Phosphorescent platinum emitters for OLED applications

Abstract

Platinum (II) complexes and methods of making and using the same are described herein. The design of the platinum (II) complex results in emission with high quantum yield and fast radiation decay rate in the blue spectral region at room temperature. The platinum (II) complexes can be used for manufacturing efficient blue light emitting OLEDs.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 625,646, filed on January 26, 2024, the disclosure of which is incorporated herein by reference. Technical field

[0003] The disclosed invention generally belongs to the following field: platinum(II) complexes and their use as phosphorescent blue dopants in organic electronic devices such as organic light - emitting diodes (OLEDs). Background art

[0004] In the past decade, multiple examples of phosphorescent blue platinum(II) complexes supported by N - heterocyclic carbene (NHC) ligands have been reported. For example, Strassner et al. (Dalton Trans. 2013, 42, 9847; Chem. Eur. J. 2019, 25, 14495) reported a series of blue - emitting bidentate Pt(C^C)acac complexes. Che et al. (J. Mater. Chem. C 2022, 10, 10271) reported a series of dark - blue NHC - pincer Pt(II) complexes. However, these examples of bidentate or tridentate platinum complexes suffer from unwanted structural distortions in the excited state and weak electrochemical stability, which in turn have hindered their development and limited their applications.

[0005] Platinum(II) complexes with tetradentate ligands are more stable and robust due to stronger chelation effects and ligand rigidity. Different types of NHC - supported tetradentate platinum(II) complexes have been reported, one of which is based on the C^C^C^N ligand system (where C* represents NHC coordination and C refers to phenyl carbanion coordination). Kim et al. (Nat. Photonics 2022, 16, 212) reported benzimidazole - based NHC - supported platinum(II) complexes that emit light in the dark - blue region. Applying two NHC moieties can help achieve even higher - lying metal - center triplet excited states ( 3 MC). Considering the stability issues related to the trans - effect, two phenolate moieties can be installed as weak - field ligands in the trans - position of the NHC, resulting in the unique ligand system O^C*^C*^O. Che et al. (Chem. Commun. 2011, 47, 9075; US8957217B2) reported that the Pt(II) - O^C*^C*^O complex has blue light emission at 443 nm, where the phenolate acts as a typical electron donor to form a donor - acceptor structure with the imidazole - based NHC and from a high - energy 3 MLCT perturbation3 ILCT generates blue light emission. Che et al. also reported vacuum-deposited devices that exhibited blue electrophosphorescence. Subsequently, Che et al. (Chem. Sci. 2013, 4, 2630) fabricated deep blue OLEDs using a Pt(II)-O^C*^C*^O complex as a phosphorescent blue dopant.

[0006] Despite the good coordination geometry of these fused 6,6,6-metal ring compounds, the Pt-O^C*^C*^O complex still faces the following problems: (i) high turn-on voltage, and (ii) large EQE roll-off. Thus, devices fabricated with the Pt-O^C*^C*^O complex suffer from the following problems: (i) high triplet energy, which mainly comes from a higher LUMO, and (ii) slow radiative decay rate (k r small), and thus a longer emission lifetime (τ).

[0007] There is still a need to develop blue emitters with improved properties such as high emission quantum yield and fast radiative decay rate, etc.

[0008] Therefore, an object of the present invention is to provide new platinum(II) complexes that emit in the blue region with improved properties.

[0009] A further object of the present invention is to provide devices containing the new platinum(II) complexes.

[0010] A further object of the present invention is to provide methods of using the new platinum(II) complexes. Summary of the Invention

[0011] Platinum(II) complexes that can emit in the blue region and their preparation and use methods are described. The platinum(II) complexes comprise a platinum(II) atom coordinated by a ligand containing a benzimidazole-based NHC and a phenolate moiety. In some forms, the phenolate moiety of the ligand contains one or more large substituents, such as large phenyl groups, etc., for example 3,5-di-tert-butyl-phenyl (ditBuPh) and / or 2,6-dimethyl-phenyl (diMePh). Compared with previously reported imidazole-based Pt(II)-O^C*^C*^O complexes, the structures of the disclosed Pt(II) complexes allow for a significant increase in the emission quantum yield and the radiative decay rate constant. For example, the Pt(II) complexes have a high emission quantum yield (i.e., Ф em ≥ 30%, such as 30% to 90%, 30% to 85%, or 30% to 80%, etc., measured in the film above), a short emission lifetime (i.e., τ em or τ ≤ 5.5 μs or ≤ 5 μs and at least about 2 μs, such as about 2.25 μs, etc.), and / or a fast radiative decay rate (i.e., k r≥ 1.0×10 5 s -1 and at most about 6.0×10 5 s -1 , such as about 3.4×10 5 s -1 etc.) emit in the blue region (λ max between 420 nm and 490 nm, such as 441 - 454 nm), as measured in the film at room temperature. Without being bound by any theory, the improved emission properties of the Pt(II) complexes can be attributed to the geometric structures of these metal complexes (e.g., reduced planarity and altered orientation between the NHC and the phenolate ring) and the π-conjugation of the extended acceptor units.

[0012] In some forms, the platinum(II) complexes can have the following structure:

[0013]

[0014] wherein: (i) each occurrence of R1 - R8 can independently be hydrogen, deuterium, halide (e.g., fluoride, chloride, bromide, iodide, etc.), hydroxyl, amino, amide, thiol, cyano, nitro, alkoxy, carbonyl, substituted or unsubstituted C1 - C 12 alkyl, substituted or unsubstituted C1 - C 12 alkenyl, substituted or unsubstituted C1 - C 12 alkynyl, substituted or unsubstituted aryl (e.g., phenyl), substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero - polyaryl, or two adjacent groups among R1 - R8 and the carbon atom to which they are attached can together form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero - polyaryl; and (ii) the substituents, when present, can independently be unsubstituted C1 - C 12 alkyl, unsubstituted C1 - C 12 alkenyl, unsubstituted C1 - C 12 alkynyl, unsubstituted aryl (e.g., phenyl), aryl (e.g., phenyl) substituted by one or more unsubstituted aryl (e.g., unsubstituted phenyl) and / or one or more unsubstituted alkyl (e.g., unsubstituted C1 - C 12 alkyl), unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero - polyaryl, hetero - polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, amino, or halide.

[0015] In some forms, the platinum(II) complex may have the following structure:

[0016] ,

[0017] wherein R1 to R4 may be defined as in Formula I above.

[0018] In some forms, the platinum(II) complex may have the following structure:

[0019] ,

[0020] wherein R1 to R4 may be defined as in Formula I above.

[0021] In some forms, the platinum(II) complex may have the following structure:

[0022] ,

[0023] wherein: (i) each occurrence of X1 to X4 may independently be nitrogen or CR 16 ; (ii) R2 to R5 and R 16 may be defined as for R1 to R8 of Formula I above; (iii) n1 is an integer from 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2; (iv) R 14 and R 15 may independently be hydrogen, deuterium, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C 12 alkenyl, or substituted or unsubstituted C1-C 12 alkynyl, or R 14 and R 15 on two adjacent carbon atoms may together form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl; and (v) substituents when present may be defined as for Formula I above.

[0024] In some forms, X1 and X4 may independently be nitrogen or CR 16 ; X2 and X3 may be CR 16 ; R 16 may be hydrogen, a halide, unsubstituted C1-C 12 alkyl, unsubstituted aryl, or aryl substituted with one or more unsubstituted C1-C 12 alkyl; R2 to R5 may independently be hydrogen, deuterium, amino, unsubstituted C1-C 12An alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group, or R2 and R3, R3 and R4, or R4 and R5 together with the carbon atoms to which they are attached may jointly form a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group; and the substituents, when present, may independently be unsubstituted C1-C 12 An alkyl group, an unsubstituted aryl group (e.g., phenyl), an aryl group (e.g., phenyl) substituted by one or more unsubstituted aryl groups (e.g., phenyl) and / or one or more unsubstituted alkyl groups, an unsubstituted heteroaryl group, a heteroaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, an unsubstituted polyaryl group, a polyaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, an unsubstituted hetero-polyaryl group, a hetero-polyaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, or an amino group. In some forms, X1-X3 may be CR 16 and X4 may independently be nitrogen or CR 16 , R 16 may be hydrogen, deuterium, a halide, an unsubstituted C1-C 12 alkyl group (e.g., an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , where R9-R 13 may independently be hydrogen, deuterium, or an unsubstituted C1-C 12 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.).

[0025] In some forms, each occurrence of R1-R8 may independently be hydrogen, deuterium, a halide, a substituted or unsubstituted C1-C 12 alkyl group, a substituted or unsubstituted C1-C 12 alkenyl group, a substituted or unsubstituted C1-C 12 alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group.

[0026] In some forms, each occurrence of R1-R8 may independently be hydrogen, deuterium, a halide, a substituted or unsubstituted C1-C 12 alkyl group, or a substituted or unsubstituted aryl group.

[0027] In some forms, each occurrence of R1-R8 may independently be hydrogen, deuterium, a halide (e.g., fluoride, chloride, or bromide), an unsubstituted C1-C 12An alkyl group (e.g., an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9 to R 13 can independently be hydrogen, deuterium, an unsubstituted C1-C 12 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), an unsubstituted phenyl group, an unsubstituted heteroaryl group, or an amino group. In some forms, R9 to R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.). In some forms, R9 and R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R 10 to R 12 can be hydrogen, deuterium. In some forms, R 10 and R 12 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R9, R 11 and R 13 can be hydrogen or deuterium.

[0028] In some forms, when the platinum(II) complex has the structure of Formula II or II', R1 to R4 can independently be hydrogen, deuterium, a halide, an unsubstituted C1-C 12 alkyl group (e.g., an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9 to R 13 can independently be hydrogen, deuterium, an unsubstituted C1-C 12 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), an unsubstituted phenyl group, an unsubstituted heteroaryl group, or an amino group. In some forms, R9 to R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.). In some forms, R9 and R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R 10 to R 12 can be hydrogen or deuterium. In some forms, R 10and R 12 may independently be hydrogen, deuterium or an unsubstituted C1-C6 alkyl group (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R9, R 11 and R 13 may be hydrogen or deuterium.

[0029] In some forms, when the platinum(II) complex has the structure of Formula II’, R1-R4 may independently be hydrogen, a halide, an unsubstituted C1-C 12 alkyl group (for example, an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9-R 13 may independently be hydrogen, deuterium, an unsubstituted C1-C 12 alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), an unsubstituted phenyl group, an unsubstituted heteroaryl group, or an amino group. Optionally, in these forms, at least one of R1-R4 is not hydrogen (for example, R4 may be a halide, an unsubstituted C1-C6 alkyl group, or , R9-R 13 may independently be hydrogen, deuterium or an unsubstituted C1-C6 alkyl group).

[0030] In some forms, the platinum(II) complex may have any one of the following structures:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] 。

[0044] Typically, platinum(II) complexes emit in the blue region, with their maximum emission wavelength (λ max ) in the range of 420 nm to 490 nm, 430 nm to 490 nm, 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 465 nm, or 440 nm to 470 nm, such as 441 nm to 454 nm, etc.

[0045] In some forms, the emission quantum yield (Ф em ) of the platinum(II) complex can be at least 30%, at least 35%, at least 45%, at least 50%, at least 60%, at least 70%, in the range of 30% to 90%, in the range of 30% to 85%, in the range of 30% to 80%, in the range of 35% to 85%, in the range of 35% to 80%, in the range of 45% to 85%, in the range of 45% to 80%, in the range of 50% to 85%, or in the range of 50% to 80%; the emission lifetime (τ em ) is ≤ 5.5 μs, ≤ 5 μs, ≤ 4 μs, ≤ 3 μs, ≤ 2 μs, ≤ 1 μs, in the range of 0.5 μs to 5 μs, in the range of 1 μs to 5 μs, or in the range of 2 μs to 5 μs, such as about 2.25 μs, etc.; and / or the radiative decay rate (k r ) is at least 1.0 × 10 5 s -1 、at least 1.5 × 10 5 s -1 、at least 2.0 × 10 5 s -1 、in the range of 1.0 × 10 5 s -1 to 6.0 × 10 5 s -1 、in the range of 1.0 × 10 5 s -1 to 5.0 × 10 5 s -1 、in the range of 1.5 × 10 5 s -1 to 6.0 × 10 5 s -1 、in the range of 1.5 × 10 5 s -1 to 5.0 × 105 s -1 within the range of, at 2.0 × 10 5 s -1 to 6.0 × 10 5 s -1 within the range of, at 2.0 × 10 5 s -1 to 5.0 × 10 5 s -1 within the range of, at 1.0 × 10 5 s -1 to 4.0 × 10 5 s -1 within the range of, at 1.5 × 10 5 s -1 to 4.0 × 10 5 s -1 within the range of, at 2.0 × 10 5 s -1 to 4.0 × 10 5 s -1 within the range of, or at 3.0 × 10 5 s -1 to 6.0 × 10 5 s -1 within the range of, such as about 3.4 × 10 5 s -1 etc., and the above are measured in the film at room temperature.

