800 nm. In the spectral range from 700 to 350 nm, the excitonic peaks of MoS2were designated as A, B, C, D from right to left, respectively. Among these excitons, A presents the K-point transition from valence band to conduction band, which demonstrates the band gap of material. Consequently, A-excitonic wavelength can be employed to infer the thicknesses of MoS2nanosheets, owing to the layer-dependent characteristics. Nevertheless, within the range below 700 nm, the dominance of scattering background necessitates the conversion of the original extinction spectrum into its second derivatives. This mathematical transformation was recommended as an essential data processing step to reduce the peak shift caused by the broad background (Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; Hanlon, D.; Scheuschner, N.; Maultzsch, J.; Houben, L.; Duesberg, G. S.; Donegan, J. F.; Nicolosi, V.; Coleman, J. N. Edge and Confinement Effects Allow in Situ Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun.2014, 5, 4576; Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon, D.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater.2017, 29, 243–255). The second derivative transformation of A exciton is presented in FIG. 18B with the x-axis unit in energy (eV). As expected, at a high centrifuge rate of 2500 rpm, the resultant exfoliated MoS2nanosheets exhibit their minimum4886-5650-6109.1Page 44 of 224 094876-000020WOPTthicknesses with an approximate A-excitonic transition of 1.85 eV (λA= 671 nm). In contrast, the thicker ones are observed when A-excitonic transition energy falls below 1.85 eV at lower centrifuge rates. The full second derivative transformation and A-excitonic wavelengths at different centrifuge rates are shown in FIG.30A – FIG.30B and FIG.18C. Compared to the fitted models and corresponding reported equations, (Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater. 2020, 32, 6550–6565; Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; Hanlon, D.; Scheuschner, N.; Maultzsch, J.; Houben, L.; Duesberg, G. S.; Donegan, J. F.; Nicolosi, V.; Coleman, J. N. Edge and Confinement Effects Allow in Situ Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun.2014, 5, 4576; Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon, D.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater. 2017, 29, 243–255) the resultant exfoliated MoS2nanosheets exhibit thicknesses varying from 4–7 layers. However, it is imperative to emphasize that UV-vis extinction spectrum only provides an approximate estimation about thicknesses of predominant population of nanosheets. As mentioned, scattering background plays a key role in understanding thickness-related aspects. In addition, the inherent nature of redox exfoliation, which leads to the absorption of POMs on the surface of 2D TMD nanosheets, might contribute to the peak shifts. This effect might be pronounced when POMs species exhibit comparable sizes, at least 1 nm in height (Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater.2020, 32, 6550–65650. The surface absorption of negatively charged POMs is supported by comparing the Zeta potentials of redox-exfoliated MoS2and sonication-induced exfoliated MoS2, shown in FIG. 18D. A similar observation was recorded, shown in FIG. 31A – FIG. 31D, with redox-exfoliated WS2(ε235as normalization metric).

[0178] As complementary data, statistical analysis based on height retrace from AFM was conducted. The height profiles of redox-exfoliated MoS2dispersion are presented in FIG.19A – FIG. 19H. It is crucial to note that the actual thickness of a single layer is not identical to the theoretical one, owing to factors such as solvent effects and the presence of POMs absorbed on the nanosheets’ surface. To address this issue, an internal reference, known as “step height”, is employed (Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered4886-5650-6109.1Page 45 of 224 094876-000020WOPTTransition Metal Dichalcogenides. Chem. Mater.2020, 32, 6550–6565; Backes, C.; Smith, R. J.; McEvoy, N.; Berner, N. C.; McCloskey, D.; Nerl, H. C.; O’Neill, A.; King, P. J.; Higgins, T.; Hanlon, D.; Scheuschner, N.; Maultzsch, J.; Houben, L.; Duesberg, G. S.; Donegan, J. F.; Nicolosi, V.; Coleman, J. N. Edge and Confinement Effects Allow in Situ Measurement of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun.2014, 5, 4576; Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon, D.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater.2017, 29, 243–255). The solution is based on the observation that incomplete exfoliation results in staircase-like height profile. As illustrated in our data, a step height of approximate 2.0 to 3.0 nm was found and attributed to the thickness of a single layer, which is consistent with previous reports (Jawaid, A. M.; Ritter, A. J.; Vaia, R. A. Mechanism for Redox Exfoliation of Layered Transition Metal Dichalcogenides. Chem. Mater. 2020, 32, 6550–6565). Herein, we emphasize that statistical analysis is a time-intensive process and susceptible to misinterpretation of data due to the intricacies involved in samples preparation, given that the standard sample preparation method for AFM analysis typically involves extensive dilution and drop-casting. This results in random orientation of nanosheets and their tendency to self-aggregate. Fortunately, the issue can be effectively overcome by the recent self-assembled thin film formation technique (FIG. 28A – FIG.28D) (Yu, X.; Prévot, M. S.; Guijarro, N.; Sivula, K. Self-Assembled 2D WSe2Thin Films for Photoelectrochemical Hydrogen Production. Nat. Commun.2015, 6, 7596; Yun, T.; Kim, J.-S.; Shim, J.; Choi, D. S.; Lee, K. E.; Koo, S. H.; Kim, I.; Jung, H. J.; Yoo, H.-W.; Jung, H.-T.; Kim, S. O. Ultrafast Interfacial Self-Assembly of 2D Transition Metal Dichalcogenides Monolayer Films and Their Vertical and In-Plane Heterostructures. ACS Appl. Mater. Interfaces 2017, 9, 1021–1028). By leveraging this method, uniform and flat lying nanosheets can be achieved on the deposited substrates, facilitating the population height retrace analysis of 2D exfoliated TMDs (FIG. 32A – FIG. 32E). According to the height profile analysis of over 300 exfoliated MoS2nanosheets, we deduced the average thickness of 9.7 4.2 nm, corresponding to approximately 5 layers. To further validate the probed species being indeed exfoliated materials, we compared the height and amplitude retrace profiles (FIG.33A – FIG.33B) with the shape images captured by transmission electron microscopy (TEM) (FIG. 19E – FIG. 19H). Finally, XRD measurements were carried out to compare bulk and thin film exfoliated MoS2(FIG.19D). As a consequence of restacking, the in-plane (hk0) reflections experience disappearance or substantial attenuation.4886-5650-6109.1Page 46 of 224 094876-000020WOPTMeanwhile, (00l) reflections, attributed to the interlayer thickness, significantly enhances. Similar analyses for redox-exfoliated WS2are shown in FIG.34A – FIG.34E and FIG.35A – FIG.35D.

[0179] NHC-Functionalized Few- to Monolayered TMD Nanosheets

[0180] Having successfully attained few- to monolayered MoS2and WS2nanosheets, we proceeded with functionalization experiments involving NHC15OH[OMs] adsorbate and the exfoliated TMDs. Following the complete dissolution of the molecule in dichloromethane (DCM), redox-exfoliated MoS2in anhydrous acetonitrile (a-ACN) was introduced, and the system was allowed to stand undisturbed for 24 h. Typically, depending on the molar ratio between the NHCs and the redox-exfoliated MoS2, abrupt compression resulting in precipitation could be directly observed within a matter of minutes. The resultant black powder was centrifuged and washed by DCM to remove unreacted NHCs. FIG. 20A illustrates the XRD patterns of thin film NHC15OH[OMs]-functionalized MoS2. Interestingly, diffraction patterns of the novel material reveal two distinct and prominent peaks at 7.98 and 24.25 (2θ), which can be attributed to the molecular intercalation occurring between MoS2layers. We assign these new peaks corresponding to the (002’) and (006’) reflections of the novel phase with an expanded interlayer gap of 11.1 Å compared to 6.1 Å observed in bulk MoS2. FIG.36 presents a comparative analysis of the XRD pattern between powder NHC15OH[OMs] and the magnified XRD pattern of NHC15OH[OMs]- functionalized MoS2. Within the magnified XRD pattern, the appearance of small peaks, which are negligible and similar to those observed in powder NHC15OH[OMs], indicates molecular crystallization within the structure of intercalated host. To further offer complementary evidence of interlayer entrapped NHCs, ATIR measurements were conducted on thin film samples (FIG. 20B). XPS spectra also validate the presence of NHC molecules within the NHC-functionalized samples. Only NHC-functionalized MoS2and NHC-functionalized WS2exhibit the emergence of N 1s peaks at 401.5 eV and the additional S 2p peaks at 170 eV (FIG.21A – FIG.21D and FIG. 37A – FIG.37D). These peaks are attributed to the N atoms constituting the N-heterocyclic ring and S6+atoms within the methanesulfonate groups, respectively. Subsequently, the zeta potential of the anticipated NHC-functionalized MoS2was collected, providing a preliminary assessment of the surface characteristics (FIG. 20C). Upon interaction with NHCs, the resultant material demonstrates a positive surface potential shift, compared to that of redox-exfoliated MoS2. Without being bound by theory, we hypothesize that POMs are desorbed from TMDs surface, and replaced by NHCs, which remain strongly bound, thereby destabilizing the system. This is4886-5650-6109.1Page 47 of 224 094876-000020WOPTfollowed by a self-restacking process, forming a superlattice, characterized by the expanded vdW interlayer gaps of 2D layered materials (FIG.20D).

[0181] In pursuit of achieving a complete intercalation state, a series of samples was prepared by increasing the reacted molar ratio of NHCs to TMDs. The concentration of redox- exfoliated MoS2(and WS2) within the as-prepared colloidal solution was systematically extrapolated, followed by a titration procedure (details in Experimental section herein). Surprisingly, at a high molar ratio of 15, trace amounts of multilayered MoS2are still detected on the XRD patterns, as evidenced at pronouncing (00l) and (h0l) reflections. Based on reported works, it was established that at the stage of complete intercalation, intercalated 2D layered TMDs typically illustrate a complete set of (00l) reflections (Pereira, J. M.; Tezze, D.; Niehues, I.; Asensio, Y.; Yang, H.; Mester, L.; Chen, S.; Casanova, F.; Bittner, A. M.; Ormaza, M.; Schiller, F.; Martín-García, B.; Hillenbrand, R.; Hueso, L. E.; Gobbi, M. Percolating Superconductivity in Air-Stable Organic-Ion Intercalated MoS2. Adv. Funct. Mater. 2022, 32, 2208761). In contrast, our data set consistently reveals only two reflections, namely (002’) and (006’). Without being bound by theory, we reason that there might be three plausible explanations for this experimental observation. First, most prior works reported the intercalation of 2D layered TMDs followed by Li intercalation-induced exfoliation, which caused a phase transformation from the inherent 1H to 1T at the monolayered architecture. These two phases demonstrate fundamental structural difference, leading to variation in the stacking sequence of Mo and two S layers (Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L.-J.; Loh, K. P.; Zhang, H. The Chemistry of Two-Dimensional Layered Transition Metal Dichalcogenide Nanosheets. Nat. Chem.2013, 5, 263–275). Given that 1T phase stacks in an AbC AbC order while 2H stacks in an AbA BaB order, the restacked materials after intercalation promote ordered symmetry along the direction perpendicular to the basal plane of TMDs. In our case, the exfoliated TMDs retained their initial semiconducting 2H (or 1H at monolayer) phase after redox exfoliation, as evidenced in XPS spectra (FIG. 21A – FIG. 21D). The transformation to 1T phase could be distinctly observed through the shift of both Mo 3d and S 2p peaks to lower binding energies (Fan, X.; Xu, P.; Li, Y. C.; Zhou, D.; Sun, Y.; Nguyen, M. A. T.; Terrones, M.; Mallouk, T. E. Controlled Exfoliation of MoS2Crystals into Trilayer Nanosheets. J. Am. Chem. Soc.2016, 138, 5143–5149). Secondly, we suspect that the introduction of NHCs abruptly alters the surface properties of redox-exfoliated TMDs, destabilizing the entire system and leading to rapid agglomeration. To address this hypothesis, a control experiment was4886-5650-6109.1Page 48 of 224 094876-000020WOPTset up, detailed in the Experimental section herein. Shortly, following complete intercalation and restacking process, the resultant mixture was sonicated to redisperse agglomerate materials. The system was allowed to stand undisturbed, which gives to a second re-stacking process. This procedure was optionally repeated several times to achieve a set of 5 samples, then subjected to XRD measurements. FIG.38 depicts the XRD patterns of 15-NHC / MoS2samples, which remain negligible change across different sonicating-restacking cycles. The data suggests the system achieving an equilibrium state no matter how aggressive disturbance was introduced. On the other hand, a minor peak emerges at a lower angle of 6.77 (2θ), suggesting an expansion of the MoS2interlayer space by 13.0 Å. The novel reflection indicates a slight disruption of molecular orientation after successive dispersing and restacking processes, while the (002’) reflection remains prominent. We then comprehend that additional superlattice structures might exist. Considering the elongated alkyl chain of the NHCs tail group and a comparison with the thickness of SAMs on a planar flat Au substrate (Choi, Y.; Park, C. S.; Tran, H.-V.; Li, C.-H.; Crudden, C. M.; Lee, T. R. Functionalized N-Heterocyclic Carbene Monolayers on Gold for Surface-Initiated Polymerizations. ACS Appl. Mater. Interfaces 2022, 14, 44969–44980) a broadened interlayer gap of only 5 Å renders the formation of NHCs arranged in a potentially flat bilayer-manner between two TMD monolayers. This geometric understanding is supported by prior observations employing aromatic ring systems such as metallocene, naphthalene, etc. (Divigalpitiya, W. M. R.; Frindt, R. F.; Morrison, S. R. Inclusion Systems of Organic Molecules in Restacked Single-Layer Molybdenum Disulfide. Science 1989, 246, 369–371; Tagaya, H.; Hashimoto, T.; Karasu, M.; Izumi, T.; Chiba, K. Inclusion of Substituted Ferrocenes and Aromatic Compounds into MoS2Layers as New Intercalation Compounds. Chem. Lett.1991, 20, 2113–2116; Kuo, D.-Y.; Rice, P. S.; Raugei, S.; Cossairt, B. M. Charge Transfer in Metallocene Intercalated Transition Metal Dichalcogenides. J. Phys. Chem. C 2022, 126, 13994–14002). In addition, it has been reported that the intercalation of alkylamines with shorter alkyl chain length was able to expand the interlayer space to a greater extent (Jeong, S.; Yoo, D.; Ahn, M.; Miró, P.; Heine, T.; Cheon, J. Tandem Intercalation Strategy for Single-Layer Nanosheets as an Effective Alternative to Conventional Exfoliation Processes. Nat. Commun. 2015, 6, 5763). This might arise from the bulky carbene head groups that hinder the formation of densely packed SAMs in a standing-up configuration or from the preferential geometric hybridizations with π-electron organic molecules, which will be discussed in detail later. As a result, we come up with the third hypothesis that the4886-5650-6109.1Page 49 of 224 094876-000020WOPTfunctionalization is indeed limited owing to the incomplete exfoliation of TMDs, presented in the next section.