[0046] Also disclosed are organic light-emitting elements, such as organic light-emitting diodes (OLEDs), which contain one or more light-emitting layers or two or more light-emitting layers formed using the disclosed platinum(II) complexes. Generally, the total concentration of the platinum(II) complexes in each light-emitting layer of the light-emitting layer or two or more light-emitting layers in the organic light-emitting element is at most 20 wt%, at most 10 wt%, at least 1 wt%, within the range of about 1 wt% to about 20 wt%, within the range of about 1 wt% to about 10 wt%, within the range of about 2 wt% to about 20 wt%, within the range of about 2 wt% to about 15 wt%, within or about 2 wt% to about 10 wt%, such as about 2 wt%, about 6 wt% or about 10 wt%, etc. These organic light-emitting elements can emit light in the blue region and have high performance at room temperature.

[0047] For example, the organic light-emitting element can emit light in the blue region, and its maximum luminance (L) is at least 3000 cd m -2 , at least 4000 cd m -2 , at least 5000 cd m -2, at least 6000 cd / m² -2 , at least 8000 cd / m² -2 , within the range of 3000 cd / m² -2 to 50000 cd / m² -2 , within the range of 3000 cd / m² -2 to 40000 cd / m² -2 , within the range of 3000 cd / m² -2 to 30000 cd / m² -2 , within the range of 3000 cd / m² -2 to 25000 cd / m² -2 , within the range of 3000 cd / m² -2 to 15000 cd / m² -2 , within the range of 1000 cd / m² 2 , the current efficiency (CE) at 1000 cd / m² is at least 20 cd / A -1 , at least 25 cd / A, within the range of 20 cd / A to 50 cd / A, or within the range of 20 cd / A to 45 cd / A; at 1000 cd / m² 2 , the power efficiency (PE) at 1000 cd / m² is at least 20 lm / W, within the range of 20 lm / W to 50 lm / W, or within the range of 20 lm / W to 45 lm / W; and / or at 1000 cd / m² 2 , the external quantum efficiency (EQE) at 1000 cd / m² is at least 10%, at least 15%, within the range of 10% to 35%, within the range of 10% to 30%, within the range of 10% to 25%, within the range of 15% to 35%, within the range of 15% to 30%, within the range of 15% to 25%, within the range of 20% to 30%, or within the range of 15% to 20%, such as about 20%, etc.

[0048] These high-performance organic blue light-emitting devices containing platinum(II) complexes disclosed herein can be used in various devices, such as fixed visual display units, mobile visual display units, lighting devices, wearable devices, or medical monitoring devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 Shows the TGA thermal analysis diagrams of Pt-ref1, Pt-4, Pt-7, and Pt-8.

[0050] Figures 2A to 2C Shows the crystal structures of Pt-1( Figure 2A ), Pt-4( Figure 2B ), and Pt-ref1( Figure 2C ).

[0051] Figure 3AShows the emission spectra of Pt-1, Pt-2, Pt-3, and Pt-4 in the PMMA film. Figure 3B Shows the emission spectra of Pt-5, Pt-6, Pt-7, and Pt-8 in the PMMA film.

[0052] Figures 4A to 4D Shows the EL spectra ( Figure 4A ) and performance characteristics of devices fabricated with Pt-4 at doping concentrations of 2 wt%, 6 wt%, and 10 wt%. The performance characteristics of these devices include EQE ( Figure 4B ), luminance ( Figure 4C ), and current density ( Figure 4D ). The device structure is: ITO / HAT-CN (5 nm) / TAPC (30 nm) / TCTA (5 nm) / CzSi (3 nm) / Pt-4: CzSi:BCPO (18 nm) / TSPO1 (30nm) / LiF (1.2 nm) / Al (100 nm).

[0053] Figures 5A to 5D Shows the EL spectra ( Figure 5A ) and performance characteristics of devices fabricated with Pt-8 at doping concentrations of 2 wt%, 6 wt%, and 10 wt%. The performance characteristics of these devices include EQE ( Figure 5B ), luminance ( Figure 5C ), and current density ( Figure 5D ). The device structure is: ITO / HAT-CN (5 nm) / TAPC (30 nm) / TCTA (5 nm) / CzSi (3 nm) / Pt-8: CzSi:BCPO (32 nm) / TSPO1 (30nm) / LiF (1.2 nm) / Al (100 nm).

[0054] Figure 6 Shows a non-limiting example of an organic light-emitting diode device 100 having a multilayer structure.

[0055] Figure 7 Shows the emission spectra of Pt-9, Pt-10, and Pt-11 in the PMMA film.

[0056] Figures 8A to 8D Shows the EL spectra ( Figure 8A ) and performance characteristics of devices fabricated with Pt-9 at doping concentrations of 10 wt% and 15 wt%. The performance characteristics of these devices include EQE ( Figure 8B ), luminance ( Figure 8C ), and current density ( Figure 8D)。The device structure is: ITO / HAT-CN (5 nm) / TAPC (40 nm) / TCTA (7 nm) / CzSi (3 nm) / Pt-9: CzSi (20nm) / TSPO1 (30 nm) / LiF (1.2 nm) / Al (100 nm). Detailed implementation manners

[0057] I. Definitions

[0058] It should be understood that, unless otherwise specified, the disclosed compounds, compositions, and methods are not limited to specific synthesis methods, specific analytical techniques, or specific reagents, and thus can vary. It should also be understood that the terms used herein are for the purpose of describing specific forms and embodiments only and are not intended to be limiting.

[0059] As used herein, "substituted / substituent" refers to all permitted substituents of the compounds or functional groups described herein. In the broadest sense, permitted substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, but are not limited to, halogen, hydroxy, or any other organic group having any number of carbon atoms (preferably 1 to 14 carbon atoms), and optionally containing one or more heteroatoms, such as oxygen, sulfur, or nitrogen groups, in a straight-chain, branched-chain, or cyclic structural format. Representative substituents include substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, halogen, hydroxy, alkoxy, phenoxy, aryloxy, silyl, mercapto, alkylthio, substituted alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, substituted or unsubstituted carbonyl, carboxyl, amino, amido, oxo, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphanyl, phosphoryl, phosphonyl, amino acid. Such substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted phenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, halogen, hydroxy, alkoxy, phenoxy, aryloxy, silyl, mercapto, alkylthio, substituted alkylthio, phenylthio, arylthio, cyano, isocyano, nitro, substituted or unsubstituted carbonyl, carboxyl, amino, amido, oxo, sulfinyl, sulfonyl, sulfonic acid, phosphonium, phosphanyl, phosphoryl, phosphonyl, and amino acid may be further substituted.

[0060] Heteroatoms such as nitrogen, etc. may have hydrogen substituents and / or any permitted substituents of the organic compounds described herein that satisfy the valence of the heteroatom. It is understood that "substituted" or "substituent" includes the implicit condition that such substitution is carried out in accordance with the permitted valences of the atoms being substituted and the substituents, and that such substitution results in a stable compound, i.e., a compound that does not spontaneously undergo transformation (e.g., rearrangement, cyclization, elimination, etc.).

[0061] As used herein, "alkyl" refers to a group of saturated aliphatic groups, including straight-chain alkyl, branched-chain alkyl, and cycloalkyl (alicyclic). In some forms, the straight-chain or branched-chain alkyl has 30 or fewer carbon atoms in its main chain (e.g., C1 to C 30 , branched-chain is C3 to C 30) 20 carbon atoms or fewer, 15 carbon atoms or fewer, or 10 carbon atoms or fewer. Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Similarly, cycloalkyl is a non-aromatic carbon-based ring composed of at least three carbon atoms, such as a non-aromatic monocyclic or non-aromatic polycyclic ring containing 3 to 30 carbon atoms, 3 to 20 carbon atoms, or 3 to 10 carbon atoms in its ring structure, and having 5, 6, or 7 carbons in the ring structure. Cycloalkyl groups containing a polycyclic ring system may have two or more non-aromatic rings, where two or more carbons are shared by two adjacent rings (i.e., "fused cycloalkyl rings"). Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

[0062] "Substituted alkyl" refers to an alkyl moiety having one or more substituents that replace hydrogen on one or more carbons of the hydrocarbon backbone. Such substituents can be any of the above substituents, for example, halogen (such as fluorine, chlorine, bromine, or iodine), hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl, or acyl), thiocarbonyl (such as thioester, thioacetate, or thiocarboxylate), aryl, alkoxy, aralkyl, phosphonium, phosphino, phosphonyl, phosphoryl, phosphate, phosphonate, phosphinate, amino, amido, amidine, imine, cyano, nitro, azide, oxo, mercapto, thiol, alkylthio, silyl, sulfinyl, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic, aromatic, or heteroaromatic moieties. -NRR', where R and R' are independently hydrogen, deuterium, alkyl, or aryl, and where the nitrogen atom is optionally quaternized; -SR, where R is phosphonyl, sulfinyl, silyl, hydrogen, deuterium, alkyl, or aryl; -CN; -NO2; -COOH; carboxylate; -COR, -COOR, or -CON(R)2, where R is hydrogen, deuterium, alkyl, or aryl; imino, silyl, ether, haloalkyl (e.g., -CF3, -CH2-CF3, -CCl3); -CN; -NCOCOCH2CH2; -NCOCOCHCH; and -NCS; and combinations thereof.

[0063] Those skilled in the art should understand that, if appropriate, the substituted moiety on the hydrocarbon chain itself can be substituted. For example, the substituents of a substituted alkyl can include halogen, hydroxy, nitro, thiol, amino, aralkyl, azide, imino, amido, phosphonium, phosphino, phosphonyl (including phosphonate and phosphinate), oxo, sulfonyl (including sulfate, sulfonamide, sulfamoyl, and sulfonate), and silyl, as well as ether, alkylthio, carbonyl (including ketone, aldehyde, carboxylate, and ester), haloalkyl, -CN, and the like. Cycloalkyl can be substituted in the same manner.

[0064] Unless the amount of carbon is otherwise specified, as used herein, "lower alkyl" means alkyl as defined above, but having from 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, in its backbone structure. Similarly, "lower alkenyl" and "lower alkynyl" have similar chain lengths.

[0065] As used herein, "heteroalkyl" means a straight-chain, branched-chain or cyclic carbon-containing alkyl or a combination thereof that contains at least one heteroatom in its carbon backbone. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, where the nitrogen, phosphorus and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. For example, the term "heterocycloalkyl" is a cycloalkyl as defined above, wherein at least one carbon atom of the ring is replaced by a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus).

[0066] As used herein, the term "alkenyl" is a hydrocarbon group having from 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon double bond. Alkenyl includes straight-chain alkenyl, branched-chain alkenyl and cycloalkenyl. Cycloalkenyl is a non-aromatic carbon-based ring that contains at least three carbon atoms and at least one carbon-carbon double bond in its ring structure, such as a non-aromatic monocyclic or non-aromatic polycyclic ring containing 3 to 30 carbon atoms and at least one carbon-carbon double bond, 3 to 20 carbon atoms and at least one carbon-carbon double bond, or 3 to 10 carbon atoms and at least one carbon-carbon double bond, and having 5, 6 or 7 carbons and at least one carbon-carbon double bond in its ring structure. A cycloalkenyl containing a polycyclic ring system may have two or more non-aromatic rings, where two or more carbons are common to two adjacent rings (i.e., "fused cycloalkenyl rings") and contain at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(C’D) are intended to include E and Z isomers. This may be inferred in the structural formulas herein where there are asymmetric alkenes, or it may be explicitly indicated by the bond symbol C. The term "alkenyl" as used throughout the specification, examples and claims is intended to include both "unsubstituted alkenyl" and "substituted alkenyl", the latter referring to an alkenyl moiety having one or more substituents that replace hydrogen on one or more carbons of the hydrocarbon backbone. The term "alkenyl" also includes "heteroalkenyl".

[0067] The term "substituted alkenyl" refers to an alkenyl moiety having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonium, phosphino, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, oxo, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof.

[0068] As used herein, "heteroalkenyl" refers to a straight-chain, branched-chain or cyclic carbon-containing alkenyl or a combination thereof containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorus and sulfur atoms are optionally oxidized and the nitrogen heteroatom is optionally quaternized. For example, the term "heterocyclic alkenyl" is a cycloalkenyl in which at least one ring carbon atom is replaced by a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus).

[0069] As used herein, the term "alkynyl" is a hydrocarbon group having 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. Alkynyl includes straight-chain alkynyl, branched-chain alkynyl and cycloalkynyl. Cycloalkynyl is a non-aromatic carbon-based ring containing at least three carbon atoms and at least one carbon-carbon triple bond in its ring structure, such as a non-aromatic monocyclic or non-aromatic polycyclic ring containing 3 to 30 carbon atoms and at least one carbon-carbon triple bond, 3 to 20 carbon atoms and at least one carbon-carbon triple bond, or 3 to 10 carbon atoms and at least one carbon-carbon triple bond, and having 5, 6 or 7 carbons and at least one carbon-carbon triple bond in the ring structure. The cycloalkynyl containing a polycyclic ring system can have two or more non-aromatic rings, where two or more carbons are common to two adjacent rings (i.e., "fused cycloalkynyl rings") and contain at least one carbon-carbon triple bond. The term "alkynyl" used throughout the specification, examples and claims is intended to include both "unsubstituted alkynyl" and "substituted alkynyl", the latter referring to an alkynyl moiety having one or more substituents replacing hydrogen on one or more carbons of the hydrocarbon backbone. The term "alkynyl" also includes "heteroalkynyl".