[0182] Limitation of NHC Functionalization due to Incomplete Exfoliation of TMDs

[0183] As previously stated, the redox exfoliation method yields an average thickness distribution of 4-7 layers. Considering the bulkiness of NHC15OH[OMs], it is conceivable that the functionalization process occurs primarily at the exposed basal plane of TMDs, rather than being capable of penetrating into the intrinsic vdW gap (6.1 Å) of few-layered TMDs. Consequently, the subsequent restacking leads to the formation of two distinct structures (FIG. 22A – FIG. 22B). Herein, it is crucial to note that XRD peaks arise strictly from a periodic arrangement within the crystal lattice. Therefore, the second structure (outer right), depicted in FIG.22A – FIG.22B, solely contributes to the (002) reflections, resembling the behavior observed in multilayered TMDs. Despite that, the additional presence of NHC layers, effectively separate exfoliated few-layered TMDs nanosheets, giving to the broadened full half width maximum (FMHW) of (002) peak. Akin to the observation in 15-NHC / MoS2, 15-NHC / WS2, shown in FIG. 39A – FIG.39B, demonstrates analogous finding.

[0184] To furnish visual evidence of the incomplete exfoliation, we set up the centrifuge cascade experiment (FIG.29) to collect exfoliated nanosheets at distinct fractions. Each fraction underwent screening via two different centrifuge rates enabling the custom selection of nanosheet thicknesses and sizes (Backes, C.; Higgins, T. M.; Kelly, A.; Boland, C.; Harvey, A.; Hanlon, D.; Coleman, J. N. Guidelines for Exfoliation, Characterization and Processing of Layered Materials Produced by Liquid Exfoliation. Chem. Mater.2017, 29, 243–255). Next, we prepared thin-film redox-exfoliated TMDs on Si substrates and subjected them to SEM imaging for statistical size analysis (FIG. 23A – FIG. 23H). It is observed that fractions collected at higher screening centrifuge rates exhibit nanosheets with smaller lengths and widths. This observation aligns with the concurrent shift in both A and D excitonic transitions, which can be attributed to variations in thickness and size respectively (FIG.23A – FIG.23D). Ultimately, the flat lying nanosheets reveal clear evidence of incomplete exfoliation, as indicated by the edge effects (FIG.32A – FIG.32E). FIG. 23I – FIG. 23N depicts the size distribution of 2D exfoliated few- to monolayered TMD nanosheets. Two metrics, maximum width and length, are employed for this statistical analysis, which reveals an evident shift to smaller sizes among four separated fractions.

[0185] Doping Effects of NHC15OH[OMs] Adsorbates4886-5650-6109.1Page 50 of 224 094876-000020WOPT

[0186] Chemical structures, core energy levels and electronic properties of NHC- functionalized TMDs were extracted under XPS investigations. All spectra were initially calibrated by C 1s peak at 284.8 eV. In FIG. 21A – FIG. 21D, no trace of 1T-metallic phase presents, the redox-exfoliated MoS2remain semiconducting 2H (1H at monolayer) after exfoliation. Typically, variation in spectra shape of Mo 3d and S 2p energy levels is negligible. Without being bound by theory, this indication suggests that the interactions between NHC15OH[OMs] and MoS2involve other mechanisms rather than covalent bonds. Indeed, both Mo 3d and S 2p spectra exhibit a slight shift of 0.3 eV to the lower binding energy. We then exploited the XPS low binding energy region (0-20 eV), to analyze the disparity between the material’s Fermi level (EF) and valence band (EVB). By extrapolating the slopes of the low energy spectra, we deduced the energy difference EF– EVBto be 0.9 and 1.2 eV for 15-NHC / MoS2and redox-exfoliated MoS2, respectively (FIG. 40A – FIG. 40D). It illustrates that the adopted NHC15OH[OMs] slightly elevates the valence band by donating a gentle number of electrons into MoS2framework. A similar analysis was performed with redox-exfoliated WS2and 15- NHC / WS2, shown in FIG.37A – FIG.37D and FIG.41A – FIG.41B, which achieved an identical observation. In this context, it is crucial to highlight that at the monolayered architecture, signified by a sub-nanometer thickness, the ultra-thin atomic resolution enhances the multifaced effects of physiosorbed heterojunctions. These effects are governed by mechanisms such as simple charge transfer model, dielectric screening effect, vectorial dipole-dipole interactions, among others (Zhao, Y.; Gobbi, M.; Hueso, L. E.; Samorì, P. Molecular Approach to Engineer Two-Dimensional Devices for CMOS and beyond-CMOS Applications. Chem. Rev. 2022, 122, 50–131). Consequently, a simple adsorbed molecular system could significantly perturb the energy alignments, giving to alteration of electron-phonon scattering throughout the entire 2D crystal lattice. Given the periodic nature of electron-phonon scattering, slight changes provide indication of structural alterations. In the case of 2D monolayered TMDs, electron-phonon characteristics can be elucidated through two significant vibration modes in the Raman spectra: the E12gphonon mode, representing an in-plane vibration involving both transition metal and chalcogen atoms, and the A1gmode, depicting an out-of-plane vibration, solely involving chalcogen atoms. Depending on the directional shift of these two modes, deduction regarding n- or p-type doping effects can be determined. This phenomenon has been extensively studied and reported in systems involving molecular SAMs on monolayered TMDs (Kang, D.-H.; Kim, M.-S.; Shim, J.; Jeon, J.; Park, H.-4886-5650-6109.1Page 51 of 224 094876-000020WOPTY.; Jung, W.-S.; Yu, H.-Y.; Pang, C.-H.; Lee, S.; Park, J.-H. High-Performance Transition Metal Dichalcogenide Photodetectors Enhanced by Self-Assembled Monolayer Doping. Adv. Funct. Mater.2015, 25, 4219–4227; Tarasov, A.; Zhang, S.; Tsai, M.-Y.; Campbell, P. M.; Graham, S.; Barlow, S.; Marder, S. R.; Vogel, E. M. Controlled Doping of Large-Area Trilayer MoS2with Molecular Reductants and Oxidants. Adv. Mater. 2015, 27, 1175–1181; Zhang, S.; Hill, H. M.; Moudgil, K.; Richter, C. A.; Hight Walker, A. R.; Barlow, S.; Marder, S. R.; Hacker, C. A.; Pookpanratana, S. J. Controllable, Wide-Ranging n-Doping and p-Doping of Monolayer Group 6 Transition-Metal Disulfides and Diselenides. Adv. Mater. 2018, 30, 1802991). Therefore, we performed Raman spectroscopic studies to explore the doping effects of NHC15OH[OMs] on the phonons of TMDs. Additionally, for systematic and comprehensive data collection, all samples were deposited onto 300 nm SiO2 / Si substrates, taking advantage of the Si optical transverse vibration mode as an internal reference. To avoid ambient moisture adsorption, which has been reported to partially dope TMDs, (Tongay, S.; Zhou, J.; Ataca, C.; Liu, J.; Kang, J. S.; Matthews, T. S.; You, L.; Li, J.; Grossman, J. C.; Wu, J. Broad-Range Modulation of Light Emission in Two- Dimensional Semiconductors by Molecular Physisorption Gating. Nano Lett. 2013, 13, 2831– 2836) after complete solvent evaporation, the samples were stored in an environment enriched with CaSO4desiccant under vacuum prior to any measurements.

[0187] FIG. 24A – FIG. 24F summarizes the Raman spectra and the corresponding characteristics of the E12gand A1gvibration modes of redox-exfoliated MoS2before and after exposure to NHCs. We note that Raman spectra of all three points of 15-NHC / MoS2were acquired within the same day. Hence, even though the Si optical transverse mode completely diminishes in 15-NHC / MoS2P3 due to the thick layer of deposited materials, peak shift compared to the remaining two points is avoided. Based on the collected data, both E12gand A1gmodes within 15- NHC / MoS2P1 and P2 exhibit a red shift, which is indicative of softening effect attributed to n- doping (Kang, D.-H.; Kim, M.-S.; Shim, J.; Jeon, J.; Park, H.-Y.; Jung, W.-S.; Yu, H.-Y.; Pang, C.-H.; Lee, S.; Park, J.-H. High-Performance Transition Metal Dichalcogenide Photodetectors Enhanced by Self-Assembled Monolayer Doping. Adv. Funct. Mater. 2015, 25, 4219–4227; Tarasov, A.; Zhang, S.; Tsai, M.-Y.; Campbell, P. M.; Graham, S.; Barlow, S.; Marder, S. R.; Vogel, E. M. Controlled Doping of Large-Area Trilayer MoS2with Molecular Reductants and Oxidants. Adv. Mater.2015, 27, 1175–1181; Zhang, S.; Hill, H. M.; Moudgil, K.; Richter, C. A.; Hight Walker, A. R.; Barlow, S.; Marder, S. R.; Hacker, C. A.; Pookpanratana, S. J. Controllable,4886-5650-6109.1Page 52 of 224 094876-000020WOPTWide-Ranging n-Doping and p-Doping of Monolayer Group 6 Transition-Metal Disulfides and Diselenides. Adv. Mater.2018, 30, 1802991). Another notable feature is the broadening and the evolving asymmetry of both E12gand A1gpeaks at P1 and P2 points. To elucidate this phenomenon, we extracted the FMHWs of both peaks and their Raman shifts for comparison, depicted in FIG.24C, FIG.24F. It is observed that as the E12gand A1gmodes undergo further red shift, their FMHWs broaden accordingly. This leads us to understand that NHC15OH[OMs] adsorbates transfer their electrons, which dissipate and delocalize over the finite 2D plane of TMD monolayers. Interestingly, the extent of the shift differs between two points while 15-NHC / MoS2P3 shows no changes compared to redox-exfoliated MoS2. This can be explained by the different restacked structures, as evidenced earlier. In the case of restacked few-layered structures (P3), a small amount of intercalated NHCs exhibits negligible impact. In contrast, a rich intercalation of NHCs in restacked monolayered structure demonstrates a prominent impact, which varies as a function of the entrapped NHC content. We also address that the E12gmode was reported to remain intact or undergo insignificant changes in both peak position and the FMHW, either in monolayered MoS2 or in hybrid SAMs and monolayered MoS2systems (Lee, C.; Yan, H.; Brus, L. E.; Heinz, T. F.; Hone, J.; Ryu, S. Anomalous Lattice Vibrations of Single- and Few-Layer MoS2. ACS Nano 2010, 4, 2695–2700; Li, H.; Zhang, Q.; Yap, C. C. R.; Tay, B. K.; Edwin, T. H. T.; Olivier, A.; Baillargeat, D. From Bulk to Monolayer MoS2: Evolution of Raman Scattering. Adv. Funct. Mater.2012, 22, 1385–1390; Wang, C.; He, Q.; Halim, U.; Liu, Y.; Zhu, E.; Lin, Z.; Xiao, H.; Duan, X.; Feng, Z.; Cheng, R.; Weiss, N. O.; Ye, G.; Huang, Y.-C.; Wu, H.; Cheng, H.- C.; Shakir, I.; Liao, L.; Chen, X.; Goddard III, W. A.; Huang, Y.; Duan, X. Monolayer Atomic Crystal Molecular Superlattices. Nature 2018, 555, 231–236; He, Q.; Lin, Z.; Ding, M.; Yin, A.; Halim, U.; Wang, C.; Liu, Y.; Cheng, H.-C.; Huang, Y.; Duan, X. In Situ Probing Molecular Intercalation in Two-Dimensional Layered Semiconductors. Nano Lett. 2019, 19, 6819–6826; Zhou, B.; Zhou, J.; Wang, L.; Kang, J. H.; Zhang, A.; Zhou, J.; Zhang, D.; Xu, D.; Hu, B.; Deng, S.; Huang, L.; Wong, C. W.; Huang, Y.; Duan, X. A Chemical-Dedoping Strategy to Tailor Electron Density in Molecular-Intercalated Bulk Monolayer MoS2. Nat. Synth. 2024, 3, 67–75).However, in our case, pronounced shift and broadened FMHW were recorded ( ̴ 3.5 cm-1 in P1).In the case of 15-NHC / WS2, red shift and broadened peaks were also recorded in FIG.42A – FIG. 42F. We reason that the effect is not as prominent as that of MoS2due to the ineffective functionalization, shown in FIG. 39A – FIG. 39B. Finally, the A1g- E12gpeak separation was4886-5650-6109.1Page 53 of 224 094876-000020WOPTextracted in FIG.43A – FIG.43B. As previously documented, the A1g- E12g-A1gpeak separation is approximately 19 cm-1for MoS2monolayers. At four layers and thicker, it is consistently 25 cm-1(Lee, C.; Yan, H.; Brus, L. E.; Heinz, T. F.; Hone, J.; Ryu, S. Anomalous Lattice Vibrations of Single- and Few-Layer MoS2. ACS Nano 2010, 4, 2695–2700; Li, H.; Zhang, Q.; Yap, C. C. R.; Tay, B. K.; Edwin, T. H. T.; Olivier, A.; Baillargeat, D. From Bulk to Monolayer MoS2: Evolution of Raman Scattering. Adv. Funct. Mater.2012, 22, 1385–1390). Instead, we observed a consistent separation around 25 cm-1for all 15-NHC / MoS2taken points, including the restacked redox- exfoliated MoS2. This phenomenon will be examined in detail in the coming section, which discusses the NHC functionalization of individual redox-exfoliated MoS2fractions.

[0188] Tailoring Superlattice Structures

[0189] Since the behavior of NHC-functionalized TMDs are hindered by incomplete exfoliation, we employed isolated MoS2fractions, achieved through centrifuge cascade, and subjected them to exposure with NHC15OH[OMs] adsorbates. As depicted in FIG.23A – FIG. 23N, in addition to reduced nanosheet sizes, fractions collected at higher centrifuge rates will result in thinner thicknesses and a richer population of monolayers. Hence, complete functionalization is presumable, characterized by the exclusive appearance of (002') and (006') reflections (FIG. 20A - FIG.20D). However, experimental data reveal an unexpected phenomenon. We designate fractions collected at 2000-2500 rpm, 2500-3000 rpm, 3000-4000 rpm, and >4000 rpm as F1, F2, F3, and F4 respectively. FIG. 25A shows the XRD patterns of 15-NHC / MoS2using these four fractions. These patterns consistently display trace amount of multilayered MoS2nanosheets, even in the final fraction F4. This suggests that the centrifuge cascade effectively collects not only thinner nanosheets but also smaller few-layered nanosheets. Remarkably, two superlattice structures are clearly identified as the sizes and thicknesses of MoS2nanosheets reduce. In the case of 15-NHC / MoS2F1, the predominant superlattice structure is indicated by the (002') reflection at 7.98 (2θ); we refer to this phase as (002'). Conversely, the remaining three fractions showcase a different favored phase at the lower angle 6.77 (2θ), which corresponds to an interlayer expansion of 13.0 ^, in contrast to interlayer space of 11.1^ observed at 7.98 (2θ). We refer to both this newly observed reflection and the corresponding phase as (002*).

[0190] To investigate the excitonic characteristics of NHC-functionalized TMDs, the resultant materials of each fraction were redispersed in a-ACN by a brief bath sonication (approximately 30 seconds), following complete agglomeration and removal of unreacted4886-5650-6109.1Page 54 of 224 094876-000020WOPTNHC15OH[OMs] species. We denote the sonication-induced redispersed samples as 15- NHC / MoS2RS Fx, where Fx represents for the labeled fractions. The normalized extinction spectrum and the corresponding 2ndderivatives are shown in FIG.25C and FIG.25D, respectively. The data reveals that the A-B excitonic transitions in all 15-NHC / MoS2RS Fx fractions illustrate ambiguous alterations compared to those of the in-use redox-exfoliated MoS2fractions in a-ACN. In contrast, the extinction intensity and spectra shape, particularly in the low wavelength range of 200-300 nm, change significantly. It is noteworthy that the spectra shape and extinction intensity in this lower wavelength region are influenced by the scattering background of light, indirectly indicating an overall modification in morphology of the NHC-functionalized MoS2nanosheets. Herein, we double-checked the local minimum ε345to ensure that the normalization metric remained consistent across individual fractions, confirming the reliability of the normalization for comparing alterations in spectra shape. The first fraction, F1, and the last fraction, F4 - utilized as the boundary condition - show negligible variation in ε345, remaining within acceptable experimental error margins (FIG.50A – FIG.50B). To further confirm that these observations originate from the configuration where NHC15OH[OMs] molecules remain on the basal plane of MoS2nanosheets and are undetached by sonication, we directly dropped 15-NHC / MoS2RS Fx fractions onto glasses and subjected to XRD measurement (FIG. 25B). On the other hand, we realize that NHC15OH[OMs] is poorly soluble in a-ACN, likely due to its superior polarity compared to DCM while the long carbon alkyl chain of NHC15OH[OMs] exhibits nonpolar characteristics. Then, we performed an additional control experiment using DCM instead of a- ACN for the sonication-induced redispersion step (FIG.44A – FIG.44B). In both cases, the (002*) phase of 15-NHC / MoS2RS F4 in a-ACN or DCM remains, suggesting that NHCs are strongly bound onto the basal plane of the TMD nanosheets. The transition between (002') to (002*) is obviously spotted as the sizes and thicknesses of MoS2nanosheets reduce. A single (002*) phase is attained when employing the thinnest and smallest nanosheets, regardless of sonication. Nevertheless, the primary factor influencing the phase transition warrants further study, as the centrifuge cascade produces fractions containing both smaller and thinner nanosheets.

[0191] Nature of NHC-TMD Interaction

[0192] Seeking a comprehensive explanation of the fundamental interactions between NHCs and group VI TMDs (MoS2and WS2in this work), we have reviewed literature that claims the formation of covalent bonds. Reported evidence includes a significant change in XPS spectra4886-5650-6109.1Page 55 of 224 094876-000020WOPTshape of the studied TMDs (Vera-Hidalgo, M.; Giovanelli, E.; Navío, C.; Pérez, E. M. Mild Covalent Functionalization of Transition Metal Dichalcogenides with Maleimides: A “Click” Reaction for 2H-MoS2and WS2. J. Am. Chem. Soc.2019, 141, 3767–3771; Kerwin, B.; Liu, S. E.; Sadhukhan, T.; Dasgupta, A.; Jones, L. O.; López-Arteaga, R.; Zeng, T. T.; Facchetti, A.; Schatz, G. C.; Hersam, M. C.; Marks, T. J. Trifluoromethylation of 2D Transition Metal Dichalcogenides: A Mild Functionalization and Tunable p-Type Doping Method. Angew. Chem. Int. Ed.2024, 63, e202403494). In case of a dual-phase metallic 1T and semiconducting 1H, solid-state C13NMR provides strong support if peak shift of the molecular carbon components is observed (Voiry, D.; Goswami, A.; Kappera, R.; Silva, C. de C. C. e; Kaplan, D.; Fujita, T.; Chen, M.; Asefa, T.; Chhowalla, M. Covalent Functionalization of Monolayered Transition Metal Dichalcogenides by Phase Engineering. Nat. Chem. 2015, 7, 45–49; Ries, L.; Petit, E.; Michel, T.; Diogo, C. C.; Gervais, C.; Salameh, C.; Bechelany, M.; Balme, S.; Miele, P.; Onofrio, N.; Voiry, D. Enhanced Sieving from Exfoliated MoS2Membranes via Covalent Functionalization. Nat. Mater.2019, 18, 1112–1117). However, our current observations potentially suggest the presence of interactions beyond merely strongly covalent bonding or physiosorbed heterojunctions. Without being bound by theory, we hypothesize that there are two potential scenarios for the interaction between NHCs and group VI TMDs. The first one might involve the orbital hybridization between the conjugated electron density of perpendicular π-orbitals of NHC aromatic rings and the out-of-plane orbitals of TMDs (FIG.26A). The hybridization results in additional mixed electronic states, contributed from both NHCs and TMDs (Amsterdam, S. H.; Marks, T. J.; Hersam, M. C. Leveraging Molecular Properties to Tailor Mixed-Dimensional Heterostructures beyond Energy Level Alignment. J. Phys. Chem. Lett.2021, 12, 4543–4557). As a consequence, it leads to a net change in electron density distribution, and an electron donation flows from one material to another. In our work described herein, a fraction of electrons flows from NHC15OH[OMs] adsorbates to MoS2or WS2. Among prior works reporting heterojunctions between adsorbed π-organic molecules and monolayered group VI TMDs, we address comparable references studying perylene-derivatives. In case of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA), its molecular structure renders a flat lying geometry on the MoS2monolayer (Habib, M. R.; Li, H.; Kong, Y.; Liang, T.; Obaidulla, S. M.; Xie, S.; Wang, S.; Ma, X.; Su, H.; Xu, M. Tunable Photoluminescence in a van Der Waals Heterojunction Built from a MoS2Monolayer and a PTCDA Organic Semiconductor. Nanoscale 2018, 10, 16107–16115). Density of states4886-5650-6109.1Page 56 of 224 094876-000020WOPTcalculation showed that S pzand Mo dz2 orbitals, which compose the conduction band minimum of MoS2, can hybridize with the conjugated C pzorbitals of PTCDA. In contrast to PTCDA, N,N′- diphenyl-3,4,9,10-perylenedicarboximide (PTCDI-Ph) renders a non-planar geometry on MoS2monolayer, resulting in reduced overlap of the π-orbitals with the out-of-plane MoS2orbitals. The isotropic and anisotropic geometries then affect the electronic and photoelectronic performance of the hybrid system (Obaidulla, S. M.; Habib, M. R.; Khan, Y.; Kong, Y.; Liang, T.; Xu, M. MoS2and Perylene Derivative Based Type-II Heterostructure: Bandgap Engineering and Giant Photoluminescence Enhancement. Adv. Mater. Interfaces 2020, 7, 1901197). Recently, in addition to studies involving large well-defined grown monolayers, a solution-based approach employing exfoliated 2H-WS2nanosheets and a perylene diimide derivative has been reported (Scharl, T.; Binder, G.; Chen, X.; Yokosawa, T.; Cadranel, A.; Knirsch, K. C.; Spiecker, E.; Hirsch, A.; Guldi, D. M. Noncovalent Liquid Phase Functionalization of 2H-WS2with PDI: An Energy Conversion Platform with Long-Lived Charge Separation. J. Am. Chem. Soc. 2022, 144, 5834–5840). The work demonstrated that the semiconducting phase was well preserved while additional characteristics emerged from the adsorbed species. Unfortunately, the final hybrid structure has not been fully characterized.

[0193] In the second scenario, hybridization might originate from electron donation from the in-plane carbon orbital of the N-heterocyclic ring to the transition metal dz2 orbitals (FIG.26B). To elucidate this idea, we revisit the intercalation chemistry of 2D layered TMDs (Jacobson, A. J. 7 - Organic and Organometallic Intercalation Compounds of the Transition Metal Dichalcogenides. In Intercalation Chemistry; Whittingham, M. S., Jacobson, A. J., Eds.; Academic Press, 1982; pp 229–265). In case of metallic 2D layered group IV and V TMDs, direct intercalation can be achieved in the bulk powder form. Due to their half-filled orbitals, intercalation can be explained by the Lewis acid-base model. The metallic TMDs act as electron donors, implying the possibility of saturation of the frontier metal d-orbitals and collapsing a metallic structure to a semiconducting manifold (Jawaid, A.; Pike, N. A.; Pachter, R.; Vaia, R. Basal Surface Hybridization of Group V Layered Transition Metal Dichalcogenides. ACS Mater. Au 2023, 3, 55–65). In the case of 2D layered group VI TMDs, direct intercalation of large species has not been observed in their inherent semiconducting state. The intercalation must be preceded by a pre-intercalation step, followed by an ion-exchange process. Common pre-intercalation methods involve strong reductants such as Butyllithium or direct insertion of alkali cations via4886-5650-6109.1Page 57 of 224 094876-000020WOPTelectrochemistry, which induces a phase transformation from 2H to 1T. Consequently, the resulting metallic group VI TMDs act as Lewis bases towards exchangeable cations or, in some cases, neutral molecules (Divigalpitiya, W. M. R.; Frindt, R. F.; Morrison, S. R. Inclusion Systems of Organic Molecules in Restacked Single-Layer Molybdenum Disulfide. Science 1989, 246, 369– 371; Tagaya, H.; Hashimoto, T.; Karasu, M.; Izumi, T.; Chiba, K. Inclusion of Substituted Ferrocenes and Aromatic Compounds into MoS2Layers as New Intercalation Compounds. Chem. Lett. 1991, 20, 2113–2116; Bissessur, R.; Heising, J.; Hirpo, W. Toward Pillared Layered Metal Sulfides. Intercalation of the Chalcogenide Clusters Co6Q8(PR3)6 (Q = S, Se, and Te and R = Alkyl) into MoS2. Chem. Mater. 1996, 8, 318–320; Brenner, J.; Marshall, C. L.; Ellis, L.; Tomczyk, N.; Heising, J.; Kanatzidis, M. Microstructural Characterization of Highly HDS-Active Co6S8-Pillared Molybdenum Sulfides. Chem. Mater. 1998, 10, 1244–1257; Kosidowski, L.; Powell, A. V. Naphthalene Intercalation into Molybdenum Disulfide. Chem. Commun. 1998, 2201–2202). Recently, the strategy has been progressively innovated by Xiangfeng Duan’s group (Wang, C.; He, Q.; Halim, U.; Liu, Y.; Zhu, E.; Lin, Z.; Xiao, H.; Duan, X.; Feng, Z.; Cheng, R.; Weiss, N. O.; Ye, G.; Huang, Y.-C.; Wu, H.; Cheng, H.-C.; Shakir, I.; Liao, L.; Chen, X.; Goddard III, W. A.; Huang, Y.; Duan, X. Monolayer Atomic Crystal Molecular Superlattices. Nature 2018, 555, 231–236; He, Q.; Lin, Z.; Ding, M.; Yin, A.; Halim, U.; Wang, C.; Liu, Y.; Cheng, H.-C.; Huang, Y.; Duan, X. In Situ Probing Molecular Intercalation in Two-Dimensional Layered Semiconductors. Nano Lett. 2019, 19, 6819–6826; Zhou, B.; Zhou, J.; Wang, L.; Kang, J. H.; Zhang, A.; Zhou, J.; Zhang, D.; Xu, D.; Hu, B.; Deng, S.; Huang, L.; Wong, C. W.; Huang, Y.; Duan, X. A Chemical-Dedoping Strategy to Tailor Electron Density in Molecular-Intercalated Bulk Monolayer MoS2. Nat. Synth. 2024, 3, 67–75). Apart from traditional pre-intercalation methods, positively charged alkylammonium salts were directly inserted into the interlayer gaps of a single crystal MoS2via electrochemistry. This process gave an injection of electrons into the MoS2host framework. The adopted alkylammonium salts, with various molecular structures, limited the extent of intercalation, thereby determining the number of injected electrons. Hence, a phase transformation from 2H to 1T could be controlled by custom-designed molecular structures, achieving an intercalation state through dual-charged host-guest system. From those mentioned above, the mild reducing capability of the lone pair electrons residing in the in-plane N-heterocyclic ring has the potential to generate comparable interactions without driving a phase transformation (Jones, L. O.; Mosquera, M. A.; Ratner, M. A.; Schatz, G. C. Control of Charge4886-5650-6109.1Page 58 of 224 094876-000020WOPTCarriers and Band Structure in 2D Monolayer Molybdenum Disulfide via Covalent Functionalization. ACS Appl. Mater. Interfaces 2020, 12, 4607–4615; Sadhukhan, T.; Schatz, G. C. Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide. J. Phys. Chem. C 2022, 126, 5598–5606; Jones, L. O.; Sadhukhan, T.; Schatz, G. C. Localized π Surface States on 2D Molybdenum Disulfide from Carbene-Functionalization as a Qubit Design Strategy. ACS Phys. Chem. Au 2022, 2, 277–281).