[0070] The term "substituted alkynyl" refers to an alkynyl moiety having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents can be any of the above-mentioned substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonium, phosphino, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof.

[0071] As used herein, "heteroalkynyl" refers to a straight-chain, branched-chain, or cyclic carbon-containing alkynyl or combinations thereof containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P, and S, where the nitrogen, phosphorus, and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. For example, the term "heterocyclic alkynyl" is a cyclic alkynyl in which at least one carbon atom of the ring is replaced by a heteroatom (such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus).

[0072] As used herein, "aryl" refers to a C4-C 26 aryl aromatic ring or fused ring system containing an aromatic ring and optionally one or more non-aromatic rings. Examples of aryl are benzene, tetrahydronaphthalene, indane, etc.

[0073] The term "substituted aryl" refers to an aryl in which one or more hydrogen atoms on one or more aromatic rings are replaced by one or more substituents, and these substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, alkoxy, carbonyl (such as ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl (such as CF3, -CH2-CF3, -CCl3, etc.), -CN, aryl, heteroaryl and combinations thereof.

[0074] "Heterocycle" and "heterocyclic group" are used interchangeably and refer to a cyclic group attached through a ring carbon or nitrogen atom of a monocyclic or polycyclic system containing 3 to 30 ring atoms, 3 to 20 ring atoms, 3 to 10 ring atoms or 5 to 6 ring atoms, wherein the polycyclic system contains one or more non-aromatic rings and optionally one or more aromatic rings, wherein at least one non-aromatic ring contains carbon and 1 to 4 heteroatoms, each heteroatom selected from non-peroxidized oxygen, sulfur and N(Y), where Y is absent or is H, O, C1-C 10 alkyl, phenyl or benzyl and optionally contains 1-3 double bonds and is optionally substituted by one or more substituents. A heterocyclic group is by definition different from a heteroaryl group. A heterocycle can be a heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, etc., such as piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, dihydrofuro[2,3-b]tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pyranyl, 2H-pyrrolyl, 4H-quinolizinyl, quinuclidinyl, tetrahydrofuryl, 6H-1,2,5-thiadiazinyl. The heterocyclic group can optionally be substituted by one or more substituents as defined above for alkyl and aryl groups.

[0075] The term "heteroaryl" refers to a C3-C containing one aromatic ring and one or more non-aromatic rings 26A monocyclic aromatic ring or fused ring system wherein one or more carbon atoms in the aromatic ring structure have been replaced by heteroatoms. Suitable heteroatoms include, but are not limited to, oxygen, sulfur, and nitrogen. Examples of heteroaryl groups are pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine. Examples of heteroaryl rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, hexazinyl, decahydroquinolinyl, 2H,6H-1, 5,2-dithiazinyl, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, octahydroisoquinolinyl, 1,2, 3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathiol, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridoxazole, pyridoimidazole, pyridothiazole, pyridinyl , pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 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. One or more rings may be substituted as defined below for "substituted heteroaryl."

[0076] The term "substituted heteroaryl" refers to a heteroaryl in which one or more hydrogen atoms on one or more heteroaromatic rings are replaced by one or more substituents, including but not limited to halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, alkoxy, carbonyl (such as ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl (such as CF3, -CH2-CF3, -CCl3), -CN, aryl, heteroaryl and combinations thereof.

[0077] The term "polyaryl" refers to a fused ring system containing two or more aromatic rings and optionally one or more non-aromatic rings. Examples of polyaryl are naphthalene, anthracene, phenanthrene, chrysene, pyrene, coronene, hexabenzocoronene, etc. When the fused ring system contains two or more aromatic rings and optionally one or more non-aromatic rings, and one or more carbon atoms on one or more aromatic ring structures have been replaced by heteroatoms, the fused ring system can be referred to as "heteropolyaryl" or "polyheteroaryl". The terms "heteropolyaryl" and "polyheteroaryl" are used interchangeably herein.

[0078] The term "substituted polyaryl" refers to a polyaryl in which one or more aryl groups are replaced by one or more substituents, including but not limited to halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof. When referring to polyheteroaryl, this chemical moiety can be referred to as "substituted polyheteroaryl".

[0079] The term "ring", "cyclic ring" or "cyclic group" refers to a substituted or unsubstituted monocyclic or substituted or unsubstituted polycyclic (such as those formed by a monocyclic system or a fused ring system), for example, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted cycloalkynyl, or substituted or unsubstituted heterocyclic group, which have 3 to 30 carbon atoms when geometric constraints permit. Substituted cycloalkyl, cycloalkenyl, cycloalkynyl and heterocyclic group are substituted as defined above for alkyl, alkenyl, alkynyl, or heterocyclic group, respectively.

[0080] As used herein, the term "aralkyl" is an aryl or heteroaryl having an alkyl, alkynyl or alkenyl as defined above attached to an aromatic group (such as aryl, heteroaryl, polyaryl or polyheteroaryl). An example of aralkyl is benzyl.

[0081] The terms "alkoxy" or "alkyloxy", "aryloxy" or "aryloxy" generally describe compounds represented by the formula -OR v wherein R v includes but is not limited to substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkylheteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted carbonyl, phosphonium, phosphinoalkyl, phosphonyl, sulfinyl, silyl, thiol, amide and amino. Exemplary alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy and the like. "Lower alkoxy" groups are alkoxy groups containing 1 to 6 carbon atoms. "Ether" is two functional groups covalently linked through oxygen, as defined below. Thus, an alkyl substituent that makes an alkyl an ether is or is similar to an alkoxy group and can be represented, for example, by one of -O-alkyl, -O-alkenyl, -O-alkynyl, -O-aralkyl, -O-aryl, -O-heteroaryl, -O-polyaryl, -O-polyheteroaryl, -O-heterocyclic group and the like.

[0082] The term "substituted alkoxy" refers to an alkoxy group having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the alkoxy backbone. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonium, phosphinoalkyl, phosphonyl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amide, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, oxo, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof.

[0083] As used herein, the term "ether" is represented by formula A 2 OA 1 wherein A 2 and A 1It can be independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, phosphonium, phosphinoalkyl, phosphoryl, sulfinyl, silyl, mercapto, substituted or unsubstituted carbonyl, alkoxy, amido or amino as described above.

[0084] As used herein, the term "polyether" is represented by the following formula:

[0085] ,

[0086] wherein A 3 can be independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, phosphonium, phosphinoalkyl, substituted or unsubstituted carbonyl, alkoxy, amido or amino as described above; g can be a positive integer from 1 to 30.

[0087] The term "phenoxy" is recognized in the art and refers to a compound of the formula -OR v wherein R v is C6H5 (i.e., -O-C6H5). Those skilled in the art recognize that phenoxy is one of the aryloxy groups.

[0088] The term "substituted phenoxy" refers to the phenoxy as defined above having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the benzene ring. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonium, phosphinoalkyl, phosphinoalkyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl and combinations thereof.

[0089] The terms "aryloxy" and "aryl-oxy" used interchangeably herein are represented by -O-aryl or -O-heteroaryl, wherein aryl and heteroaryl are as defined herein.

[0090] The terms "substituted aryloxy" and "substituted aryl-oxy" used interchangeably herein represent -O-aryl or -O-heteroaryl having one or more substituents replacing one or more hydrogen atoms on one or more ring atoms of aryl and heteroaryl as defined herein. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonium, phosphino, phosphinyl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof.

[0091] The term "amino" as used herein includes the following groups:

[0092] (primary amino), (secondary amino),

[0093] (tertiary amino), and (quaternary amino),

[0094] wherein E is absent, or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, wherein independently of E, R x 、R xi and R xii each independently represents substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic, substituted or unsubstituted aralkyl (such as substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic, hydroxy, alkoxy, phosphonium, phosphino, phosphinyl, sulfinyl, silyl, mercapto, amido, amino or -(CH2) m-R’’’; R’’’ represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group or an amino group; and m is an integer from 0 or 1 to 8. The term "quaternary amino" also includes those in which nitrogen, R x , R xi and R xii form, with the N + to which they are attached, a heterocyclic or heteroaryl group having 3 to 14 atoms in the ring structure. Those skilled in the art will understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0095] The terms "amide" or "amido group" are used interchangeably and refer to both "unsubstituted amido group" and "substituted amido group", and are represented by the following general formula:

[0096] ,

[0097] wherein E is absent, or E is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, or a substituted or unsubstituted heterocyclic group, wherein independently of E, R and R' each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, a phosphonyl group, a sulfinyl group, a silyl group, a thiol group, an amido group, an amino group or -(CH2) m-R''', or R and R' together with the N atom to which they are attached form a heterocycle having 3 to 14 atoms in the ring structure; R''' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group or an amino group; and m is zero or an integer ranging from 1 to 8. In some forms, when E is oxygen, a carbamate is formed. Those skilled in the art will understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0098] As used herein, "carbonyl" is well recognized in the art and includes moieties that can be represented by the following general formula:

[0099] ,

[0100] wherein X is a bond, or represents oxygen or sulfur, and R represents hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group, an amino group, or -(CH2) m -R", or a pharmaceutically acceptable salt; E" is absent, or E" is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group; R' represents hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group, an amino group or -(CH2) m-R”; R” represents a hydroxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphinoalkyl group, an amide group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as a halogen, an azide, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a hydroxyl group, a carbonyl group (such as a carboxyl group, an alkoxycarbonyl group, a formyl group or an acyl group, etc.), a silyl group, an ether, an ester, a thiocarbonyl group (such as a thioester, a thioacetate or a thiocarboxylate, etc.), an alkoxy group, a phosphonium group, a phosphinoalkyl group, a phosphoryl group, a phosphate group, a phosphonate group, a phosphinate group, an amino group (such as a quaternized amino group), an amide group, an amidine, an imine, a cyano group, a nitro group, an azido group, a mercapto group, an alkylthio group, a sulfate group, a sulfonate group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a heterocyclic group, an alkylaryl group, a haloalkyl group, -CN, an aryl group, a heteroaryl group and combinations thereof. Those skilled in the art understand that the E’’ group listed above is divalent (for example, methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl). When X is oxygen and R is as defined above, this moiety is also referred to as a carboxyl group. When X is oxygen and R is hydrogen, this formula represents “carboxylic acid”. When X is oxygen and R’ is hydrogen, this formula represents “formate”. When X is oxygen and neither R nor R’ is hydrogen, this formula represents “ester”. Generally speaking, when the oxygen atom in the above formula is replaced by a sulfur atom, this formula represents a “thiocarbonyl” group. When X is sulfur and neither R nor R’ is hydrogen, this formula represents “thioester”. When X is sulfur and R is hydrogen, this formula represents “thiocarboxylic acid”. When X is sulfur and R’ is hydrogen, this formula represents “thiocarboxylate”. When X is a bond and R is not hydrogen, the above formula represents “ketone”. When X is a bond and R is hydrogen, the above formula represents “aldehyde”.

[0101] The term “phosphinoalkyl group” is represented by the following formula:

[0102] ,

[0103] wherein, E does not exist, or E is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, wherein independently of E, R vi and R viieach independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group, etc.), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, a phosphonyl group, a sulfinyl group, a silyl group, a thiol group, an amide group, an amino group, or -(CH2) m -R''', or R vi and R vii together with the P atom to which they are attached form a heterocyclic ring having 3 to 14 atoms in the ring structure; R''' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amide group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as a halogen, an azide, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a hydroxyl group, a carbonyl group (such as a carboxyl group, an alkoxycarbonyl group, a formyl group or an acyl group, etc.), a silyl group, an ether, an ester, a thiocarbonyl group (such as a thioester, a thioacetate or a thiocarboxylate, etc.), an alkoxy group, a phosphonyl group, a phosphate group, a phosphonate group, a phosphinate group, an amino group (e.g., a quaternized amino group), an amide group, an amidine, an imine, a cyano group, a nitro group, an azido group, a mercapto group, an alkylthio group, a sulfate group, a sulfonate group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a heterocyclic group, an alkylaryl group, a haloalkyl group, -CN, an aryl group, a heteroaryl group, a polyaryl group, a polyheteroaryl group and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0104] The term "phosphonium" is represented by the following formula:

[0105] ,

[0106] wherein E is absent, or E is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, wherein independently of E, R vi , R vii and R viiieach independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (such as a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group, etc.), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphinoalkyl group, a phosphonyl group, a sulfinyl group, a silyl group, a thiol group, an amide group, an amino group, or -(CH2) m -R''', or R vi 、R vii and R viii together with the P atom to which they are attached + form a heterocycle having 3 to 14 atoms in the ring structure; R''' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphinoalkyl group, an amide group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as a halogen, an azide, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a hydroxyl group, a carbonyl group (such as a carboxyl group, an alkoxycarbonyl group, a formyl group or an acyl group, etc.), a silyl group, an ether, an ester, a thiocarbonyl group (such as a thioester, a thioacetate or a thiocarboxylate, etc.), an alkoxy group, a phosphonyl group, a phosphate ester, a phosphonate ester, a phosphinate ester, an amino group (such as a quaternized amino group), an amide group, an amidine, an imine, a cyano group, a nitro group, an azido group, a mercapto group, an alkylthio group, a sulfate ester, a sulfonate ester, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a heterocyclic group, an alkylaryl group, a haloalkyl group, -CN, an aryl group, a heteroaryl group, a polyaryl group, a polyheteroaryl group and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0107] The term "phosphonyl group" is represented by the following formula:

[0108] ,

[0109] wherein E is absent, or E is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic group, oxygen, alkoxy, aryloxy, or substituted alkoxy or substituted aryloxy, wherein independently E, R vi and R vii are independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic group, hydroxy, alkoxy, phosphonium, phosphino, phosphonyl, sulfinyl, silyl, mercapto, amido, amino or -(CH2) m -R''', or R vi and R vii together with the P atom to which they are attached form a heterocycle having 3 to 14 atoms in the ring structure; R''' represents hydroxy, substituted or unsubstituted carbonyl, substituted or unsubstituted aryl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, alkoxy, phosphonium, phosphino, amido or amino; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonyl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art will understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0110] The term "phosphonyl" defines a phosphonyl group wherein E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy, as defined above, and independently of E, Rvi and R vii are independently hydroxy, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy, as defined above. As will be understood by those of ordinary skill in the art, when E is oxygen, the phosphoryl group cannot be attached to another chemical species, for example to form an oxygen-oxygen bond or other unstable bond. When E, R vi and R vii are substituted, the substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art will understand that the E groups listed above are divalent (for example, methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0111] The term "sulfinyl" is represented by the formula:

[0112] ,

[0113] wherein E is absent, or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl (for example, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, where independently of E, R represents hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbonyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl (for example substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl), substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclic group, hydroxy, alkoxy, phosphonium, phosphino, phosphoryl, silyl, mercapto, amido, amino, or -(CH2) m-R''', or E and R together with the S atom to which they are attached form a heterocyclic ring having 3 to 14 atoms in the ring structure; R''' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (for example, methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0114] The term "sulfonyl" is represented by the following formula:

[0115] ,

[0116] wherein E does not exist, or E is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group (e.g., a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group, etc.), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group; independently of E, R represents hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (e.g., a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group, an amino group, or -(CH2)m-R''', or E and R together with the S atom to which they are attached form a heterocyclic ring having 3 to 14 atoms in the ring structure; R''' represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as a halogen, an azide, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a hydroxyl group, a carbonyl group (such as a carboxyl group, an alkoxycarbonyl group, a formyl group or an acyl group, etc.), a silyl group, an ether, an ester, a thiocarbonyl group (such as a thioester, a thioacetate or a thiocarboxylate, etc.), an alkoxy group, a phosphoryl group, a phosphate ester, a phosphonate ester, a phosphinate ester, an amino group (e.g., a quaternized amino group), an amido group, an amidine, an imine, a cyano group, a nitro group, an azido group, a mercapto group, an alkylthio group, a sulfate ester, a sulfonate ester, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a heterocyclic group, an alkylaryl group, a haloalkyl group, -CN, an aryl group, a heteroaryl group, a polyaryl group, a polyheteroaryl group and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0117] The term "sulfonic acid" refers to a sulfonyl group as defined above, where R is a hydroxyl group and E is absent, or E is a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, or a substituted or unsubstituted heteroaryl group. Such substituents can be any of the substituents described above, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0118] The term "sulfate" refers to a sulfonyl group as defined above, where E is absent, oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy, all as defined above, and R is independently a hydroxyl group, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy, all as defined above. As understood by those of ordinary skill in the art, when E is oxygen, the sulfate cannot be linked to another chemical species to form, for example, an oxygen-oxygen bond or other unstable bonds. Such substituents can be any of the substituents described above, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as carboxyl, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0119] The term "sulfonate" refers to a sulfonyl group as defined above, where E is oxygen, alkoxy, aryloxy, substituted alkoxy or substituted aryloxy, all as defined above, and R is independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amino, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, -(CH2) m -R''', where R''' represents hydroxy, substituted or unsubstituted carbonyl, aryl, cycloalkyl ring, cycloalkenyl ring, heterocycle, amido, amino, or polycycle; and m is zero or an integer ranging from 1 to 8. As understood by those of ordinary skill in the art, when E is oxygen, the sulfonate cannot be linked to another chemical species, such as forming an oxygen-oxygen bond or other unstable bonds. Such substituents can be any of the substituents described above, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphoryl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0120] The term "sulfamoyl" refers to a sulfonamide or a sulfonamide represented by the formula:

[0121] ,

[0122] wherein E does not exist, or E is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group (such as a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted cycloalkyl group, etc.), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, wherein independently of E, R and R’ each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aralkyl group (such as a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted aralkyl group, etc.), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group, an amino group or -(CH2) m -R’’’, or R and R’ together with the N atom to which they are attached form a heterocyclic ring having 3 to 14 atoms in the ring structure; R’’’ represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, a substituted or unsubstituted polyheteroaryl group, an alkoxy group, a phosphonium group, a phosphino group, an amido group or an amino group; and m is 0 or an integer ranging from 1 to 8. Such substituents can be any of the above substituents, such as a halogen, an azide, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a hydroxyl group, a carbonyl group (such as a carboxyl group, an alkoxycarbonyl group, a formyl group or an acyl group, etc.), a silyl group, an ether, an ester, a thiocarbonyl group (such as a thioester, a thioacetate or a thiocarboxylate, etc.), an alkoxy group, a phosphoryl group, a phosphate ester, a phosphonate ester, a phosphinate ester, an amino group (such as a quaternized amino group), an amido group, an amidine, an imine, a cyano group, a nitro group, an azido group, a mercapto group, an alkylthio group, a sulfate ester, a sulfonate ester, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a heterocyclic group, an alkylaryl group, a haloalkyl group, -CN, an aryl group, a heteroaryl group, a polyaryl group, a polyheteroaryl group and combinations thereof. Those skilled in the art understand that the E groups listed above are divalent (for example, methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

[0123] As used herein, the term "silyl" is represented by the formula -SiRR'R", where R, R', and R" can independently be hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted carbonyl, phosphonium, phosphinoalkyl, phosphonyl, sulfinyl, thiol, amido, amino, alkoxy, or oxo. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonyl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0124] The term "thiol" can be used interchangeably with -SR and is represented by -SR, where R can be hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl (e.g., substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, etc.), substituted or unsubstituted polyaryl, substituted or unsubstituted polyheteroaryl, substituted or unsubstituted carbonyl, phosphonium, phosphinoalkyl, amido, amino, alkoxy, oxo, phosphonyl, sulfinyl, or silyl. Such substituents can be any of the above substituents, such as halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, carbonyl (such as carboxy, alkoxycarbonyl, formyl or acyl, etc.), silyl, ether, ester, thiocarbonyl (such as thioester, thioacetate or thiocarboxylate, etc.), alkoxy, phosphonyl, phosphate, phosphonate, phosphinate, amino (such as quaternized amino), amido, amidine, imine, cyano, nitro, azido, mercapto, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamide, sulfonyl, heterocyclic group, alkylaryl, haloalkyl, -CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

[0125] The disclosed compounds and substituents can independently have two or more of the groups listed above. For example, if the compound or substituent is a straight-chain alkyl group, one hydrogen atom of the alkyl group can be replaced by a hydroxyl group, an alkoxy group, etc. Depending on the groups selected, the first group can be incorporated within the second group, or the first group can be pendant (i.e., attached) to the second group. For example, for the phrase "alkyl group containing an ester group", the ester group can be introduced into the main chain of the alkyl group. Alternatively, the ester can be attached to the main chain of the alkyl group. The nature of the groups selected will determine whether the first group is embedded or attached to the second group.

[0126] The compounds and substituents can independently be substituted by the substituents described in the "substituted" definition above.

[0127] Numerical ranges disclose each possible number that such ranges can reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, in a given carbon range of C3 - C9, the range also discloses C3, C4, C5, C6, C7, C8, and C9, as well as any sub-ranges between these numbers (e.g., C4 - C6), and any possible combinations of ranges between these values. In yet another example, a given temperature range can be from about 25ºC to 30ºC, where the range also discloses temperatures that can be independently selected from about 25ºC, 26ºC, 27ºC, 28ºC, 29ºC, and 30ºC, as well as any range between these numbers (e.g., 26ºC to 28ºC), and any possible combinations of ranges between these values.

[0128] The use of the term "about" is intended to describe values that are above or below the stated value, and the term "about" modifies the value within a range of about + / - 10%. When the term "about" is used before a numerical range (i.e., about 1 - 5) or a series of numbers (i.e., about 1, 2, 3, 4, etc.), unless otherwise stated, it is intended to modify both ends of the numerical range and / or each number listed throughout the series.

[0129] The disclosed compounds and substituents can independently have two or more of the groups listed above. For example, if the compound or substituent is a straight-chain alkyl group, one hydrogen atom of the alkyl group can be replaced by a hydroxyl group, an alkoxy group, etc. Depending on the groups selected, the first group can be incorporated within the second group, or the first group can be pendant (i.e., attached) to the second group. For example, for the phrase "alkyl group containing an ester group", the ester group can be introduced into the main chain of the alkyl group. Alternatively, the ester can be attached to the main chain of the alkyl group. The nature of the groups selected will determine whether the first group is embedded or attached to the second group.

[0130] The compounds and substituents can independently be substituted by the substituents described in the "substituted" definition above.

[0131] II. Composition

[0132] A class of platinum(II) complexes (also referred to herein as Pt(II) complexes) is described, which can emit with high efficiency in the blue region. The Pt(II) complexes contain a platinum(II) atom coordinated by a ligand containing a benzimidazole-based NHC and a phenolate moiety. In some forms, the phenolate moiety of the ligand contains one or more large substituents, such as large phenyl groups, such as 3,5-di-tert-butyl-phenyl (ditBuPh) and 2,6-dimethyl-phenyl (diMePh). Compared with previously reported imidazole-based Pt(II)-O^C*^C*^O complexes, the structure of the disclosed Pt(II) complexes allows for a significant increase in the emission quantum yield and the radiative decay rate constant. For example, the Pt(II) complexes emit in the blue spectral region (e.g., the emission maximum (λ max ) is in the range of 420 nm to 490 nm, such as 441 to 454 nm), with a high emission quantum yield (i.e., Ф em ≥ 30%, such as 30% to 90%, 30% to 85%, or 30% to 80%), a short emission lifetime (i.e., τ em or τ ≤ 5.5 μs or ≤ 5 μs and at least about 2 μs, such as about 2.25 μs), and / or a fast radiative decay rate (i.e., k r ≥ 1.0×10 5 s -1 and at most about 6.0×10 5 s -1 , such as about 3.4×10 5 s -1 ), as measured in a film at room temperature. Without being bound by any theory, the improvement in the emission performance of the Pt(II) complexes can be attributed to the geometric structure of these metal complexes (e.g., reduced planarity and altered orientation between the NHC and the phenolate ring) and the extended π-conjugation of the acceptor unit.

[0133] Organic light-emitting devices containing the platinum(II) blue emitters disclosed herein are also described, such as light-emitting diodes (OLEDs). The following examples show that doped OLEDs containing the exemplary platinum(II) emitters disclosed herein exhibit electroluminescence in the blue region (λ max in the range of about 420 to 490 nm, such as 470 to 480 nm), with an external quantum efficiency (EQE) of at least 10% at 1000 cd m -2 , such as 10 - 25% at 1000 cd m -2 , and about 20% at 1000 cd m -2 .

[0134] A. Platinum(II) Complexes

[0135] In some forms, the disclosed platinum(II) complexes can have a structure of Formula I:

[0136] ,

[0137] wherein: (i) each occurrence of R1-R8 can independently be hydrogen, deuterium, a halide (such as fluoride, chloride, bromide, iodide, etc.), a hydroxyl group, an amino group, an amide group, a thiol group, a cyano group, a nitro group, an alkoxy group, a carbonyl group, a substituted or unsubstituted C1-C 12 alkyl group, a substituted or unsubstituted C1-C 12 alkenyl group, a substituted or unsubstituted C1-C 12 alkynyl group, a substituted or unsubstituted aryl group (such as phenyl), a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group, or two adjacent groups among R1-R8 and the carbon atom to which they are attached can together form a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group; and (ii) the substituents, when present, can independently be an unsubstituted C1-C 12 alkyl group, an unsubstituted C1-C 12 alkenyl group, an unsubstituted C1-C 12 alkynyl group, an unsubstituted aryl group (such as phenyl), an aryl group (such as phenyl) substituted by one or more unsubstituted aryl groups (such as unsubstituted phenyl) and / or one or more unsubstituted alkyl groups (such as unsubstituted C1-C 12 alkyl groups), a substituted or unsubstituted heteroaryl group, a heteroaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, a substituted or unsubstituted polyaryl group, a polyaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, a substituted or unsubstituted hetero-polyaryl group, a hetero-polyaryl group substituted by one or more unsubstituted aryl groups and / or one or more unsubstituted alkyl groups, an amino group, or a halide.

[0138] In some forms, the platinum(II) complexes can have a structure of Formula II:

[0139] ,

[0140] wherein R1-R4 and the substituents, when present, can be as defined for Formula I.