[0194] We have demonstrated the first experimental functionalization of 2D nanolayered TMDs, utilizing N-Heterocyclic Carbenes. Following the desorption of POMs, a restacking process was witnessed that entrapped NHC molecules between the van der Waal layers of 2D TMDs. Remarkably, this intercalation process can occur despite the semiconducting nature of exfoliated TMDs and the cumbersome structure of NHC15OH[OMs]. Without being bound by theory, the intercalated species are hypothesized to hybridize with the basal plane of TMDs, leading to interlayer expansion and formation of superlattice structures. These structural changes are further influenced by the collective effects of both sizes and thicknesses of the nanosheet population. The NHC functionalization induces an n-doping effect, injecting and redistributing the electron density across the entire 2D plane of the TMDs. Given the extent of exfoliation as well as the complex molecular structure of NHC15OH[OMs], further investigation is warranted. In summary, our findings present a novel strategic approach to functionalize 2D layered TMDs and introduce an entirely new intercalated families built on the framework of 2D layered TMD hosts and the NHC family. Notably, the NHC-functionalized superlattice structures retain the semiconducting monolayer characteristics, even at the restacked multilayer configuration.

[0195] Monolayer Behavior of Tailored Superlattice Structures

[0196] Recently, it has been reported that a semiconducting multilayered superlattice structures also demonstrate monolayer-like behavior, evidenced by strong photoluminescent intensity characteristic of monolayer architecture, attributed to the direct excitonic transitions (Wang, C.; He, Q.; Halim, U.; Liu, Y.; Zhu, E.; Lin, Z.; Xiao, H.; Duan, X.; Feng, Z.; Cheng, R.; Weiss, N. O.; Ye, G.; Huang, Y.-C.; Wu, H.; Cheng, H.-C.; Shakir, I.; Liao, L.; Chen, X.; Goddard III, W. A.; Huang, Y.; Duan, X. Monolayer Atomic Crystal Molecular Superlattices. Nature 2018, 555, 231–236; He, Q.; Lin, Z.; Ding, M.; Yin, A.; Halim, U.; Wang, C.; Liu, Y.; Cheng, H.-C.; Huang, Y.; Duan, X. In Situ Probing Molecular Intercalation in Two-Dimensional Layered Semiconductors. Nano Lett. 2019, 19, 6819–6826; Zhou, B.; Zhou, J.; Wang, L.; Kang, J. H.;4886-5650-6109.1Page 59 of 224 094876-000020WOPTZhang, A.; Zhou, J.; Zhang, D.; Xu, D.; Hu, B.; Deng, S.; Huang, L.; Wong, C. W.; Huang, Y.; Duan, X. A Chemical-Dedoping Strategy to Tailor Electron Density in Molecular-Intercalated Bulk Monolayer MoS2. Nat. Synth. 2024, 3, 67–75). Building on these concepts, we further investigated the E12gand A1gvibration modes, along with the photoluminescent properties, of individual MoS2fractions and their respective NHC-functionalized derivatives. FIG.51A – FIG. 51L presents the Raman spectra, highlighting the characteristics of the E12gand A1gvibration modes for MoS2F1-4 and their respective NHC-functionalized counterparts. From the fractional data set, all redox-exfoliated MoS2fractional thin films illustrate similar vibrational characteristics, with a slight shift of the A1gmode position to a lower Raman shift and a slight reduction in the FMHWs across samples F1 to F4. It suggests that MoS2F4 does contain a richer proportion of thinner nanosheets. Despite that, the FMHWs are still larger than the reported one for monolayers (19.0 cm-1) (Lee, C.; Yan, H.; Brus, L. E.; Heinz, T. F.; Hone, J.; Ryu, S. Anomalous Lattice Vibrations of Single- and Few-Layer MoS2. ACS Nano 2010, 4, 2695–2700; Li, H.; Zhang, Q.; Yap, C. C. R.; Tay, B. K.; Edwin, T. H. T.; Olivier, A.; Baillargeat, D. From Bulk to Monolayer MoS2: Evolution of Raman Scattering. Adv. Funct. Mater. 2012, 22, 1385–1390). This can be attributed to the high concentration of redox-exfoliated MoS2Fx (0.1 mM, compared to 0.0125 mM used for AFM analysis) during the thin-film fabrication process, leading to the formation of a restacked multilayered thin film. In contrast, the corresponding 15-NHC / MoS2Fx samples display vibrational variations across samples F1 to F4 in both peak positions and FMHWs. In all four functionalized fractions, a softening effect, characterized by a red shift to lower Raman shift in both E12gand A1gmodes, accompanied by the broadened FMHWs of their respective peaks. The observation is consistent with our previous Raman data set for functionalized, fractional- combined, redox-exfoliated MoS2. The effect is most pronounced in 15-NHC / MoS2F4, which is rich in restacked monolayers, further supporting the influence of incomplete exfoliation on functionalization. As a result, despite the separation introduced by the NHCs, the overall restacked multilayered superlattice structures do not exhibit the vibrational characteristics typical of monolayered MoS2, as indicated by an A1g– E12gpeak separation similar to that of bulk MoS2. We attribute this phenomenon to lattice disorder, as well as the applied strain and doping carriers induced by the NHC functionalization (Busch, R. T.; Sun, L.; Austin, D.; Jiang, J.; Miesle, P.; Susner, M. A.; Conner, B. S.; Jawaid, A.; Becks, S. T.; Mahalingam, K.; Velez, M. A.; Torsi, R.; Robinson, J. A.; Rao, R.; Glavin, N. R.; Vaia, R. A.; Pachter, R.; Joshua Kennedy, W.; Vernon, J.4886-5650-6109.1Page 60 of 224 094876-000020WOPTP.; Stevenson, P. R. Exfoliation Procedure-Dependent Optical Properties of Solution Deposited MoS2Films. Npj 2D Mater. Appl. 2023, 7, 1–13). The related calculations and discussions will be detailed in the experimental section herein.

[0197] FIG. 49A – FIG. 49B provide an overview of the photoluminescent behavior observed in all four 15-NHC / MoS2Fx samples. Additional photoluminescent data for individual MoS2Fx and their respective 15-NHC / MoS2Fx is shown in FIG. 52A – FIG. 52D. The high photoluminescent intensity supports our hypothesis that when TMD (MoS2in this case) monolayers are extensively spaced by foreign species (NHCs), even if they are restacked in superlattice configurations, they retain the characteristics typical of individual monolayers. The data shows an increase in photoluminescent intensity across four fractions, indicating an enhanced periodicity in the arrangement of the restacked monolayers. It is important to note that the lower energy region (1.6-1.8 eV) corresponds to the A-excitonic transition, representing the optical band gap and encompassing contributions from both excitons and trions. Unlike conventional undoped MoS2monolayers, where the spectral profile of the direct A-excitonic transition is sharp and primarily dominated by excitons, the spectra observed in all four functionalized fractions exhibit a broader profile, suggesting an increased trion content. Additionally, the optical band gaps illustrate a slight shift from F1 to F4 with the highest energy reaching 1.74 eV in 15-NHC / MoS2F4. However, this optical band gap remains smaller than that reported for undoped MoS2monolayers (1.85 eV) (Splendiani, A.; Sun, L.; Zhang, Y.; Li, T.; Kim, J.; Chim, C.-Y.; Galli, G.; Wang, F. Emerging Photoluminescence in Monolayer MoS2. Nano Lett.2010, 10, 1271–1275). We hypothesized that this phenomenon is due to the quantity of injected electrons by the doping species (NHCs), which not only increase the trion content but also progressively modifies the overall band gap structure of MoS2. Moreover, the photoluminescent behavior confirm that our electron injection approach via using NHC functionalization, does not cause a phase transition, thereby preserving TMDs' semiconducting properties. Based on the photoluminescent data and the deduced valence band edge at low energy region in XPS, a band gap structure of MoS2and NHC-functionalized MoS2is constructed in FIG.49B.

[0198] Various Embodiments of the Invention

[0199] Embodiments include those listed below.

[0200] Embodiment 1. A method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition4886-5650-6109.1Page 61 of 224 094876-000020WOPTmetal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0201] Embodiment 2. The method of embodiment 1, wherein the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.

[0202] Embodiment 3. The method of embodiment 1 or embodiment 2, wherein the exfoliating is conducted by a redox exfoliation process.

[0203] Embodiment 4. The method of any one of embodiments 1-3, wherein the N- heterocyclic carbene precursor has a structure of Formula (I):Formula (I), wherein: A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1is an optionally substituted linker.

[0204] Embodiment 5. The method of any one of embodiments 1-4, wherein the N- heterocyclic carbene precursor has a structure of Formula (I-A): Formula (I-A),4886-5650-6109.1Page 62 of 224 094876-000020WOPTwherein: A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3and R5, or R3and R6, or R4and R5, or R4and R6may be taken together to form a ring, wherein the ring is optionally substituted.

[0205] Embodiment 6. The method of any one of embodiments 1-5, wherein the N- heterocyclic carbene precursor has the structure of Formula (I-B):4886-5650-6109.1Page 63 of 224 094876-000020WOPTFormula (I-B), wherein: A- is a counterion; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7is H, OR8, SR9, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8is H, or optionally substituted alkyl, and R9is H, or optionally substituted alkyl.

[0206] Embodiment 7. The method of any one of embodiments 1-6, wherein the N- heterocyclic carbene precursor is4886-5650-6109.1Page 64 of 224 094876-000020WOPT.

[0207] Embodiment 8. The method of any one of embodiments 1-7, wherein the at least one N-heterocyclic carbene precursor forms a self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0208] Embodiment 9. The method of any one of embodiments 1-8, wherein the self- assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self- assembled monolayer.

[0209] Embodiment 10. The method of any one of embodiments 1-9, wherein the self- assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0210] Embodiment 11. The method of embodiment 10, wherein the at least one N- heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:4886-5650-6109.1Page 65 of 224 094876-000020WOPTR1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0211] Embodiment 12. The method of embodiment 10 or embodiment 11, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 66 of 224 094876-000020WOPTR5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0212] Embodiment 13. The method of any one of embodiments 10-12, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B): Formula (II-B), wherein:nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;4886-5650-6109.1Page 67 of 224 094876-000020WOPTR1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0213] Embodiment 14. The method of any one of embodiments 10-13, wherein the at least one N-heterocyclic carbene is .

[0214] Embodiment 15. The method of any one of embodiments 10-13, wherein the at least one N-heterocyclic carbene is the same or different.4886-5650-6109.1Page 68 of 224 094876-000020WOPT

[0215] Embodiment 16. The method of any one of embodiments 1-15, wherein the at least one bulk transition metal dichalcogenide comprises a two-dimensional (2D) structure.

[0216] Embodiment 17. The method of embodiment 16, wherein the 2D structure comprises one layer, or a plurality of layers.

[0217] Embodiment 18. The method of any one of embodiments 1-17, wherein the at least one bulk transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen.

[0218] Embodiment 19. The method of embodiment 18, wherein Mais a Group 6 transition metal.

[0219] Embodiment 20. The method of embodiment 18 or embodiment 19, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).

[0220] Embodiment 21. The method of any one of embodiments 18-20, wherein the Group 6 transition metal is molybdenum (Mo).

[0221] Embodiment 22. The method of any one of embodiments 1-21, wherein the at least one bulk transition metal dichalcogenide is MoS2.

[0222] Embodiment 23. The method of any one of embodiments 1-22, wherein the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure.

[0223] Embodiment 24. The method of embodiment 23, wherein the 2D structure comprises one layer, or a plurality of layers.

[0224] Embodiment 25. The method of any one of embodiments 1-24, wherein the at least one exfoliated transition metal dichalcogenide has the formula: MbXb2, wherein: Mbis a Group 4-10 transition metal; and Xbis a chalcogen.

[0225] Embodiment 26. The method of embodiment 25, wherein Mbis a Group 6 transition metal.4886-5650-6109.1Page 69 of 224 094876-000020WOPT

[0226] Embodiment 27. The method of embodiment 25 or embodiment 26, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).

[0227] Embodiment 28. The method of any one of embodiments 25-27, wherein the Group 6 transition metal is molybdenum (Mo).

[0228] Embodiment 29. The method of any one of embodiments 1-28, wherein the at least one exfoliated transition metal dichalcogenide is MoS2.

[0229] Embodiment 30. The method of any one of embodiments 1-29, wherein the reaction of the at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor to make the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0230] Embodiment 31. The method of any one of embodiments 1-30, wherein the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide comprises at least one N-heterocyclic carbene.

[0231] Embodiment 32. The method of embodiment 31, wherein the at least one N- heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0232] Embodiment 33. The method of embodiment 31 or embodiment 32, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A):4886-5650-6109.1Page 70 of 224 094876-000020WOPTFormula (II-A), wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0233] Embodiment 34. The method of any one of embodiments 31-33, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 71 of 224 094876-000020WOPTFormula (II-B), wherein: nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0234] Embodiment 35. The method of any one of embodiments 31-34, wherein the at least one N-heterocyclic carbene is4886-5650-6109.1Page 72 of 224 094876-000020WOPT.

[0235] Embodiment 36. A N-heterocyclic carbene functionalized transition metal dichalcogenide made by the method of any one of embodiments 1-35.

[0236] Embodiment 37. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 36, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide is insulating, semiconducting, conducting, semi-metallic, metallic, or any combination thereof.

[0237] Embodiment 38. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 36, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide is semiconducting.

[0238] Embodiment 39. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 36, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide is a semiconductor.

[0239] Embodiment 40. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 36-39, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a self-assembled monolayer (SAM).4886-5650-6109.1Page 73 of 224 094876-000020WOPT

[0240] Embodiment 41. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 40, wherein the self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0241] Embodiment 42. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 40 or embodiment 41, wherein the self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0242] Embodiment 43. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 42, wherein the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0243] Embodiment 44. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 42 or embodiment 43, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),4886-5650-6109.1Page 74 of 224 094876-000020WOPTwherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0244] Embodiment 45. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 42-44, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 75 of 224 094876-000020WOPTFormula (II-B), wherein: nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0245] Embodiment 46. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 42-45, wherein the at least one N-heterocyclic carbene is4886-5650-6109.1Page 76 of 224 094876-000020WOPT.

[0246] Embodiment 47. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 42-45, wherein the at least one N-heterocyclic carbene is the same or different.

[0247] Embodiment 48. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 36-47, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers, wherein the intercalated layers comprise at least one N-heterocyclic carbene.

[0248] Embodiment 49. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 48, wherein the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:4886-5650-6109.1Page 77 of 224 094876-000020WOPTR1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0249] Embodiment 50. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 48 or embodiment 49, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 78 of 224 094876-000020WOPTR5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0250] Embodiment 51. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 48-50, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B): Formula (II-B), wherein:nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;4886-5650-6109.1Page 79 of 224 094876-000020WOPTR1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0251] Embodiment 52. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 48-51, wherein the at least one N-heterocyclic carbene is .4886-5650-6109.1Page 80 of 224 094876-000020WOPT

[0252] Embodiment 53. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 48-51, wherein the at least one N-heterocyclic carbene is the same or different.

[0253] Embodiment 54. An article of manufacture comprising a N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 36-53.

[0254] Embodiment 55. The article of manufacture of embodiment 54, wherein the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

[0255] Embodiment 56. The article of manufacture of embodiment 54, wherein the article of manufacture is a semiconductor.

[0256] Embodiment 57. An article of manufacture comprising a N-heterocyclic carbene functionalized transition metal dichalcogenide made by the method of any one of embodiments 1- 35.

[0257] Embodiment 58. The article of manufacture of embodiment 57, wherein the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

[0258] Embodiment 59. The article of manufacture of embodiment 57, wherein the article of manufacture is a semiconductor.

[0259] Embodiment 60. Use of the N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 36-53.

[0260] Embodiment 61. Use of the N-heterocyclic carbene functionalized transition metal dichalcogenide made by the method of any one of embodiments 1-35.

[0261] Embodiment 62. A N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N- heterocyclic carbene.

[0262] Embodiment 63. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 62, wherein the at least one N-heterocyclic carbene has a structure of Formula (II):4886-5650-6109.1Page 81 of 224 094876-000020WOPTFormula (II), wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0263] Embodiment 64. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 62 or embodiment 63, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 82 of 224 094876-000020WOPTR4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0264] Embodiment 65. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-64, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B): Formula (II-B), wherein:nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;4886-5650-6109.1Page 83 of 224 094876-000020WOPTR1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0265] Embodiment 66. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-65, wherein the at least one N-heterocyclic carbene is .4886-5650-6109.1Page 84 of 224 094876-000020WOPT

[0266] Embodiment 67. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-64, wherein the at least one N-heterocyclic carbene is the same or different.

[0267] Embodiment 68. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-67, wherein the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen.

[0268] Embodiment 69. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 68, wherein Mais a Group 6 transition metal.

[0269] Embodiment 70. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 68 or embodiment 69, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).

[0270] Embodiment 71. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 68-70, wherein the Group 6 transition metal is molybdenum (Mo).

[0271] Embodiment 72. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-71, wherein the at least one transition metal dichalcogenide is MoS2.

[0272] Embodiment 73. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-72, wherein the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide.

[0273] Embodiment 74. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 73, wherein the at least one exfoliated transition metal dichalcogenide has the formula: MbXb2, wherein: Mbis a Group 4-10 transition metal; and Xbis a chalcogen.4886-5650-6109.1Page 85 of 224 094876-000020WOPT

[0274] Embodiment 75. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 74, wherein Mbis a Group 6 transition metal.

[0275] Embodiment 76. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 74 or embodiment 75, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).

[0276] Embodiment 77. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 74-76, wherein the Group 6 transition metal is molybdenum (Mo).

[0277] Embodiment 78. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 73-77, wherein the at least one exfoliated transition metal dichalcogenide is MoS2.

[0278] Embodiment 79. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 73-78, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface.

[0279] Embodiment 80. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-79, wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0280] Embodiment 81. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 80, wherein the self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0281] Embodiment 82. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 73-78, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.

[0282] Embodiment 83. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 82, wherein the at least one exfoliated basal plane is functionalized with the at least one N-heterocyclic carbene.

[0283] Embodiment 84. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 73-78, wherein the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure.4886-5650-6109.1Page 86 of 224 094876-000020WOPT

[0284] Embodiment 85. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 84, wherein the 2D structure comprises one layer, or a plurality of layers.

[0285] Embodiment 86. The N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-84, wherein the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers.

[0286] Embodiment 87. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 86, wherein the intercalated layers comprise the at least one N- heterocyclic carbene.

[0287] Embodiment 88. An article of manufacture comprising a N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-87.

[0288] Embodiment 89. The article of manufacture of embodiment 88, wherein the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

[0289] Embodiment 90. The article of manufacture of embodiment 88, wherein the article of manufacture is a semiconductor.

[0290] Embodiment 91. Use of the N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of embodiments 62-87.

[0291] Embodiments include those listed below.

[0292] In various embodiments of the present invention, N-heterocyclic carbene is represented as N-heterocyclic carbene. In various embodiments of the present invention, N- heterocyclic carbene precursor is represented as N-heterocyclic carbene precursor. In various embodiments of the present invention, N-heterocyclic carbene adsorbate is represented as N- heterocyclic carbene adsorbate. In various embodiments of the present invention, N-heterocyclic carbene functionalized transition metal dichalcogenide is represented as N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0293] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal4886-5650-6109.1Page 87 of 224 094876-000020WOPTdichalcogenide to produce at least one exfoliated transition metal dichalcogenide; and reacting the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0294] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide; and reacting at least a portion of the at least one exfoliated transition metal dichalcogenide with at least one N- heterocyclic carbene precursor.

[0295] In some embodiments, the N-heterocyclic carbene adsorbate is a N-heterocyclic carbene precursor.

[0296] In some embodiments, the N-heterocyclic carbene precursor has a structure of Formula (I). In some embodiments, the N-heterocyclic carbene precursor has a structure of Formula (I-A). In some embodiments, the N-heterocyclic carbene precursor has a structure of Formula (I-B). In some embodiments, the N-heterocyclic carbene precursor of Formula (I) is a N- heterocyclic carbene precursor of Formula (I-A). In some embodiments, the N-heterocyclic carbene precursor of Formula (I) is a N-heterocyclic carbene precursor of Formula (I-B). In some embodiments, the N-heterocyclic carbene precursor of Formula (I-A) is a N-heterocyclic carbene precursor of Formula (I-B).

[0297] In some embodiments, the N-heterocyclic carbene has a structure of Formula (II). In some embodiments, the N-heterocyclic carbene has a structure of Formula (II-A). In some embodiments, the N-heterocyclic carbene has a structure of Formula (II-B). In some embodiments, the N-heterocyclic carbene of Formula (II) is a N-heterocyclic carbene of Formula (II-A). In some embodiments, the N-heterocyclic carbene of Formula (II) is a N-heterocyclic carbene of Formula (II-B). In some embodiments, the N-heterocyclic carbene of Formula (II-A) is a N-heterocyclic carbene of Formula (II-B).

[0298] Additional embodiments include those listed below.

[0299] In various embodiments, the present invention aims to establish an effective method for functionalizing 2D TMDs. The work described herein focuses on using redox exfoliation to produce 2D nanolayered MoS2, thereby affording few- to monolayered nanosheets. Additionally, nanosheets with varied sizes and thicknesses were collected for characterization and evaluation.4886-5650-6109.1Page 88 of 224 094876-000020WOPTSubsequently, exposure of the exfoliated materials to selected organic ligands induced functionalization, leading to the formation of self-assembled monolayers (SAMs) of organic molecules on the basal plane of exfoliated MoS2nanosheets. Consequently, a new family of 2D materials was created with custom-designed interlayer expansions.

[0300] In various embodiments of the present invention, the work described herein demonstrates the successful exfoliation of 2D nanolayered MoS2, primarily achieving nanosheets with fewer than 5 layers. Crucially, the exfoliated materials retained their semiconducting properties without any indication of phase transformation. Subsequent exposure to organic adsorbates led to functionalization of the basal plane of the MoS2nanosheets, leading to the formation of new structures with entrapped molecules between the interlayer gaps of the 2D materials. These novel 2D structures exhibited interlayer expansion, which could be modulated for targeted applications.

[0301] Additional embodiments include those listed below.

[0302] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor. In various embodiments, the present invention provides a N-heterocyclic carbene functionalized transition metal dichalcogenide made by a method of the present invention. In various embodiments, the present invention provides an article of manufacture comprising a N- heterocyclic carbene functionalized transition metal dichalcogenide made by a method of the present invention.

[0303] In various embodiments, the present invention provides a N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N-heterocyclic carbene. In various embodiments, the present invention provides an article of manufacture comprising a N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0304] Additional embodiments include those listed below.4886-5650-6109.1Page 89 of 224 094876-000020WOPT

[0305] Embodiment 92. A N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N- heterocyclic carbene.

[0306] Embodiment 93. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

[0307] Embodiment 94. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 90 of 224 094876-000020WOPTR2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R3aand R4aare not both absent, and wherein R5aand R6aare not both absent; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0308] Embodiment 95. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 91 of 224 094876-000020WOPTFormula (II-B), wherein: nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0309] Embodiment 96. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV):4886-5650-6109.1Page 92 of 224 094876-000020WOPTFormula (IV) wherein: Z1ais C; Z2ais C; R10ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12aand R13aare not both absent, and wherein R14aand R15aare not both absent; and4886-5650-6109.1Page 93 of 224 094876-000020WOPTbetween Z1aand Z2aindicates a bond that may be a single bond or a double bond; or R12aand R14a, or R12aand R15a, or R13aand R14a, or R13aand R15amay be taken together to form a ring, wherein the ring is optionally substituted.

[0310] Embodiment 97. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one N-heterocyclic carbene is .

[0311] Embodiment 98. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen.

[0312] Embodiment 99. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 98, wherein Mais a Group 6 transition metal.

[0313] Embodiment 100. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 98, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).4886-5650-6109.1Page 94 of 224 094876-000020WOPT

[0314] Embodiment 101. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 99, wherein the Group 6 transition metal is molybdenum (Mo) or tungsten (W).

[0315] Embodiment 102. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one transition metal dichalcogenide is MoS2or WS2.

[0316] Embodiment 103. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one N- heterocyclic carbene forms a self-assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0317] Embodiment 104. The N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, wherein the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0318] Embodiment 105. A method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0319] Embodiment 106. The method of embodiment 105, wherein the at least one N- heterocyclic carbene precursor has a structure of Formula (I):4886-5650-6109.1Page 95 of 224 094876-000020WOPTFormula (I), wherein: A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1is an optionally substituted linker.

[0320] Embodiment 107. The method of embodiment 105, wherein the at least one N- heterocyclic carbene precursor has a structure of Formula (III): Formula (III) wherein:A1-is a counterion; Z1is C; Z2is C; R10is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 96 of 224 094876-000020WOPTR11is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12and R13are not both absent, and wherein R14and R15are not both absent; and between Z1and Z2indicates a bond that may be a single bond or a double bond; or R12and R14, or R12and R15, or R13and R14, or R13and R15may be taken together to form a ring, wherein the ring is optionally substituted.

[0321] Embodiment 108. The method of embodiment 105, wherein the N-heterocyclic carbene precursor has the structure of Formula (I-B):4886-5650-6109.1Page 97 of 224 094876-000020WOPTFormula (I-B), wherein: A- is a counterion; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7is H, OR8, SR9, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8is H, or optionally substituted alkyl, and R9is H, or optionally substituted alkyl.

[0322] Embodiment 109. An article of manufacture comprising at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of embodiment 92.4886-5650-6109.1Page 98 of 224 094876-000020WOPT

[0323] Embodiment 110. The article of manufacture of embodiment 109, wherein the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

[0324] Embodiment 111. The article of manufacture of embodiment 109, wherein the article of manufacture is a semiconductor or has semiconducting properties.

[0325] Additional embodiments include those listed below.

[0326] In various embodiments, the present invention provides a N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N-heterocyclic carbene.

[0327] In some embodiments, the at least one N-heterocyclic carbene is chemically bonded to the at least one transition metal dichalcogenide. In some embodiments, the at least one N- heterocyclic carbene is chemically bonded to an at least one transition metal of the at least one transition metal dichalcogenide. In some embodiments, the chemical bond is a covalent bond, ionic bond, or combination thereof. In some embodiments, the at least one N-heterocyclic carbene is chemically bonded to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is chemically bonded to the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is chemically bonded to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0328] In some embodiments, the at least one N-heterocyclic carbene is physiosorbed to the at least one transition metal dichalcogenide. In some embodiments, the at least one N- heterocyclic carbene is physiosorbed to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is physiosorbed to the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is physiosorbed to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0329] In some embodiments, the at least one N-heterocyclic carbene is chemisorbed to the at least one transition metal dichalcogenide. In some embodiments, the at least one N- heterocyclic carbene is chemisorbed to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is chemisorbed to the at least one4886-5650-6109.1Page 99 of 224 094876-000020WOPTexfoliated surface of the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one N-heterocyclic carbene is chemisorbed to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0330] In various embodiments, the present invention provides at least one transition metal dichalcogenide, wherein the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen.

[0331] In some embodiments, Mais a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.

[0332] In some embodiments, Mais a Group 6 transition metal.

[0333] In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).