[0141] In some forms, the platinum(II) complexes can have the following structure:

[0142] ,

[0143] wherein R1-R4 can be as defined above for Formula I.

[0144] In some forms, the platinum(II) complex can have a structure of Formula III:

[0145] ,

[0146] wherein R2 to R5 and the substituents, when present, can be as defined for Formula I; each occurrence of X1 to X4 is independently CR 16 or nitrogen, and R 16 can be as defined for R1 to R8 of Formula I; n1 is an integer from 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2; R 14 and R 15 can independently be hydrogen, deuterium, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C 12 alkenyl, or substituted or unsubstituted C1-C 12 alkynyl, or R 14 and R 15 on two adjacent carbon atoms together with the carbon atoms to which they are attached can form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl.

[0147] In some forms, n1 can be 1, and R 14 and R 15 can be hydrogen or deuterium. In some forms, n1 can be 2, and R 14 and R 15 on two adjacent carbon atoms can be hydrogen, deuterium or can together with the carbon atoms to which they are attached form a substituted or unsubstituted aryl, such as unsubstituted aryl, for example unsubstituted phenyl.

[0148] In some forms, X1 and / or X4 can be nitrogen, and X2 and X3 can be CR 16 . In some forms, X1 can be nitrogen, and X2 to X4 can be CR 16 . In some forms, X4 can be nitrogen, and X1 to X3 can be CR 16 . In some forms, X1 to X4 can be CR 16 . In some forms, R 16 can be hydrogen, deuterium, halide, substituted or unsubstituted C1-C 12 alkyl, or substituted or unsubstituted aryl, wherein the substituents, when present, can independently be unsubstituted C1-C 12alkyl, unsubstituted aryl, aryl substituted by one or more unsubstituted aryl or one or more unsubstituted alkyl, unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero-polyaryl, hetero-polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, amino, or halide.

[0149] In some forms, X1 to X3 can be CR 16 and X4 can independently be nitrogen or CR 16 , R 16 can be hydrogen, deuterium, halide, unsubstituted C1-C 12 alkyl (e.g., unsubstituted C1-C6 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and R9 to R 13 can independently be hydrogen, deuterium or unsubstituted C1-C 12 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.).

[0150] In some forms, for any of the formulas described herein, R2 to R5 can be hydrogen, deuterium, halide, amino, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl, or two adjacent groups among R2 to R5 (e.g., R2 and R3, R3 and R4, or R4 and R5) can together with the carbon atom to which they are attached form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl; and the substituents when present can independently be unsubstituted C1-C 12 alkyl, unsubstituted aryl, aryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero-polyaryl, hetero-polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, amino, or halide.

[0151] In some forms, for any of the formulas described herein, n1, R 14 and R 15can be in any form defined herein; X1 and X4 can be nitrogen or CR 16 ; X2 and X3 can be CR 16 ; R 16 can be hydrogen, deuterium, halide, unsubstituted C1-C 12 alkyl, unsubstituted aryl, or aryl substituted by one or more unsubstituted C1-C 12 alkyl; R2-R5 can be hydrogen, deuterium, amino, unsubstituted C1-C 12 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl, or two adjacent groups among R2-R5 (such as R2 and R3, R3 and R4, or R4 and R5) and the carbon atoms to which they are attached can together form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl; and the substituents, when present, can independently be unsubstituted C1-C 12 alkyl, unsubstituted aryl (such as phenyl), aryl (such as phenyl) substituted by one or more unsubstituted aryl (such as phenyl) and / or one or more unsubstituted alkyl, unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero-polyaryl, hetero-polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, or amino.

[0152] In some forms, for any formula described herein, each occurrence of R1-R8 can independently be hydrogen, deuterium, halide (such as fluoride, chloride, or bromide), hydroxy, amino, amido, mercapto, cyano, nitro, alkoxy, carbonyl, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C 12 alkenyl, substituted or unsubstituted C1-C 12 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl; and the substituents, when present, can independently be unsubstituted C1-C 12 alkyl, unsubstituted C1-C 12 alkenyl, unsubstituted C1-C 12 alkynyl, or halide.

[0153] In some forms, for any formula described herein, each occurrence of R1-R8 can independently be hydrogen, deuterium, halide, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C12 Alkenyl, substituted or unsubstituted C1-C 12 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl.

[0154] In some forms, for any formula described herein, each occurrence of R1-R8 can independently be hydrogen, deuterium, halide, substituted or unsubstituted C1-C 12 Alkyl, or substituted or unsubstituted aryl.

[0155] In some forms, for any formula described herein, each occurrence of R1-R8 can independently be hydrogen, deuterium, halide (e.g., fluoride, chloride or bromide), unsubstituted C1-C 12 Alkyl (e.g., unsubstituted C1-C6 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9-R 13 can independently be hydrogen, deuterium, unsubstituted C1-C 12 Alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), unsubstituted phenyl, unsubstituted hetero-polyaryl, or amino, such as hydrogen, deuterium or unsubstituted C1-C 12 Alkyl, etc.

[0156] In some forms, for any formula described herein, R9-R 13 can independently be hydrogen, deuterium or unsubstituted C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R9, R 11 and R 13 can be hydrogen or deuterium.

[0157] In some forms, R9-R 13 can independently be hydrogen, deuterium or unsubstituted C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.). In some forms, R9 and R 13 can independently be hydrogen, deuterium or unsubstituted C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R 10 -R 12 can be hydrogen or deuterium. In some forms, R 10 and R 12 can independently be hydrogen, deuterium or unsubstituted C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R9, R 11 and R13 may be hydrogen or deuterium.

[0158] In some forms, for any formula described herein, a substituted or unsubstituted aryl (as an R group and / or a substituent of an R group) may be a substituted or unsubstituted phenyl, such as , where R9~R 13 may independently be hydrogen, deuterium, unsubstituted C1~C 12 alkyl, unsubstituted phenyl, unsubstituted heteroaryl, or amino.

[0159] In some forms, for any formula described herein, a substituted or unsubstituted heteroaryl (as an R group or a substituent of an R group) may be , and each occurrence of R 17 ~R 20 may be hydrogen, deuterium, unsubstituted C1~C 12 alkyl, unsubstituted phenyl, or phenyl substituted by one or more unsubstituted C1~C 12 alkyl and / or unsubstituted phenyl.

[0160] In some forms, for any formula described herein, R2 and R3 together, R3 and R4 together, or R4 and R5 together may be or ( represents the point of attachment to the benzene ring carbon atom); R 21 may be hydrogen, deuterium, unsubstituted C1~C 12 alkyl, unsubstituted phenyl, or phenyl substituted by one or more unsubstituted C1~C 12 alkyl and / or unsubstituted phenyl.

[0161] In some forms, for any formula described herein, an amino group (as an R group or a substituent of an R group) may be -NR 22 R 23 , where R 22 and R 23 may independently be hydrogen, deuterium, unsubstituted C1~C 12 alkyl, unsubstituted phenyl, or phenyl substituted by one or more unsubstituted C1~C 12 alkyl and / or unsubstituted phenyl.

[0162] In some forms, when the platinum(II) complex has the structure of Formula II or II’, R1~R4 may independently be hydrogen, deuterium, halide, unsubstituted C1~C 12an alkyl group (e.g., an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9 to R 13 can independently be hydrogen, deuterium, an unsubstituted C1-C 12 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), an unsubstituted phenyl group, an unsubstituted heteroaryl group, or an amino group. In some forms, R9 to R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.). In some forms, R9 and R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R 10 to R 12 can be hydrogen or deuterium. In some forms, R 10 and R 12 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), and R9, R 11 and R 13 can be hydrogen or deuterium.

[0163] In some forms, when the platinum(II) complex has the structure of formula II’, R1 to R4 can independently be hydrogen, deuterium, a halide, an unsubstituted C1-C 12 alkyl group (e.g., an unsubstituted C1-C6 alkyl group, an unsubstituted C1-C4 alkyl group or an unsubstituted C1-C3 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9 to R 13 can independently be hydrogen, deuterium, an unsubstituted C1-C 12 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), an unsubstituted phenyl group, an unsubstituted heteroaryl group, or an amino group. Optionally, in these forms, at least one of R1 to R4 is not hydrogen (e.g., R4 can be a halide, an unsubstituted C1-C6 alkyl group, or , and R9 to R 13 can independently be hydrogen, deuterium, or an unsubstituted C1-C6 alkyl group).

[0164] For any formula described herein, when present, the alkyl group can be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group (monocyclic or polycyclic). The terms "cyclic alkyl group" and "cycloalkyl group" are used interchangeably herein. Exemplary alkyl groups include straight-chain C1-C 12 alkyl groups, branched-chain C4-C 12 alkyl groups, cyclic C3-C 12 alkyl groups, straight-chain C1-C 10 alkyl groups, branched-chain C4-C 10 alkyl groups, cyclic C3-C 10 alkyl groups, straight-chain C1-C8 alkyl groups, branched-chain C4-C8 alkyl groups, cyclic C3-C8 alkyl groups, straight-chain C1-C6 alkyl groups, branched-chain C4-C6 alkyl groups, cyclic C3-C6 alkyl groups, straight-chain C1-C4 alkyl groups, cyclic C3-C4 alkyl groups, such as straight-chain C1-C 10 、C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3 or C1-C2 alkyl groups, branched-chain C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5 or C3-C4 alkyl groups, or cyclic C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5 or C3-C4 alkyl groups. The cyclic alkyl group can be a monocyclic or polycyclic alkyl group, such as C4-C 12 、C4-C 10 、C4-C9, C4-C8, C4-C7, C4-C6 or C4-C5 monocyclic or polycyclic alkyl groups. In some forms, the alkyl group can be methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl or n-butyl.

[0165] For any formula described herein, when present, the alkenyl group can be a straight-chain alkenyl group, a branched-chain alkenyl group, or a cyclic alkenyl group (monocyclic or polycyclic). The terms "cyclic alkenyl group" and "cycloalkenyl group" are used interchangeably herein. Exemplary alkenyl groups include straight-chain C2-C 12 alkenyl groups, branched-chain C4-C 12 alkenyl groups, cyclic C3-C 12 alkenyl groups, straight-chain C2-C 10 alkenyl groups, branched-chain C4-C 10 alkenyl groups, cyclic C3-C 10 alkenyl groups, straight-chain C2-C8 alkenyl groups, branched-chain C4-C8 alkenyl groups, cyclic C3-C8 alkenyl groups, straight-chain C2-C6 alkenyl groups, branched-chain C4-C6 alkenyl groups, cyclic C3-C6 alkenyl groups, straight-chain C2-C4 alkenyl groups, cyclic C3-C4 alkenyl groups, such as straight-chain C2-C 10, C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3 alkenyl, branched C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4 alkenyl, or cyclic C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4 alkenyl. The cyclic alkenyl can be a monocyclic or polycyclic alkenyl, such as C4-C 12 , C4-C 10 , C4-C9, C4-C8, C4-C7, C4-C6 or C4-C5 monocyclic or polycyclic alkenyl.

[0166] For any chemical formula described herein, when present, the alkynyl can be a straight-chain alkynyl, a branched alkynyl or a cyclic alkynyl (monocyclic or polycyclic). The terms "cyclic alkynyl" and "cycloalkynyl" are used interchangeably herein. Exemplary alkynyls include straight-chain C2-C 12 alkynyl, branched C4-C 12 alkynyl, cyclic C3-C 12 alkynyl, straight-chain C2-C 10 alkynyl, branched C4-C 10 alkynyl, cyclic C3-C 10 alkynyl, straight-chain C2-C8 alkynyl, branched C4-C8 alkynyl, cyclic C3-C8 alkynyl, straight-chain C2-C6 alkynyl, branched C4-C6 alkynyl, cyclic C3-C6 alkynyl, straight-chain C1-C4 alkynyl, cyclic C3-C4 alkynyl, such as straight-chain C2-C 10 , C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3 alkynyl, branched C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4 alkynyl, or cyclic C3-C9, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4 alkynyl. The cyclic alkynyl can be a monocyclic or polycyclic alkynyl, such as C4-C 12 , C4-C 10 , C4-C9, C4-C8, C4-C7, C4-C6 or C4-C5 monocyclic or polycyclic alkynyl.

[0167] For any formula described herein, when present, the aryl can be C4-C 30 aryl, C4-C 20 aryl, C4-C 12 aryl, C4-C 11 aryl, C4-C9 aryl, C5-C 30 aryl, C5-C 20 aryl, C5-C 12 aryl, C5-C11 Aryl, C5-C9 aryl, C6-C 20 Aryl, C6-C 12 Aryl, C6-C 11 Aryl or C6-C9 aryl. It should be understood that the aryl can be heteroaryl, such as C4-C 30 Heteroaryl, C4-C 20 Heteroaryl, C4-C 12 Heteroaryl, C4-C 11 Heteroaryl, C4-C9 heteroaryl, C5-C 30 Heteroaryl, C5-C 20 Heteroaryl, C5-C 12 Heteroaryl, C5-C 11 Heteroaryl, C5-C9 heteroaryl, C6-C 30 Heteroaryl, C6-C 20 Heteroaryl, C6-C 12 Heteroaryl, C6-C 11 Heteroaryl or C6-C9 heteroaryl.