[0334] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0335] In some embodiments, the at least one transition metal dichalcogenide is MoS2. In some embodiments, the at least one transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one transition metal dichalcogenide is WS2.

[0336] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide.

[0337] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one N- heterocyclic carbene forms a self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0338] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one N- heterocyclic carbene forms a self-assembled monolayer (SAM) or partial self-assembled4886-5650-6109.1Page 100 of 224 094876-000020WOPTmonolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0339] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0340] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) or partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0341] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0342] In some embodiments, the self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene. In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0343] In some embodiments, the at least one N-heterocyclic carbene is the same or different. In some embodiments, the at least one N-heterocyclic carbene precursor is the same or different.

[0344] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.4886-5650-6109.1Page 101 of 224 094876-000020WOPT

[0345] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide; and reacting the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0346] In various embodiments, the present invention provides a method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

[0347] In some embodiments, reacting the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor is performed under conditions sufficient to make the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0348] In some embodiments, reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N- heterocyclic carbene precursor is performed under conditions sufficient to make the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0349] In some embodiments, reacting the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor is performed under conditions effective to make the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide.

[0350] In some embodiments, reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N- heterocyclic carbene precursor is performed under conditions effective to make the at least one N- heterocyclic carbene functionalized transition metal dichalcogenide.

[0351] In some embodiments, the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.4886-5650-6109.1Page 102 of 224 094876-000020WOPT

[0352] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.

[0353] In some embodiments, the exfoliating is conducted by a redox exfoliation process.

[0354] In some embodiments, the at least one N-heterocyclic carbene precursor forms a self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0355] In some embodiments, the at least one N-heterocyclic carbene precursor forms a partial self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0356] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer.

[0357] In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0358] In some embodiments, the self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0359] In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0360] In some embodiments, the at least one bulk transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0361] In some embodiments, the at least one bulk transition metal dichalcogenide has the formula: McXc2, wherein: Mcis a Group 4-10 transition metal; and Xcis a chalcogen.

[0362] In some embodiments, Mcis a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.

[0363] In some embodiments, Mcis a Group 6 transition metal.

[0364] In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).4886-5650-6109.1Page 103 of 224 094876-000020WOPT

[0365] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0366] In some embodiments, the at least one bulk transition metal dichalcogenide is MoS2. In some embodiments, the at least one bulk transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one transition metal dichalcogenide is WS2.

[0367] In some embodiments, the at least one exfoliated transition metal dichalcogenide has the formula: MbXb2, wherein: Mbis a Group 4-10 transition metal; and Xbis a chalcogen.

[0368] In some embodiments, Mbis a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.

[0369] In some embodiments, Mbis a Group 6 transition metal.

[0370] In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).

[0371] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0372] In some embodiments, the at least one exfoliated transition metal dichalcogenide is MoS2. In some embodiments, the at least one exfoliated transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one exfoliated transition metal dichalcogenide is WS2.

[0373] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0374] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface.

[0375] In some embodiments, the reaction of the at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor to make the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide.4886-5650-6109.1Page 104 of 224 094876-000020WOPT

[0376] In some embodiments, the at least one N-heterocyclic carbene functionalized transition metal dichalcogenide comprises at least one N-heterocyclic carbene.

[0377] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide is insulating, semiconducting, conducting, semi-metallic, metallic, or any combination thereof.

[0378] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide is semiconducting.

[0379] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide is a semiconductor.

[0380] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a self-assembled monolayer (SAM). In some embodiments, the self- assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self- assembled monolayer. In some embodiments, the self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0381] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a partial self-assembled monolayer (SAM). In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0382] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers. In some embodiments, the intercalated layers comprise the at least one N-heterocyclic carbene.

[0383] In some embodiments, the N-heterocyclic carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers, wherein the intercalated layers comprise at least one N-heterocyclic carbene.

[0384] In some embodiments, the at least one N-heterocyclic carbene forms a self- assembled monolayer (SAM) or partial self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0385] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the4886-5650-6109.1Page 105 of 224 094876-000020WOPTpartial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0386] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane. In some embodiments, the at least one exfoliated basal plane is functionalized with the at least one N-heterocyclic carbene. In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0387] In various embodiments, the present invention provides an article of manufacture comprising at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of the present invention.

[0388] In some embodiments, the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device, semiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

[0389] In some embodiments, the article of manufacture is a semiconductor. In some embodiments, the article of manufacture is a semiconductor, or has semiconducting properties.

[0390] In various embodiments, the present invention provides for use of the N- heterocyclic carbene functionalized transition metal dichalcogenide of the present invention.

[0391] In various embodiments, the present invention provides for use of the N- heterocyclic carbene functionalized transition metal dichalcogenide made by the method of the present invention.

[0392] Additional embodiments include those listed below.

[0393] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor has a structure of Formula (I): Formula (I),4886-5650-6109.1Page 106 of 224 094876-000020WOPTwherein: A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1is an optionally substituted linker.

[0394] In some embodiments, the optionally substituted linker comprises at least one carbon-carbon double bond. In some embodiments, the optionally substituted linker is an optionally substituted alkylene, or optionally substituted alkenylene.

[0395] In some embodiments, R1is ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2is ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0396] In some embodiments, A- is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0397] In some embodiments, the N-heterocyclic carbene precursor of Formula (I) may be represented by the N-heterocyclic carbene precursor of Formula (I-1), wherein the N-heterocyclic carbene precursor of Formula (I-1) has the following structure:Formula (I-1), wherein A-, R1, R2, and Q1are as defined for the N-heterocyclic carbene precursor of Formula (I).

[0398] In some embodiments, the N-heterocyclic carbene precursor of Formula (I) may be represented by the N-heterocyclic carbene precursor of Formula (I-2), wherein the N-heterocyclic carbene precursor of Formula (I-2) has the following structure:4886-5650-6109.1Page 107 of 224 094876-000020WOPTFormula (I-2), wherein A-, R1, R2, and Q1are as defined for the N-heterocyclic carbene precursor of Formula (I).

[0399] Additional embodiments include those listed below.

[0400] In various embodiments, the present invention provides a N-heterocyclic carbene precursor, wherein the N-heterocyclic carbene precursor has a structure of Formula (I-A): Formula (I-A), wherein:A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 108 of 224 094876-000020WOPTR4is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3and R5, or R3and R6, or R4and R5, or R4and R6may be taken together to form a ring, wherein the ring is optionally substituted.

[0401] In some embodiments, R3and R4are not both absent, and R5and R6are not both absent. In some embodiments, R3and R4are not both absent. In some embodiments, R5and R6are not both absent.

[0402] In some embodiments, the ring comprises at least one carbon-carbon double bond. In some embodiments, the ring is an optionally substituted aromatic ring. In some embodiments, the ring is an optionally substituted benzene ring. In some embodiments, the ring is an aromatic ring. In some embodiments, the ring is a benzene ring.

[0403] In some embodiments, A- is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0404] In some embodiments, R1is ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2is ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0405] In some embodiments, R3is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0406] In some embodiments, R4is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.4886-5650-6109.1Page 109 of 224 094876-000020WOPT

[0407] In some embodiments, R5is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0408] In some embodiments, R6is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0409] In some embodiments, R3is absent, H, halo, OR50, SR51, or NR52R53, wherein R50is H, or optionally substituted alkyl; wherein R51is H, or optionally substituted alkyl; wherein R52is H, or optionally substituted alkyl; and wherein R53is H, or optionally substituted alkyl.

[0410] In some embodiments, R4is absent, H, halo, OR54, SR55, or NR56R57, wherein R54is H, or optionally substituted alkyl; wherein R55is H, or optionally substituted alkyl; wherein R56is H, or optionally substituted alkyl; and wherein R57is H, or optionally substituted alkyl.

[0411] In some embodiments, R5is absent, H, halo, OR58, SR59, or NR60R61, wherein R58is H, or optionally substituted alkyl; wherein R59is H, or optionally substituted alkyl; wherein R60is H, or optionally substituted alkyl; and wherein R61is H, or optionally substituted alkyl

[0412] In some embodiments, R6is absent, H, halo, OR62, SR63, or NR64R65, wherein R62is H, or optionally substituted alkyl; wherein R63is H, or optionally substituted alkyl; wherein R64is H, or optionally substituted alkyl; and wherein R65is H, or optionally substituted alkyl.

[0413] In some embodiments, if R4and R5are absent, then the bond between the carbon attached to R3and the carbon attached to R6is a carbon-carbon double bond.

[0414] In some embodiments, if R4and R6are absent, then the bond between the carbon attached to R3and the carbon attached to R5is a carbon-carbon double bond.

[0415] In some embodiments, if R3and R5are absent, then the bond between the carbon attached to R4and the carbon attached to R6is a carbon-carbon double bond.

[0416] In some embodiments, if R3and R6are absent, then the bond between the carbon attached to R4and the carbon attached to R5is a carbon-carbon double bond.

[0417] In some embodiments, the N-heterocyclic carbene precursor of Formula (I-A) may be represented by the N-heterocyclic carbene precursor of Formula (I-A-1), wherein the N- heterocyclic carbene precursor of Formula (I-A-1) has the following structure:4886-5650-6109.1Page 110 of 224 094876-000020WOPTFormula (I-A-1), wherein A-, R1, R2, R3, R4, R5, and R6are as defined for the N-heterocyclic carbene precursor of Formula (I-A).

[0418] In some embodiments, the N-heterocyclic carbene precursor of Formula (I-A) may be represented by the N-heterocyclic carbene precursor of Formula (I-A-2), wherein the N- heterocyclic carbene precursor of Formula (I-A-2) has the following structure:Formula (I-A-2), wherein A-, R1, R2, R3, R4, R5, and R6are as defined for the N-heterocyclic carbene precursor of Formula (I-A).

[0419] Additional embodiments include those listed below.

[0420] In some embodiments, the present invention provides a N-heterocyclic carbene precursor, wherein the N-heterocyclic carbene precursor has the structure of Formula (I-B):4886-5650-6109.1Page 111 of 224 094876-000020WOPTFormula (I-B), wherein: A- is a counterion; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7is H, OR8, SR9, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8is H, or optionally substituted alkyl, and R9is H, or optionally substituted alkyl.

[0421] In some embodiments, R1is ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2is ethyl, propyl, isopropyl, butyl, pentyl, or decyl.4886-5650-6109.1Page 112 of 224 094876-000020WOPT

[0422] In some embodiments, A- is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0423] In some embodiments, the N-heterocyclic carbene precursor of Formula (I-B) may be represented by the N-heterocyclic carbene precursor of Formula (I-B-1), wherein the N- heterocyclic carbene precursor of Formula (I-B-1) has the following structure:Formula (I-B-1), wherein A-, R1, R2, n, and R7are as defined for the N-heterocyclic carbene precursor of Formula (I-B).

[0424] In some embodiments, the N-heterocyclic carbene precursor of Formula (I-B) may be represented by the N-heterocyclic carbene precursor of Formula (I-B-2), wherein the N- heterocyclic carbene precursor of Formula (I-B-2) has the following structure:4886-5650-6109.1Page 113 of 224 094876-000020WOPTFormula (I-B-2), wherein A-, R1, R2, n, and R7are as defined for the N-heterocyclic carbene precursor of Formula (I-B).

[0425] Additional embodiments include those listed below.

[0426] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor is4886-5650-6109.1Page 114 of 224 094876-000020WOPT.

[0427] In variousat least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor is4886-5650-6109.1Page 115 of 224 094876-000020WOPT.

[0428] In variousat least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor is4886-5650-6109.1Page 116 of 224 094876-000020WOPT.

[0429] Additional em w.

[0430] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.4886-5650-6109.1Page 117 of 224 094876-000020WOPT

[0431] In some embodiments, the optionally substituted linker comprises at least one carbon-carbon double bond. In some embodiments, the optionally substituted linker is an optionally substituted alkylene, or optionally substituted alkenylene.

[0432] In some embodiments, R1ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0433] Additional embodiments include those listed below.

[0434] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),wherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;4886-5650-6109.1Page 118 of 224 094876-000020WOPTR5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

[0435] In some embodiments, wherein R3aand R4aare not both absent, and wherein R5aand R6aare not both absent. In some embodiments, wherein R3aand R4aare not both absent. In some embodiments, wherein R5aand R6aare not both absent.

[0436] In some embodiments, the ring comprises at least one carbon-carbon double bond. In some embodiments, the ring is an optionally substituted aromatic ring. In some embodiments, the ring is an optionally substituted benzene ring. In some embodiments, the ring is an aromatic ring. In some embodiments, the ring is a benzene ring.

[0437] In some embodiments, R1ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0438] In some embodiments, R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0439] In some embodiments, R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0440] In some embodiments, R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted4886-5650-6109.1Page 119 of 224 094876-000020WOPTcyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0441] In some embodiments, R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0442] In some embodiments, R3ais absent, H, halo, OR50a, SR51a, or NR52aR53a, wherein R50ais H, or optionally substituted alkyl; wherein R51ais H, or optionally substituted alkyl; wherein is H, or optionally substituted alkyl; and wherein R53ais H, or optionally substituted alkyl.

[0443] In some embodiments, R4ais absent, H, halo, OR54a, SR55a, or NR56aR57a, wherein R54ais H, or optionally substituted alkyl; wherein R55ais H, or optionally substituted alkyl; wherein R56ais H, or optionally substituted alkyl; and wherein R57ais H, or optionally substituted alkyl.

[0444] In some embodiments, R5ais absent, H, halo, OR58a, SR59a, or NR60aR61a, wherein R58ais H, or optionally substituted alkyl; wherein R59ais H, or optionally substituted alkyl; wherein R60ais H, or optionally substituted alkyl; and wherein R61ais H, or optionally substituted alkyl. In some embodiments, R6ais absent, H, halo, OR62a, SR63a, or NR64aR65a, wherein R62ais H, or optionally substituted alkyl; wherein R63ais H, or optionally substituted alkyl; wherein R64ais H, or optionally substituted alkyl; and wherein R65ais H, or optionally substituted alkyl.

[0446] In some embodiments, if R4aand R5aare absent, then the bond between the carbon attached to R3aand the carbon attached to R6ais a carbon-carbon double bond.

[0447] In some embodiments, if R4aand R6aare absent, then the bond between the carbon attached to R3aand the carbon attached to R5ais a carbon-carbon double bond.

[0448] In some embodiments, if R3aand R5aare absent, then the bond between the carbon attached to R4aand the carbon attached to R6ais a carbon-carbon double bond.

[0449] In some embodiments, if R3aand R6aare absent, then the bond between the carbon attached to R4aand the carbon attached to R5ais a carbon-carbon double bond.

[0450] Additional embodiments include those listed below.

[0451] In some embodiments, the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 120 of 224 094876-000020WOPTFormula (II-B), wherein: nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

[0452] In some embodiments, R1ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R2ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0453] Additional embodiments include those listed below.4886-5650-6109.1Page 121 of 224 094876-000020WOPT

[0454] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene is .

[0455] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor has a structure of Formula (III): Formula (III) wherein:A1-is a counterion; Z1is C;4886-5650-6109.1Page 122 of 224 094876-000020WOPTZ2is C; R10is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and between Z1and Z2indicates a bond that may be a single bond or a double bond; or R12and R14, or R12and R15, or R13and R14, or R13and R15may be taken together to form a ring, wherein the ring is optionally substituted.

[0456] In some embodiments, R12and R13are not both absent, and wherein R14and R15are not both absent. In some embodiments, R12and R13are not both absent. In some embodiments, R14and R15are not both absent.4886-5650-6109.1Page 123 of 224 094876-000020WOPT

[0457] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor has a structure of Formula (III): Formula (III) wherein:A1-is a counterion; Z1is C; Z2is C; R10is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally4886-5650-6109.1Page 124 of 224 094876-000020WOPTsubstituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15is absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12and R13are not both absent, and wherein R14and R15are not both absent; and between Z1and Z2indicates a bond that may be a single bond or a double bond; or R12and R14, or R12and R15, or R13and R14, or R13and R15may be taken together to form a ring, wherein the ring is optionally substituted.

[0458] In some embodiments, if R12is absent and R14is absent, then the bond between Z1and Z2is a double bond. In some embodiments, if R12is absent and R15is absent, then the bond between Z1and Z2is a double bond.

[0459] In some embodiments, if R13is absent and R14is absent, then the bond between Z1and Z2is a double bond. In some embodiments, if R13is absent and R15is absent, then the bond between Z1and Z2is a double bond.

[0460] In some embodiments, the ring comprises at least one carbon-carbon double bond. In some embodiments, the ring is an optionally substituted aromatic ring. In some embodiments, the ring is an optionally substituted benzene ring. In some embodiments, the ring is an aromatic ring. In some embodiments, the ring is a benzene ring.

[0461] In some embodiments, A1-is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0462] In some embodiments, R10is ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11is ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0463] In some embodiments, R12is absent, H, halo, OR16, SR17, or NR18R19, wherein R16is H, or optionally substituted alkyl; wherein R17is H, or optionally substituted alkyl; wherein R18is H, or optionally substituted alkyl; and wherein R19is H, or optionally substituted alkyl.

[0464] In some embodiments, R13is absent, H, halo, OR20, SR21, or NR22R23, wherein R20is H, or optionally substituted alkyl; wherein R21is H, or optionally substituted alkyl; wherein R22is H, or optionally substituted alkyl; and wherein R23is H, or optionally substituted alkyl.4886-5650-6109.1Page 125 of 224 094876-000020WOPT

[0465] In some embodiments, R14is absent, H, halo, OR24, SR25, or NR26R27, wherein R24is H, or optionally substituted alkyl; wherein R25is H, or optionally substituted alkyl; wherein R26is H, or optionally substituted alkyl; and wherein R27is H, or optionally substituted alkyl.

[0466] In some embodiments, R15is absent, H, halo, OR28, SR29, or NR30R31, wherein R28is H, or optionally substituted alkyl; wherein R29is H, or optionally substituted alkyl; wherein R30is H, or optionally substituted alkyl; and wherein R31is H, or optionally substituted alkyl.

[0467] In some embodiments, the N-heterocyclic carbene precursor of Formula (III) may be represented by the N-heterocyclic carbene precursor of Formula (III-1), wherein the N- heterocyclic carbene precursor of Formula (III-1) has the following structure: Formula (III-1), wherein A1-, R10, R11, R12, R13, R14, R15, Z1and Z2carbene precursor of Formula (III).

[0468] In some embodiments, the N-heterocyclic carbene precursor of Formula (III) may be represented by the N-heterocyclic carbene precursor of Formula (III-2), wherein the N- heterocyclic carbene precursor of Formula (III-2) has the following structure:Formula (III-2), wherein A1-, R10, R11, R12, R13, R14, R15, Z1and Z2are as defined for the N-heterocyclic carbene precursor of Formula (III).

[0469] Additional embodiments include those listed below.4886-5650-6109.1Page 126 of 224 094876-000020WOPT

[0470] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor has the structure of Formula (III-A):Formula (III-A), wherein: A1e-is a counterion; peis 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16; qeis 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16; D1eis CH2, O, S, or NR34e, where R34eis H, or optionally substituted alkyl; D2eis CH2, O, S, or NR35e, where R35eis H, or optionally substituted alkyl; R10eis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11eis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R32eis H, OR12e, SR13e, NR14eR15e, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R12eis H, or optionally substituted alkyl; and R13eis H, or optionally substituted alkyl; wherein R14eis H, or optionally substituted alkyl; and wherein R15eis H, or optionally substituted alkyl; and4886-5650-6109.1Page 127 of 224 094876-000020WOPTR33eis H, OR16e, SR17e, NR18eR19e, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R16eis H, or optionally substituted alkyl; R17eis H, or optionally substituted alkyl; R18eis H, or optionally substituted alkyl; and R19eis H, or optionally substituted alkyl.

[0471] In some embodiments, A1e-is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0472] In some embodiments, R10eis ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11eis ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0473] In some embodiments, the N-heterocyclic carbene precursor of Formula (III-A) may be represented by the N-heterocyclic carbene precursor of Formula (III-A-1), wherein the N- heterocyclic carbene precursor of Formula (III-A-1) has the following structure:Formula (III-A-1), where A1e-, R10e, R11e, R32e, R33e, D1e, D2e, peand qeare as defined for the N-heterocyclic carbene precursor of Formula (III-A).

[0474] In some embodiments, the N-heterocyclic carbene precursor of Formula (III-A) may be represented by the N-heterocyclic carbene precursor of Formula (III-A-2), wherein the N- heterocyclic carbene precursor of Formula (III-A-2) has the following structure:4886-5650-6109.1Page 128 of 224 094876-000020WOPTFormula (III-A-2), where A1e-, R10e, R11e, R32e, R33e, D1e, D2e, peand qeare as defined for the N-heterocyclic carbene precursor of Formula (III-A).

[0475] Additional embodiments include those listed below.

[0476] In various embodiments, the present invention provides at least one N-heterocyclic carbene precursor, wherein the at least one N-heterocyclic carbene precursor has a structure of Formula (III-B):Formula (III-B), wherein: A1f-is a counterion; R10fis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and4886-5650-6109.1Page 129 of 224 094876-000020WOPTR11fis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0477] In some embodiments, A1f-is Cl-, Br-, I-, -OMs, -OTf, -BF4, or -PF6. In some embodiments, -OMs is represented by CH3SO3-. In some embodiments, -OTf is represented by CF3SO3-.

[0478] In some embodiments, the N-heterocyclic carbene precursor of Formula (III-B) may be represented by the N-heterocyclic carbene precursor of Formula (III-B-1), wherein the N- heterocyclic carbene precursor of Formula (III-B-1) has the following structure:Formula (III-B-1), where A1f-, R10f, and R11fare as defined for the N-heterocyclic carbene precursor of Formula (III- B).

[0479] In some embodiments, the N-heterocyclic carbene precursor of Formula (III-B) may be represented by the N-heterocyclic carbene precursor of Formula (III-B-2), wherein the N- heterocyclic carbene precursor of Formula (III-B-2) has the following structure:4886-5650-6109.1Page 130 of 224 094876-000020WOPTFormula (III-B-2), where A1f-, R10f, and R11fare as defined for the N-heterocyclic carbene precursor of Formula (III- B).

[0480] Additional embodiments include those listed below.

[0481] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV): Formula (IV)wherein: Z1ais C; Z2ais C; R10ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally4886-5650-6109.1Page 131 of 224 094876-000020WOPTsubstituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and between Z1aand Z2aindicates a bond that may be a single bond or a double bond; or R12aand R14a, or R12aand R15a, or R13aand R14a, or R13aand R15amay be taken together to form a ring, wherein the ring is optionally substituted.

[0482] In some embodiments, wherein R12aand R13aare not both absent, and wherein R14aand R15aare not both absent. In some embodiments, wherein R12aand R13aare not both absent. In some embodiments, wherein R14aand R15aare not both absent.

[0483] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV):Formula (IV) wherein: Z1ais C; Z2ais C; R10ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally4886-5650-6109.1Page 132 of 224 094876-000020WOPTsubstituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12aand R13aare not both absent, and wherein R14aand R15aare not both absent; and between Z1aand Z2aindicates a bond that may be a single bond or a double bond; or R12aand R14a, or R12aand R15a, or R13aand R14a, or R13aand R15amay be taken together to form a ring, wherein the ring is optionally substituted.

[0484] In some embodiments, if R12ais absent and R14ais absent, then the bond between Z1aand Z2ais a double bond. In some embodiments, if R12ais absent and R15ais absent, then the bond between Z1aand Z2ais a double bond.

[0485] In some embodiments, if R13ais absent and R14ais absent, then the bond between Z1aand Z2ais a double bond. In some embodiments, if R13ais absent and R15ais absent, then the bond between Z1aand Z2ais a double bond.

[0486] In some embodiments, the ring comprises at least one carbon-carbon double bond. In some embodiments, the ring is an optionally substituted aromatic ring. In some embodiments, the ring is an optionally substituted benzene ring. In some embodiments, the ring is an aromatic ring. In some embodiments, the ring is a benzene ring.

[0487] In some embodiments, R10ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11ais ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0488] Additional embodiments include those listed below.4886-5650-6109.1Page 133 of 224 094876-000020WOPT

[0489] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV-A): Formula (IV-A)wherein: Z1bis C; Z2bis C; R10bis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11bis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12bis absent, H, halo, OR16b, SR17b, or NR18bR19b, wherein R16bis H, or optionally substituted alkyl; wherein R17bis H, or optionally substituted alkyl; wherein R18bis H, or optionally substituted alkyl; and wherein R19bis H, or optionally substituted alkyl; R13bis absent, H, halo, OR20b, SR21b, or NR22bR23b, wherein R20bis H, or optionally substituted alkyl; wherein R21bis H, or optionally substituted alkyl; wherein R22bis H, or optionally substituted alkyl; and wherein R23bis H, or optionally substituted alkyl; R14bis absent, H, halo, OR24b, SR25b, or NR26bR27b, wherein R24bis H, or optionally substituted alkyl; wherein R25bis H, or optionally substituted alkyl; wherein R26bis H, or optionally substituted alkyl; and wherein R27bis H, or optionally substituted alkyl. R15bis absent, H, halo, OR28b, SR29b, or NR30bR31b, wherein R28bis H, or optionally substituted alkyl; wherein R29bis H, or optionally substituted alkyl; wherein R30bis H, or optionally substituted alkyl; and wherein R31bis H, or optionally substituted alkyl; and4886-5650-6109.1Page 134 of 224 094876-000020WOPTbetween Z1band Z2bindicates a bond that may be a single bond or a double bond; or R12band R14b, or R12band R15b, or R13band R14b, or R13band R15bmay be taken together to form a ring, wherein the ring is optionally substituted.

[0490] In some embodiments, wherein R12band R13bare not both absent, and wherein R14band R15bare not both absent. In some embodiments, wherein R12band R13bare not both absent. In some embodiments, wherein R14band R15bare not both absent.

[0491] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV-A):Formula (IV-A) wherein: Z1bis C; Z2bis C; R10bis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11bis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12bis absent, H, halo, OR16b, SR17b, or NR18bR19b, wherein R16bis H, or optionally substituted alkyl; wherein R17bis H, or optionally substituted alkyl; wherein R18bis H, or optionally substituted alkyl; and wherein R19bis H, or optionally substituted alkyl; R13bis absent, H, halo, OR20b, SR21b, or NR22bR23b, wherein R20bis H, or optionally substituted alkyl; wherein R21bis H, or optionally substituted alkyl; wherein R22bis H, or optionally substituted alkyl; and wherein R23bis H, or optionally substituted alkyl;4886-5650-6109.1Page 135 of 224 094876-000020WOPTR14bis absent, H, halo, OR24b, SR25b, or NR26bR27b, wherein R24bis H, or optionally substituted alkyl; wherein R25bis H, or optionally substituted alkyl; wherein R26bis H, or optionally substituted alkyl; and wherein R27bis H, or optionally substituted alkyl. R15bis absent, H, halo, OR28b, SR29b, or NR30bR31b, wherein R28bis H, or optionally substituted alkyl; wherein R29bis H, or optionally substituted alkyl; wherein R30bis H, or optionally substituted alkyl; and wherein R31bis H, or optionally substituted alkyl; and wherein R12band R13bare not both absent, and wherein R14band R15bare not both absent; and between Z1band Z2bindicates a bond that may be a single bond or a double bond; or R12band R14b, or R12band R15b, or R13band R14b, or R13band R15bmay be taken together to form a ring, wherein the ring is optionally substituted.

[0492] In some embodiments, if R12bis absent and R14bis absent, then the bond between Z1band Z2bis a double bond. In some embodiments, if R12bis absent and R15bis absent, then the bond between Z1band Z2bis a double bond.

[0493] In some embodiments, if R13bis absent and R14bis absent, then the bond between Z1band Z2bis a double bond. In some embodiments, if R13bis absent and R15bis absent, then the bond between Z1band Z2bis a double bond.