[0168] For any formula described herein, the polyaryl can be C8-C 30 Polyaryl, C8-C 20 Polyaryl, C8-C 12 Polyaryl, C8-C 11 Polyaryl, C 10 -C 30 Polyaryl, C 10 -C 20 Polyaryl, C 10 -C 12 Polyaryl, C 10 -C 11 Polyaryl or C 12 -C 20 Polyaryl. It should be understood that the aryl can be hetero-polyaryl, such as C 10 -C 30 Hetero-polyaryl, C 10 -C 20 Hetero-polyaryl, C 10 -C 12 Hetero-polyaryl, C 10 -C 11 Hetero-polyaryl, or C 12 -C 20 Hetero-polyaryl.

[0169] Exemplary platinum(II) complexes are presented below.

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] 。

[0183] The photophysical properties of the platinum(II) complexes disclosed herein can be evaluated by a number of parameters such as emission lifetime (“τ em ” or “τ”), radiative decay rate (“k r ”), emission quantum yield (“Φ em ”), and / or maximum emission wavelength (“λ max ”).

[0184] Techniques for measuring τ em , k r , Φ em and λ max of platinum(II) complexes are known. For example, these parameters can be obtained by measuring the emission spectra of platinum(II) complexes. For example, based on the measured emission decay profile, τ em of a platinum(II) complex can be obtained as follows: (i) monitoring the emission decay intensity as a function of time using a Quanta Ray GCR 150-10 pulsed Nd:YAG laser system (pulse output: 355 nm), and (ii) determining τ em by fitting an exponential decay of Equation (1) using Origin software, where I0 is the initial emission intensity, I(t) is the emission intensity at time t, τ is the emission lifetime, and t is time.

[0185]

[0186] k rcan be used for k r = Ф em / τ em to obtain. The Ф values of these Pt complexes can be measured by known methods, such as direct measurement or relative methods. For example, the Ф em value of the platinum(II) complex in solution or film can be directly obtained by absolute measurement using a Hamamatsu C11347 Quantaurus-QY absolute PL quantum yield spectrometer (PL stands for photoluminescence). For example, the Ф em value is directly given by the software provided with the instrument. The λ em of the platinum(II) complex can be measured directly from the emission spectrum. max

[0187] Exemplary solutions suitable for measuring τ em 、k r 、Ф em and / or λ max of platinum(II) complexes include solutions containing organic solvents. Exemplary organic solvents suitable for forming the measurement solution include, but are not limited to, dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, chlorobenzene, and toluene, and combinations thereof. Optionally, the solution for measuring τ em 、k r 、Ф em and / or λ max of platinum(II) complexes is degassed with an inert gas (such as nitrogen, argon, or helium or a combination thereof). Optionally, the solution for measuring τ em 、k r 、Ф em and / or λ max of platinum(II) complexes is deoxygenated by a known freeze-pump-thaw method.

[0188] Solutions for measuring τ em 、k r 、Ф em and / or λ max ​Suitable films include films having a thickness between 10 nm and 50 μm (including the end values), between 10 nm and 10 μm (including the end values), between 10 nm and 5 μm (including the end values), between 10 nm and 1 μm (including the end values), between 10 nm and 500 nm (including the end values), or between 10 nm and 200 nm (including the end values). The film may also contain an organic compound as a thermal material. Exemplary organic compounds that can be used as the host material in the film include, but are not limited to, 1,3-bis(N-carbazolyl)benzene (mCP), 3,3′-bis(9H-carbazol-9-yl)-1,1′-biphenyl (mCBP), poly(methyl methacrylate) (PMMA), polystyrene (PS), 2,8-bis(diphenylphosphoryl)dibenzofuran (PPF), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO).

[0189] In some forms, the platinum(II) complexes disclosed herein can have a maximum emission wavelength (λ max ) in the range of 420 nm to 490 nm, 430 nm to 490 nm, 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 465 nm, or 440 nm to 470 nm (e.g., 441 nm to 454 nm), optionally based on the emission spectrum of the platinum(II) complex as described above.

[0190] In some forms, the emission quantum yield (Ф em ) of the platinum(II) complexes disclosed herein can be at least 30%, at least 35%, at least 45%, at least 50%, at least 60%, at least 70%, in the range of 30% to 90%, in the range of 30% to 85%, in the range of 30% to 80%, in the range of 35% to 85%, in the range of 35% to 80%, in the range of 45% to 85%, in the range of 45% to 80%, in the range of 50% to 85%, or in the range of 50% to 80%, as measured at room temperature in a film, optionally based on the emission spectrum of the platinum(II) complex as described above.

[0191] In some forms, the emission lifetime (τ em ) of the platinum(II) complexes disclosed herein can be ≤5.5 μs, ≤5 μs, ≤4 μs, ≤3 μs, ≤2 μs, ≤1 μs, in the range of 0.5 μs to 5 μs, in the range of 1 μs to 5 μs, or in the range of 2 μs to 5 μs, e.g., about 2.25 μs, as measured at room temperature in a film, optionally based on the emission spectrum of the platinum(II) complex as described above.

[0192] In some forms, the radiative decay rate (k r ) of the platinum(II) complexes disclosed herein can be at least 1.0 × 10 5 s -1 , at least 1.5 × 10 5 s -1 , at least 2.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 4.0 × 10 5 s -1 , in the range of 1.5× 10 5 s -1 to 4.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 4.0 × 10 5 s -1 , or in the range of 3.0× 10 5 s -1 to 6.0 × 10 5 s -1 , such as about 3.4 × 10 5 s -1, The above was measured in the film at room temperature, optionally based on the emission spectrum of the platinum(II) complex as described above.

[0193] In some forms, the platinum(II) complexes disclosed herein can have a τ within any of the ranges described above em , k r , Ф em and / or λ max。

[0194] B. Devices Containing Platinum(II) Complexes

[0195] Organic light-emitting elements containing one or more platinum(II) complexes are described, such as light-emitting diodes (OLEDs) or light-emitting electrochemical cells (“LEECs”). Devices containing one or more OLEDs and the OLED containing one or more platinum(II) complexes include, but are not limited to, stationary visual display units, mobile visual display units, and illumination devices, such as smartphones, televisions, monitors, digital cameras, tablets, and lighting appliances, wearable devices, and medical monitoring devices that typically operate at room temperature.

[0196] In some forms, the platinum(II) complex can be incorporated into the light-emitting layer. The light-emitting layer can further contain one or more light-emitting organic dyes. When the organic dye is incorporated into the light-emitting layer, the platinum(II) complex and the dye can have any suitable weight ratio, such as 4:1, 8:1, 10:1, 12:1, 15:1, or 20:1. In some forms, the platinum(II) complex in the light-emitting layer acts as a sensitizer to transfer energy to the organic dye. In some forms, the platinum(II) complex has a higher singlet state than the organic dye.

[0197] In some forms, the light-emitting layer can be incorporated into an organic light-emitting element, such as an OLED. The organic light-emitting element can contain one or more light-emitting layers, and each light-emitting layer can contain one or more of the disclosed platinum(II) complexes. In some forms, when two or more light-emitting layers are included in the organic light-emitting element, the light-emitting layer or each light-emitting layer further contains one or more host materials, such as those described above. Typically, the total concentration of one or more host materials is greater than the total concentration of one or more platinum(II) complexes in the light-emitting layer or each light-emitting layer in two or more light-emitting layers. The term “total concentration of one or more platinum(II) complexes” refers to the sum of the weights of one or more platinum(II) complexes relative to the sum of the weights of all materials used in one light-emitting layer in an organic light-emitting device (such as an OLED). The term “total concentration of one or more host materials” refers to the sum of the weights of one or more host materials relative to the sum of the weights of all materials used in one light-emitting layer in an organic light-emitting device (such as an OLED).

[0198] The organic light-emitting device may contain an appropriate amount of a platinum(II) complex in the light-emitting layer of the device or in each of two or more light-emitting layers. For example, the total concentration of one or more platinum(II) complexes in the light-emitting layer or in each of two or more light-emitting layers is at most 20 wt%, at most 10 wt%, at least 1 wt%, in the range of about 1 wt% to about 20 wt%, in the range of about 1 wt% to about 10 wt%, in the range of about 2 wt% to about 20 wt%, or in the range of about 2 wt% to about 10 wt%, such as about 2 wt, about 6 wt%, or about 10 wt%.

[0199] In some forms, the organic light-emitting element (e.g., OLED) may further include an anode, a cathode, a hole transport region, and / or an electron transport region. The hole transport region may include a hole injection layer and / or a hole transport layer and optionally an electron blocking layer. The electron transport region may include an electron transport layer and / or an electron injection layer and optionally a hole blocking layer. The light-emitting layer may be located between the anode and the cathode. The hole transport region may be located between the anode and the light-emitting layer. The electron transport region may be located between the cathode and the light-emitting layer. The specific elements and the arrangement of the elements in each hole transport region and electron transport region depend on the specific use.

[0200] Figure 6 An exemplary OLED containing the disclosed platinum(II) complex is shown. As Figure 6 shown, the exemplary OLED 100 includes multiple layers, from bottom to top, a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an optional electron blocking layer 105, an emission layer 106, an optional hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, and a cathode 110. The emission layer 106 is formed of one or more platinum(II) complexes disclosed herein. Suitable materials for forming the anode, hole injection layer, hole transport layer, optional electron blocking layer, optional hole blocking layer, electron transport layer, electron injection layer, and cathode are known in the art, see, for example, those described in Hong, et al., Adv. Mater. 2021, 2005630; Lee, et al., InfoMat. 2021, 3, 61 - 81; and Jou, et al., J. Mater. Chem. C, 2015, 3, 2974 - 3002. The size of each layer in the OLED, such as the shape, length, width, and / or thickness of each layer, may vary according to the specific use of the OLED. More specific exemplary OLEDs are described in the following examples.

[0201] These organic light-emitting devices containing the disclosed platinum(II) complexes may be in the blue region (λmax Emitting with high performance in the range of 420 nm to 490 nm, such as 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 480 nm, 440 nm to 480 nm, 450 nm to 480 nm, 460 nm to 480 nm, or 470 nm to 480 nm). The performance of the OLED containing the disclosed platinum(II) complex can be evaluated using known parameters, such as maximum brightness (L), current efficiency (CE) at 1000 cd m -2 , power efficiency (PE) at 1000 cd m -2 , and / or external quantum efficiency (EQE) at 1000 cd m -2 .

[0202] Techniques for measuring brightness, current efficiency, power efficiency, and / or external quantum efficiency are known. For example, the maximum brightness is measured at which any increase in voltage does not result in an increase in brightness (if the voltage is further increased, the device may burn out). For example, the EQE, CE, and PE of an electroluminescent device can be obtained by using a Keithley 2400 source meter and an absolute external quantum efficiency measurement system (C9920-12, Hamamatsu Photonics), where all devices can be encapsulated in a 200 nm thick Al2O3 film deposited by atomic layer deposition (ALD) in a Kurt J. Lesker SPECTROS system before measurement.

[0203] In some forms, an OLED containing 2 wt% to 10 wt% of the disclosed platinum(II) complex can emit in the blue region (λ max in the range of about 420 nm to about 490 nm, such as in the range of 470 nm to 480 nm), with a maximum brightness (L) of at least 3000 cd m -2 , at least 4000 cd m -2 , at least 5000 cd m -2 , at least 6000 cd m -2 , at least 8000 cdm -2 , in the range of 3000 cd m -2 to 50000 cd m -2 , in the range of 3000 cd m -2 to 40000 cd m -2 , in the range of 3000cd m -2 to 30000 cd m -2 , in the range of 3000 cd m -2from 0 to 25000 cd m -2 within the range, or between 3000 cd m -2 and 15000 cd m -2 within the range.

[0204] In some forms, an OLED containing 2 wt% to 10 wt% of the disclosed platinum(II) complex can emit in the blue region (λ max in the range of about 420 nm to about 490 nm, for example in the range of 470 nm to 480 nm), with a CE of at least 20 cd A -2 at 1000 cd m -1 , at least 25 cd / A, in the range of 20 cd / A to 50 cd / A, or in the range of 20 cd / A to 45 cd / A.

[0205] In some forms, an OLED containing 2 wt% to 10 wt% of the disclosed platinum(II) complex can emit in the blue region (λ max in the range of about 420 nm to about 490 nm, for example in the range of 470 nm to 480 nm), with a PE of at least 20 lm / W 2 at 1000 cd / m, in the range of 20 lm / W to 50 lm / W, or in the range of 20 lm / W to 45 lm / W.

[0206] In some forms, an OLED containing 2 wt% to 10 wt% of the disclosed platinum(II) complex can emit in the blue region (λ max in the range of about 420 nm to about 490 nm, for example in the range of 470 nm to 480 nm), with an EQE of at least 10%, at least 15%, in the range of 10% to 35%, in the range of 10% to 30%, in the range of 10% to 25%, in the range of 15% to 35%, in the range of 15% to 30%, in the range of 15% to 25%, in the range of 20% to 30%, or in the range of 15% to 20%, for example about 20% 2 at 1000 cd / m.

[0207] In some forms, an OLED containing 2 wt% to 10 wt% of the disclosed platinum(II) complex can emit in the blue region (λ max in the range of about 420 nm to about 490 nm, for example in the range of 470 nm to 480 nm), with a maximum brightness (L), a CE at 1000 cd m -2 , a PE at 1000 cd / m 2 and / or a PE at 1000 cd / m2 The EQE at [specific time] is within any of the above ranges.

[0208] More specific examples of the maximum luminance, current efficiency, power efficiency, and external quantum efficiency of exemplary OLEDs containing exemplary platinum(II) complexes are described in the following examples.

[0209] III. Preparation Methods and Their Reagents

[0210] A. Platinum(II) Complexes

[0211] The platinum(II) complexes and ligands described herein can be synthesized using methods known in the field of organic chemical synthesis. For example, ligands can be purchased from commercial chemical manufacturers or can be prepared according to procedures reported and / or adapted in the literature. Those skilled in the art of synthesis know the selection of appropriate synthesis conditions, reagents, post-reaction work-up conditions, and purification techniques (as needed).

[0212] Exemplary syntheses of the carbene ligands L1 to L8 and Pt(II) complexes Pt-1 to Pt-8 are shown below and discussed in the examples.

[0213]

[0214]

[0215] The reaction conditions are as follows: (i) NaH, room temperature for 0.5 h, DMF; (ii) overnight at room temperature; (iii) H2, Pd / C, EtOH, room temperature for 2 h; (iv) HCOOH, reflux for 12 h; (v) CH2Br2, 120°C for 72 h; (vi) BBr3, DCM, 0°C to room temperature for 12 h; (vii) Pt(COD)Cl2, NEt3, EtOH, reflux for 6 h.

[0216] B. Organic Light-Emitting Devices

[0217] Also described is a method of manufacturing an organic light-emitting device (e.g., an OLED) that contains one or more of the platinum(II) complexes described herein. As described above, methods of preparing OLEDs containing one or more platinum(II) complexes are well known in the field of organic electronics. Such methods of manufacturing OLEDs can involve vacuum deposition or solution processing techniques such as spin coating and inkjet printing. The selection of suitable materials (anodes, cathodes, hole transport layers, electron transport layers, etc.) and manufacturing parameters (e.g., deposition conditions or solvent selection) required to manufacture OLEDs containing the platinum(II) complexes described herein are known in the art. In some forms, the preparation of OLEDs can be carried out by vacuum deposition or solution processing techniques such as spin coating and ink printing (e.g., inkjet printing or roll-to-roll printing). Exemplary and non-limiting methods of manufacturing OLEDs containing one or more platinum(II) complexes are described in the Examples.

[0218] IV. Methods of Use

[0219] The platinum(II) complexes described herein emit in the blue spectral region (λ max between 420 nm and 490 nm, such as 441 - 454 nm), with a high emission quantum yield (i.e., Ф em ≥ 30%, such as 30% to 90%, 30% to 85%, or 30% to 80%), a short emission lifetime (i.e., τ em or τ ≤ 5.5 μs or ≤ 5 μs and at least about 2 μs, such as about 2.25 μs), and / or a fast radiative decay rate (i.e., k r ≥ 1.0×10 5 s -1 and at most about 6.0×10 5 s -1 , such as about 3.4×10 5 s -1 ), as measured in a film at room temperature or other low temperatures (e.g., temperatures in the range of 285 K to 300 K).

[0220] The platinum(II) blue emitters can be incorporated into organic electronic devices, which include but are not limited to OLEDs or light-emitting electrochemical cells (LEECs). OLEDs using the platinum(II) complexes can emit electroluminescence in the blue spectral region (λ max between about 400 - 500 nm, such as 470 - 480 nm), with a high EQE of at least 10% at 1000 cd m -2 , such as 10 - 35% at 1000 cdm -2 , such as about 20% at 1000 cd m -2 .

[0221] Such OLEDs can be used in commercial applications such as smartphones, TVs, displays, digital cameras, tablets, lighting fixtures for normal room temperature operation, stationary visual display units, mobile visual display units, lighting units, keyboards, clothes, ornaments, clothing accessories, wearable devices, medical monitoring devices, wallpapers, tablet PCs, laptop computers, advertising panels, panel display units, household appliances, and office appliances.

[0222] The disclosed Pt(II) complexes, devices, and methods can be further understood through the paragraphs enumerated below.

[0223] Paragraph 1. A platinum(II) complex having the following structure:

[0224] ,

[0225] wherein:

[0226] (i) Each occurrence of X1 to X4 is independently nitrogen or CR 16 ;

[0227] (ii) Each occurrence of R1 to R8 and R 16 are independently hydrogen, deuterium, halide (such as fluoride, chloride, bromide, iodide, etc.), hydroxyl, amino, amide, thiol, cyano, nitro, alkoxy, carbonyl, substituted or unsubstituted C1 - C 12 alkyl, substituted or unsubstituted C1 - C 12 alkenyl, substituted or unsubstituted C1 - C 12 alkynyl, substituted or unsubstituted aryl (such as phenyl), substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero - polyaryl, or two adjacent groups among R1 to R8 and R 16 can together form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero - polyaryl with the carbon atom to which they are attached;

[0228] (iii) n1 is an integer from 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2;

[0229] (iv) R 14 and R 15 are independently hydrogen, deuterium, substituted or unsubstituted C1 - C 12 alkyl, substituted or unsubstituted C1 - C 12 alkenyl, or substituted or unsubstituted C1 - C 12 alkynyl, or R 14 and R 15They may together with the carbon atoms to which they are attached form a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted hetero-polyaryl; and

[0230] (v) When present, the substituents are independently unsubstituted C1-C 12 alkyl, unsubstituted C1-C 12 alkenyl, unsubstituted C1-C 12 alkynyl, unsubstituted aryl (such as phenyl), aryl (such as phenyl) substituted by one or more unsubstituted aryl (such as unsubstituted phenyl) and / or one or more unsubstituted alkyl (such as unsubstituted C1-C 12 alkyl), unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero-polyaryl, hetero-polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, amino, or halide.

[0231] Paragraph 2. The platinum(II) complex of Paragraph 1, wherein the platinum(II) has the following structure:

[0232] .

[0233] Paragraph 3. The platinum(II) complex of Paragraph 1, wherein X1 and X4 are independently nitrogen or CR 16 ; X2 and X3 are CR 16 ; R 16 is hydrogen, deuterium, halide, unsubstituted C1-C 12 alkyl, unsubstituted aryl or aryl substituted by one or more unsubstituted C1-C 12 alkyl; R2-R5 are independently hydrogen, deuterium, amino, unsubstituted C1-C 12 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl, or R2 and R3, R3 and R4 or R4 and R5 together with the carbon atoms to which they are attached form a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted hetero-polyaryl; and when present, the substituents are independently unsubstituted C1-C 12alkyl, unsubstituted aryl (e.g., phenyl), aryl (e.g., phenyl) substituted with one or more unsubstituted aryl (e.g., phenyl) and / or one or more unsubstituted alkyl, unsubstituted heteroaryl, heteroaryl substituted with one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted with one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero - polyaryl, hetero - polyaryl substituted with one or more unsubstituted aryl and / or one or more unsubstituted alkyl, or amino.

[0234] Paragraph 4. The platinum(II) complex of Paragraph 1 or 2, wherein each occurrence of R1 - R8 is independently hydrogen, deuterium, halide, substituted or unsubstituted C1 - C 12 alkyl, substituted or unsubstituted C1 - C 12 alkenyl, substituted or unsubstituted C1 - C 12 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero - polyaryl.

[0235] Paragraph 5. The platinum(II) complex of Paragraph 4, wherein each occurrence of R1 - R8 is independently hydrogen, deuterium, halide, substituted or unsubstituted C1 - C 12 alkyl, or substituted or unsubstituted aryl.

[0236] Paragraph 6. The platinum(II) complex of Paragraph 4 or Paragraph 5, wherein each occurrence of R1 - R8 is independently hydrogen, deuterium, halide (e.g., fluoride, chloride or bromide), unsubstituted C1 - C 12 alkyl (e.g., unsubstituted C1 - C6 alkyl, unsubstituted C1 - C4 alkyl or unsubstituted C1 - C3 alkyl, such as methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, tert - butyl, etc.), or , and wherein R9 - R 13 are independently hydrogen, deuterium, unsubstituted C1 - C 12 alkyl, unsubstituted phenyl, unsubstituted hetero - polyaryl, or amino, optionally wherein R9 - R 13 are independently hydrogen, deuterium or unsubstituted C1 - C6 alkyl (such as methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, tert - butyl, etc.).

[0237] Paragraph 7. The platinum(II) complex according to any one of Paragraphs 1 - 6, wherein the platinum(II) complex has any one of the following structures:

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] 。

[0251] Paragraph 8. The platinum(II) complex according to any one of paragraphs 1 to 7, wherein the maximum emission wavelength (λ max ) of the platinum(II) complex is in the range of 420 nm to 490 nm, 430 nm to 490 nm, 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 465 nm, or 440 nm to 470 nm, for example, in the range of 441 nm to 454 nm.

[0252] Paragraph 9. The platinum(II) complex according to any one of paragraphs 1 to 8, wherein the emission quantum yield (Ф em ) of the platinum(II) complex is at least 30%, at least 35%, at least 45%, at least 50%, at least 60%, at least 70%, in the range of 30% to 90%, in the range of 30% to 85%, in the range of 30% to 80%, in the range of 35% to 85%, in the range of 35% to 80%, in the range of 45% to 85%, in the range of 45% to 80%, in the range of 50% to 85%, or in the range of 50% to 80%, as measured in a film at room temperature.

[0253] Paragraph 10. The platinum(II) complex according to any one of paragraphs 1 to 9, wherein the emission lifetime (τ em) is ≤ 5.5 μs or ≤ 5 μs, ≤ 4 μs, ≤ 3 μs, ≤ 2 μs, ≤ 1 μs, in the range of 0.5 μs to 5 μs, in the range of 1 μs to 5 μs, or in the range of 2 μs to 5 μs, for example, about 2.25 μs, which is measured in the film at room temperature.

[0254] Paragraph 11. The platinum(II) complex according to any one of paragraphs 1 to 10, wherein the radiative decay rate (k r ) is at least 1.0 × 10 5 s -1 , at least 1.5 × 10 5 s -1 , at least 2.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 4.0× 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 4.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 4.0 ×10 5 s-1 within, or at 3.0 × 10 5 s -1 to 6.0 × 10 5 s -1 within, for example, about 3.4 × 10 5 s -1 , as measured in the film at room temperature.

[0255] Paragraph 12. An organic light-emitting device comprising a light-emitting layer or two or more light-emitting layers, wherein each light-emitting layer in the light-emitting layer or two or more light-emitting layers contains one or more platinum(II) complexes described in any one of Paragraphs 1 to 11, and optionally wherein the organic light-emitting device emits light in the blue spectral region.

[0256] Paragraph 13. The organic light-emitting device of Paragraph 12, wherein the total concentration of one or more platinum(II) complexes in each light-emitting layer in the light-emitting layer or two or more light-emitting layers is at most 20 wt%, at most 10 wt%, at least 1 wt%, within a range of about 1 wt% to about 20 wt%, within a range of about 1 wt% to about 10 wt%, within a range of about 2 wt% to about 20 wt% or about 2 wt% to about 10 wt%, for example, about 2 wt%, about 6 wt% or about 10 wt%.

[0257] Paragraph 14. The organic light-emitting device of Paragraph 12 or 13, which further comprises an anode, a cathode, a hole transport region and an electron transport region,

[0258] wherein the hole transport region contains a hole injection layer and / or a hole transport layer, and optionally an electron blocking layer,

[0259] wherein the electron transport region contains an electron transport layer and / or an electron injection layer, and optionally a hole blocking layer,

[0260] wherein the light-emitting layer is located between the anode and the cathode,

[0261] wherein the hole transport region is located between the anode and the light-emitting layer, and

[0262] wherein the electron transport region is located between the cathode and the light-emitting layer.

[0263] Paragraph 15. The organic light-emitting device according to any one of Paragraphs 12 to 14, wherein the organic light-emitting device emits light in the blue region, optionally at λ max , the λ maxIn the range of 420 nm to 490 nm, such as 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 480 nm, 440 nm to 480 nm, 450 nm to 480 nm, 460 nm to 480 nm, or 470 nm to 480 nm.

[0264] Paragraph 16. The organic light-emitting element according to any one of paragraphs 12 to 15, wherein the maximum brightness (L) of the organic light-emitting element is at least 3000 cd m -2 , at least 4000 cd m -2 , at least 5000 cd m -2 , at least 6000 cd m -2 , at least 8000 cd m -2 , in the range of 3000 cd m -2 to 50000 cd m -2 , in the range of 3000 cd m -2 to 40000 cd m -2 , in the range of 3000 cd m -2 to 30000 cd m -2 , in the range of 3000 cd m -2 to 25000 cd m -2 , or in the range of 3000 cd m -2 to 15000 cd m -2 .

[0265] Paragraph 17. The organic light-emitting element according to any one of paragraphs 12 to 16, wherein the current efficiency (CE) of the organic light-emitting element at 1000 cd / m 2 is at least 20 cd A -1 , at least 25 cd / A, in the range of 20 cd / A to 50 cd / A, or in the range of 20 cd / A to 45 cd / A.