[0494] In some embodiments, the ring comprises at least one carbon-carbon double bond. In some embodiments, the ring is an optionally substituted aromatic ring. In some embodiments, the ring is an optionally substituted benzene ring. In some embodiments, the ring is an aromatic ring. In some embodiments, the ring is a benzene ring.

[0495] In some embodiments, R10bis ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11bis ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0496] Additional embodiments include those listed below.

[0497] In various embodiments, the present invention provides a N-heterocyclic carbene, wherein the N-heterocyclic carbene has the structure of Formula (IV-B):4886-5650-6109.1Page 136 of 224 094876-000020WOPTFormula (IV-B), wherein: pcis 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16; qcis 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16; D1cis CH2, O, S, or NR34c, where R34cis H, or optionally substituted alkyl; D2cis CH2, O, S, or NR35c, where R35cis H, or optionally substituted alkyl; R10cis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11cis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R32cis H, OR12c, SR13c, NR14cR15c, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R12cis H, or optionally substituted alkyl; and R13cis H, or optionally substituted alkyl; wherein R14cis H, or optionally substituted alkyl; and wherein R15cis H, or optionally substituted alkyl; and R33cis H, OR16c, SR17c, NR18cR19c, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R16cis H, or optionally substituted alkyl; R17cis H, or optionally substituted alkyl; R18cis H, or optionally substituted alkyl; and R19cis H, or optionally substituted alkyl.4886-5650-6109.1Page 137 of 224 094876-000020WOPT

[0498] In some embodiments, R10cis ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11cis ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0499] Additional embodiments include those listed below.

[0500] In various embodiments, the present invention provides at least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene is .

[0501] In variousat least one N-heterocyclic carbene, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV-C):Formula (IV-C), wherein:4886-5650-6109.1Page 138 of 224 094876-000020WOPTR10dis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R11dis H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0502] In some embodiments, R10dis ethyl, propyl, isopropyl, butyl, pentyl, or decyl. In some embodiments, R11dis ethyl, propyl, isopropyl, butyl, pentyl, or decyl.

[0503] Additional embodiments include those listed below.

[0504] In various embodiments, the present invention provides a carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one carbene.

[0505] In some embodiments, the at least one carbene is chemically bonded to the at least one transition metal dichalcogenide. In some embodiments, the at least one carbene is chemically bonded to an at least one transition metal of the at least one transition metal dichalcogenide. In some embodiments, the chemical bond is a covalent bond, ionic bond, or combination thereof. In some embodiments, the at least one carbene is chemically bonded to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one carbene is chemically bonded to the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one carbene is chemically bonded to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0506] In some embodiments, the at least one carbene is physiosorbed to the at least one transition metal dichalcogenide. In some embodiments, the at least one carbene is physiosorbed to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one carbene is physiosorbed to the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one carbene is physiosorbed to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0507] In some embodiments, the at least one carbene is chemisorbed to the at least one transition metal dichalcogenide. In some embodiments, the at least one carbene is chemisorbed to the at least one exfoliated transition metal dichalcogenide. In some embodiments, the at least one carbene is chemisorbed to the at least one exfoliated surface of the at least one exfoliated transition4886-5650-6109.1Page 139 of 224 094876-000020WOPTmetal dichalcogenide. In some embodiments, the at least one carbene is chemisorbed to the at least one exfoliated basal plane of the at least one exfoliated transition metal dichalcogenide.

[0508] In various embodiments, the present invention provides at least one transition metal dichalcogenide, wherein the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and Xais a chalcogen.

[0509] In some embodiments, Mais a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.

[0510] In some embodiments, Mais a Group 6 transition metal.

[0511] In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).

[0512] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0513] In some embodiments, the at least one transition metal dichalcogenide is MoS2. In some embodiments, the at least one transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one transition metal dichalcogenide is WS2.

[0514] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide.

[0515] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one carbene forms a self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0516] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one carbene forms a self-assembled monolayer (SAM) or partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.4886-5650-6109.1Page 140 of 224 094876-000020WOPT

[0517] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one carbene forms a self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0518] In some embodiments, the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one carbene forms a self-assembled monolayer (SAM) or partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.

[0519] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0520] In some embodiments, the self-assembled monolayer (SAM) comprises at least one carbene. In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one carbene.

[0521] In some embodiments, the at least one carbene is the same or different. In some embodiments, the at least one carbene precursor is the same or different.

[0522] In various embodiments, the present invention provides a method of making at least one carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor.

[0523] In various embodiments, the present invention provides a method of making at least one carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide; and reacting the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor.4886-5650-6109.1Page 141 of 224 094876-000020WOPT

[0524] In various embodiments, the present invention provides a method of making at least one carbene functionalized transition metal dichalcogenide, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor.

[0525] In some embodiments, reacting the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor is performed under conditions sufficient to make the at least one carbene functionalized transition metal dichalcogenide.

[0526] In some embodiments, reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor is performed under conditions sufficient to make the at least one carbene functionalized transition metal dichalcogenide.

[0527] In some embodiments, reacting the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor is performed under conditions effective to make the at least one carbene functionalized transition metal dichalcogenide.

[0528] In some embodiments, reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor is performed under conditions effective to make the at least one carbene functionalized transition metal dichalcogenide.

[0529] In some embodiments, the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.

[0530] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane.

[0531] In some embodiments, the exfoliating is conducted by a redox exfoliation process.

[0532] In some embodiments, the at least one carbene precursor forms a self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0533] In some embodiments, the at least one N-heterocyclic carbene precursor forms a partial self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.4886-5650-6109.1Page 142 of 224 094876-000020WOPT

[0534] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer.

[0535] In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0536] In some embodiments, the self-assembled monolayer (SAM) comprises at least one carbene.

[0537] In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one N-heterocyclic carbene.

[0538] In some embodiments, the at least one bulk transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0539] In some embodiments, the at least one bulk transition metal dichalcogenide has the formula: McXc2, wherein: Mcis a Group 4-10 transition metal; and Xcis a chalcogen.

[0540] In some embodiments, Mcis a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.

[0541] In some embodiments, Mcis a Group 6 transition metal.

[0542] In some embodiments,chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).

[0543] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0544] In some embodiments, the at least one bulk transition metal dichalcogenide is MoS2. In some embodiments, the at least one bulk transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one transition metal dichalcogenide is WS2.

[0545] In some embodiments, the at least one exfoliated transition metal dichalcogenide has the formula: MbXb2, wherein: Mbis a Group 4-10 transition metal; and Xbis a chalcogen.

[0546] In some embodiments, Mbis a Group 4 transition metal, or Group 5 transition metal, or Group 6 transition metal, or Group 7 transition metal, or Group 8 transition metal, or Group 9 transition metal, or Group 10 transition metal.4886-5650-6109.1Page 143 of 224 094876-000020WOPT

[0547] In some embodiments, Mbis a Group 6 transition metal.

[0548] In some embodiments, the chalcogen is sulfur (S), selenium (Se), or tellurium (Te). In some embodiments the chalcogen is sulfur (S). In some embodiments, the chalcogen is selenium (Se). In some embodiments, the chalcogen is tellurium (Te).

[0549] In some embodiments, the Group 6 transition metal is molybdenum (Mo). In some embodiments, the Group 6 transition metal is molybdenum (Mo) or tungsten (W). In some embodiments, the Group 6 transition metal is tungsten (W).

[0550] In some embodiments, the at least one exfoliated transition metal dichalcogenide is MoS2. In some embodiments, the at least one exfoliated transition metal dichalcogenide is MoS2or WS2. In some embodiments, the at least one exfoliated transition metal dichalcogenide is WS2.

[0551] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0552] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface.

[0553] In some embodiments, the reaction of the at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one carbene precursor to make the at least one carbene functionalized transition metal dichalcogenide.

[0554] In some embodiments, the at least one carbene functionalized transition metal dichalcogenide comprises at least one carbene.

[0555] In some embodiments, the carbene functionalized transition metal dichalcogenide is insulating, semiconducting, conducting, semi-metallic, metallic, or any combination thereof.

[0556] In some embodiments, the carbene functionalized transition metal dichalcogenide is semiconducting.

[0557] In some embodiments, the carbene functionalized transition metal dichalcogenide is a semiconductor.

[0558] In some embodiments, the carbene functionalized transition metal dichalcogenide comprises a self-assembled monolayer (SAM). In some embodiments, the self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the self-assembled monolayer (SAM) comprises at least one carbene.4886-5650-6109.1Page 144 of 224 094876-000020WOPT

[0559] In some embodiments, the carbene functionalized transition metal dichalcogenide comprises a partial self-assembled monolayer (SAM). In some embodiments, the partial self- assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self- assembled monolayer. In some embodiments, the partial self-assembled monolayer (SAM) comprises at least one carbene.

[0560] In some embodiments, the carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers. In some embodiments, the intercalated layers comprise the at least one carbene.

[0561] In some embodiments, the carbene functionalized transition metal dichalcogenide comprises a superstructure comprising intercalated layers, wherein the intercalated layers comprise at least one carbene.

[0562] In some embodiments, the at least one carbene forms a self-assembled monolayer (SAM) or partial self-assembled monolayer (SAM) on the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

[0563] In some embodiments, the self-assembled monolayer (SAM) is a homogenous self- assembled monolayer, or heterogenous self-assembled monolayer. In some embodiments, the partial self-assembled monolayer (SAM) is a homogenous self-assembled monolayer, or heterogenous self-assembled monolayer.

[0564] In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated basal plane. In some embodiments, the at least one exfoliated basal plane is functionalized with the at least one carbene. In some embodiments, the at least one exfoliated transition metal dichalcogenide comprises a two-dimensional (2D) structure. In some embodiments, the 2D structure comprises one layer, or a plurality of layers.

[0565] In various embodiments, the present invention provides an article of manufacture comprising at least one carbene functionalized transition metal dichalcogenide of the present invention.

[0566] In some embodiments, the article of manufacture is an energy storage device, energy storage material, sensing device, sensing mater...

Claims

CLAIMS What is claimed is:

1. A N-heterocyclic carbene functionalized transition metal dichalcogenide, comprising: at least one transition metal dichalcogenide; and at least one N-heterocyclic carbene.

2. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one N-heterocyclic carbene has a structure of Formula (II): Formula (II), wherein:R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1ais an optionally substituted linker.

3. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one N-heterocyclic carbene has a structure of Formula (II-A): Formula (II-A),4886-5650-6109.1Page 216 of 224 094876-000020WOPTwherein: R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R3ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R4ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R5ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R6ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; wherein R3aand R4aare not both absent, and wherein R5aand R6aare not both absent; or R3aand R5a, or R3aand R6a, or R4aand R5a, or R4aand R6amay be taken together to form a ring, wherein the ring is optionally substituted.

4. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one N-heterocyclic carbene has the structure of Formula (II-B):4886-5650-6109.1Page 217 of 224 094876-000020WOPTFormula (II-B), wherein: nais 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R1ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and R7ais H, OR8a, SR9a, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl, wherein R8ais H, or optionally substituted alkyl, and R9ais H, or optionally substituted alkyl.

5. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one N-heterocyclic carbene has a structure of Formula (IV):4886-5650-6109.1Page 218 of 224 094876-000020WOPTFormula (IV) wherein: Z1ais C; Z2ais C; R10ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R11ais H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R12ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R13ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R14ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally substituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R15ais absent, H, halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylamino, optionally4886-5650-6109.1Page 219 of 224 094876-000020WOPTsubstituted amino, hydroxy, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and wherein R12aand R13aare not both absent, and wherein R14aand R15aare not both absent; and between Z1aand Z2aindicates a bond that may be a single bond or a double bond; or R12aand R14a, or R12aand R15a, or R13aand R14a, or R13aand R15amay be taken together to form a ring, wherein the ring is optionally substituted.

6. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one N-heterocyclic carbene is .

7. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one transition metal dichalcogenide has the formula: MaXa2, wherein: Mais a Group 4-10 transition metal; and4886-5650-6109.1Page 220 of 224 094876-000020WOPTXais a chalcogen.

8. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 7, wherein Mais a Group 6 transition metal.

9. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 7, wherein the chalcogen is sulfur (S), selenium (Se), or tellurium (Te).

10. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 8, wherein the Group 6 transition metal is molybdenum (Mo) or tungsten (W).

11. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one transition metal dichalcogenide is MoS2or WS2.

12. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, and wherein the at least one N-heterocyclic carbene forms a self- assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide.

13. The N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, wherein the at least one transition metal dichalcogenide is an at least one exfoliated transition metal dichalcogenide, wherein the at least one exfoliated transition metal dichalcogenide comprises at least one exfoliated surface, wherein the at least one exfoliated surface comprises at least one exfoliated basal plane, and wherein the at least one N-heterocyclic carbene forms a self-assembled monolayer (SAM) or a partial self-assembled monolayer (SAM) on at least a portion of the at least one exfoliated basal plane.4886-5650-6109.1Page 221 of 224 094876-000020WOPT14. A method of making at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of claim 1, comprising: providing at least one bulk transition metal dichalcogenide; exfoliating the at least one bulk transition metal dichalcogenide to produce at least one exfoliated transition metal dichalcogenide comprising at least one exfoliated surface; and reacting at least a portion of the at least one exfoliated surface of the at least one exfoliated transition metal dichalcogenide with at least one N-heterocyclic carbene precursor.

15. The method of claim 14, wherein the at least one N-heterocyclic carbene precursor has a structure of Formula (I): Formula (I), wherein:A- is a counterion; R1is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; R2is H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl; and Q1is an optionally substituted linker.

16. An article of manufacture comprising at least one N-heterocyclic carbene functionalized transition metal dichalcogenide of any one of claims 1-13.

17. The article of manufacture of claim 16, wherein the article of manufacture is an energy storage device, energy storage material, sensing device, sensing material, semiconductor electronic device,4886-5650-6109.1Page 222 of 224 094876-000020WOPTsemiconductor electronic material, semiconductor optoelectronic device, or semiconductor optoelectronic material.

18. The article of manufacture of claim 16, wherein the article of manufacture is a semiconductor or has semiconducting properties.4886-5650-6109.1Page 223 of 224 094876-000020WOPT

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