[0266] Paragraph 18. The organic light-emitting element according to any one of paragraphs 12 to 17, wherein the power efficiency (PE) of the organic light-emitting element at 1000 cd / m 2 is at least 20 lm / W, in the range of 20 lm / W to 50 lm / W, or in the range of 20 lm / W to 45 lm / W.

[0267] Paragraph 19. The organic light-emitting element according to any one of paragraphs 12 to 18, wherein the organic light-emitting element at 1000 cd / m 2The external quantum efficiency (EQE) at [time] is at least 10%, at least 15%, in the range of 10% to 35%, in the range of 10% to 30%, in the range of 10% to 25%, in the range of 15% to 35%, in the range of 15% to 30%, in the range of 15% to 25%, in the range of 20% to 30%, or in the range of 15% to 20%, for example, about 20%.

[0268] Paragraph 20. The organic light-emitting device according to any one of paragraphs 12 to 19, wherein the organic light-emitting device is an organic light-emitting diode ("OLED") or a light-emitting electrochemical cell ("LEEC").

[0269] Paragraph 21. The organic light-emitting device according to any one of paragraphs 12 to 20, wherein each light-emitting layer of the light-emitting layer or two or more light-emitting layers further comprises an organic dye, and wherein one or more platinum(II) complexes act as sensitizers to transfer energy to the organic dye.

[0270] Paragraph 22. The organic light-emitting device according to any one of paragraphs 12 to 20, wherein each light-emitting layer of the light-emitting layer or two or more light-emitting layers further comprises an organic dye, and wherein one or more platinum(II) complexes have a higher singlet state than the organic dye.

[0271] Paragraph 23. The organic light-emitting device according to any one of paragraphs 12 to 22, wherein each light-emitting layer of the light-emitting layer or two or more light-emitting layers is formed by vacuum evaporation deposition, spin coating, ink printing, or roll-to-roll printing.

[0272] Paragraph 24. A device comprising one or more organic light-emitting devices according to any one of paragraphs 12 to 23, wherein the device is a stationary visual display unit, a mobile visual display unit, a lighting device, a wearable device, a light therapy device, or a medical monitoring device.

[0273] Examples

[0274] Example 1. Synthesis and Characterization of Exemplary Platinum(II) Complexes and OLEDs Incorporating the Platinum(II) Complexes

[0275] Efficient blue emitters are based on Pt(II) complexes containing Pt(II) atoms coordinated by ligands containing benzimidazole-based NHC and phenolate moieties. In some forms, the phenolate moiety of the ligand contains one or more large substituents, such as large phenyl groups, such as 3,5-di-tert-butyl-phenyl (ditBuPh) and 2,6-dimethyl-phenyl (diMePh). Without being bound by any theory, the geometric structure of these Pt(II) complexes (e.g., reduced planarity and altered orientation between the NHC and phenolate rings) and the extended π-conjugation of the acceptor unit allow for improved emission properties of the Pt(II) complexes, such as increased emission quantum yield and radiative decay rate constant compared to previously reported imidazole-based Pt(II)-O^C*^C*^O complexes. The exemplary Pt(II) complexes described herein demonstrate that such Pt(II) complexes emit in the blue region, with high emission quantum yield (i.e., Ф em ≥ 30%, e.g., 30% to 90%, 30% to 85%, or 30% to 80%, measured in film), short emission lifetime (i.e., τ em or τ ≤ 5.5 μs or ≤ 5 μs and at least about 2 μs, e.g., about 2.25 μs), and / or fast radiative decay rate (i.e., k r ≥ 1.0×10 5 s -1 and at most about 6.0×10 5 s -1 , e.g., about 3.4×10 5 s -1 ), as measured in film at room temperature. The results of doped OLEDs using the exemplary Pt(II) emitters demonstrate electroluminescence in the blue spectral region (λ max at about 420 - 490 nm, e.g., 470 - 480 nm), with an EQE of 10 - 35% at 1000 cd m -2 , e.g., about 20% at 1000 cd m -2 .

[0276] Materials and Methods

[0277] Synthesis and Characterization of Exemplary Pt(II) Complexes

[0278] Unless otherwise specified, the solvents used for synthesis are of analytical grade. Anhydrous solvents can be obtained commercially from J&K Scientific Co., Ltd, Beijing. NMR spectra were recorded on Advance Neo 400, Advance III HD500 and Advance Neo 600 Bruker FT-NMR spectrometers. Chemical shifts were calibrated relative to the solvent residual signal or relative to the signal of tetramethylsilane. All NMR measurements were carried out at room temperature. High-resolution mass spectrometry (ESI-MS) was measured on a Bruker impact II Q TOF mass spectrometer. Elemental analysis was performed at the Beijing Institute of Chemistry, Chinese Academy of Sciences.

[0279] In the synthetic procedures described below, as an example procedure, the precursors of 4 are illustrated, and unless otherwise specified, the precursors of the corresponding steps in other complexes are carried out as shown in 5.

[0280] Scheme 1. Synthesis of 3-methoxy-2',6'-dimethyl-N-(2-nitrophenyl)-[1,1'-biphenyl]-4-amine (4b)

[0281]

[0282] In a 250 mL three-necked round-bottom flask, 1.45 g (6.38 mmol, 1 equiv) of 3-methoxy-2',6'-dimethyl-[1,1'-biphenyl]-4-amine (4a) was dissolved in 25 mL of anhydrous DMF. At room temperature, under a stream of argon, 0.57 g (14.3 mmol, 2.2 equiv, 60 wt% in mineral oil) of NaH was slowly added to the solution over 10 min. The suspension was stirred for 0.5 h, and 0.81 mL (7.66 mmol, 1.2 equiv) of 1-fluoro-2-nitrobenzene was added dropwise over 10 min to give a purple suspension. After stirring at room temperature for 16 h, the mixture was diluted with diethyl ether and quenched with saturated NH4Cl solution. The organic layer was diluted with 200 mL of ether, washed three times with saturated NaCl solution, combined, dried over MgSO4, and purified using a silica gel column (eluent: n-hexane:DCM = 5 / 1). After evaporation, 1.79 g of an orange solid was obtained (yield: 81%). 11H NMR (500 MHz, CDCl3) δ 9.52 (s, 1H), 8.22 (d, J = 8.6 Hz, 1H), 7.42 (dd, J = 14.6, 7.4 Hz, 2H), 7.36 (d, J = 8.6 Hz, 1H), 7.23 - 7.16 (m, 1H), 7.14 (d, J = 7.3 Hz, 2H), 6.85 - 6.72 (m, 3H), 3.85 (s, 3H), 2.11 (s, 6H).

[0283]

[0284] Yield: 49%. 1 1H NMR (400 MHz, CDCl3) δ 9.45 (s, 1H), 8.20 (dd, J = 8.6, 1.5 Hz, 1H), 7.43 - 7.33 (m, 2H), 7.29 - 7.23 (m, 1H), 7.22 - 7.14 (m, 1H), 7.08 - 6.88 (m, 2H), 6.77 (ddd, J = 8.4, 6.9, 1.2 Hz, 1H), 3.88 (s, 3H).

[0285]

[0286] Yield: 93%. 1 1H NMR (400 MHz, CDCl3) δ 9.37 (s, 1H), 8.23 (dd, J = 8.6, 1.3 Hz, 1H), 7.49 - 7.38 (m, 1H), 7.24 - 7.19 (m, 1H), 6.95 (dd, J = 8.5, 3.0 Hz, 1H), 6.90 (dd, J = 10.7, 3.1 Hz, 1H), 6.87 - 6.81 (m, 1H), 3.71 (s, 3H), 1.40 (s, 9H). 19 19F NMR (377 MHz, CDCl3) δ -117.36 - -117.50 (m).

[0287]

[0288] Yield: 58%. 11H NMR (400 MHz, CDCl3) δ 9.51 (s, 1H), 8.22 (dd, J = 8.6, 1.4 Hz, 1H), 7.46 (t, J = 1.8 Hz, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.41 (d, J = 1.8 Hz, 2H), 7.40 - 7.33 (m, 2H), 3.95 (s, 3H), 1.40 (s, 18H).

[0289]

[0290] Yield: 18%. 1 1H NMR (500 MHz, CDCl3) δ 9.48 (s, 1H), 8.43 (d, J = 2.2 Hz, 1H), 7.65 (dd, J = 8.9, 2.2 Hz, 1H), 7.45 - 7.41 (m, 2H), 7.37 (dd, J = 8.9, 5.3 Hz, 3H), 7.21 - 7.16 (m, 1H), 7.03 - 6.97 (m, 2H), 3.90 (s, 3H), 1.38 (s, 18H).

[0291]

[0292] Yield: 41%. 1 1H NMR (500 MHz, CDCl3) δ 9.50 (s, 1H), 8.02 (s, 1H), 7.46 (d, J = 7.6 Hz, 1H), 7.37 (d, J = 8.8 Hz, 1H), 7.18 (dd, J = 11.6, 7.8 Hz, 3H), 7.11 (d, J = 7.3 Hz, 2H), 7.02 (d, J = 8.4 Hz, 2H), 3.91 (s, 3H), 2.08 (s, 6H).

[0293]

[0294] Yield: 71%. 11H NMR (500 MHz, CDCl3) δ 9.52 (s, 1H), 8.19 (dd, J = 8.6, 1.4 Hz, 1H), 7.38 - 7.32 (m, 1H), 7.30 (dd, J = 8.6, 1.2 Hz, 1H), 7.21 - 7.14 (m, 2H), 7.11 (d, J = 7.4 Hz, 2H), 7.05 (d, J = 8.3 Hz, 1H), 6.94 (dd, J = 8.3, 2.0 Hz, 1H), 6.75 (ddd, J = 8.4, 6.8, 1.4 Hz, 1H), 3.93 (s, 3H), 2.10 (s, 6H). HRMS (ESI) [M+H] + : Calculated m / z 349.1554, found 349.1544.

[0295]

[0296] Yield: 70%. 1 1H NMR (400 MHz, CDCl3) δ 9.50 (s, 1H), 8.19 (d, J = 8.5 Hz, 1H), 7.39 - 7.27 (m, 3H), 7.20 (d, J = 7.3 Hz, 3H), 7.03 (d, J = 8.3 Hz, 1H), 6.94 (d, J = 8.3 Hz, 1H), 6.75 (t, J = 7.6 Hz, 1H), 3.95 (s, 3H), 2.73 (dt, J = 13.7, 6.8 Hz, 2H), 1.12 (dd, J = 6.7, 2.6 Hz, 12 H). HRMS (ESI) [M+H] + : Calculated m / z 405.2180, found 405.2170.

[0297] Scheme 2. Synthesis of 1-(3-methoxy-2',6'-dimethyl-[1,1'-biphenyl]-4-yl)-1H-benzo[d]imidazole (4c)

[0298]

[0299] In a 300 mL round-bottom flask, 3.58 g (10.3 mmol, 1 equiv) of 3-methoxy-2',6'-dimethyl-N-(2-nitrophenyl)-[1,1'-biphenyl]-4-amine (4b) was dissolved in 150 mL of ethanol, and 0.79 g of Pd / C (10 wt%) was added. The mixture was purged with hydrogen and stirred at room temperature for 1 h. After the complete conversion of 4b, the mixture was passed through celite with DCM as the eluent and concentrated under reduced pressure. 25 mL (0.66 mol, 64 equiv) of HCOOH was added and refluxed for 12 h. After completion was confirmed by TLC, the reaction was quenched with NaHCO3 solution, extracted three times with DCM, and dried over Na2SO4. The solvent was removed under reduced pressure, and the product was purified by flash column chromatography on silica gel (eluent: hexane / acetone = 4 / 1) to give an off-white solid (yield: 2.89 g, 86%). 1 1H NMR (400 MHz, CDCl3) δ 8.19 (s, 1H), 7.89 (d, J = 7.1 Hz, 1H), 7.48(d, J = 8.2 Hz, 1H), 7.42 - 7.37 (m, 1H), 7.37 - 7.31 (m, 2H), 7.25 - 7.20(m, 1H), 7.17 (d, J = 7.4 Hz, 2H), 6.92 (d, J = 6.5 Hz, 2H), 3.78 (s, 3H),2.14 (s, 6H).

[0300]

[0301] Yield: 93%. 1 1H NMR (400 MHz, CDCl3) δ 8.08 (s, 1H), 7.87 (d, J = 8.5 Hz,1H), 7.50 - 7.38 (m, 2H), 7.31 (s, 1H), 7.29 (t, J = 1.8 Hz, 2H), 7.13 (d, J= 7.9 Hz, 2H), 3.80 (s, 3H).

[0302]

[0303] Yield: 85%. 11H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H), 7.94 - 7.85 (m, 1H), 7.43 - 7.34 (m, 3H), 7.17 (dd, J = 10.5, 3.1 Hz, 1H), 7.03 (dd, J = 7.6, 3.1 Hz, 1H), 3.06 (s, 3H), 1.44 (s, 9H). 19 19F NMR (377 MHz, CDCl3) δ -116.83 (dd, J = 10.5, 7.8 Hz).

[0304]

[0305] Yield: 97%. 1 1H NMR (400 MHz, CDCl3) δ 8.12 (s, 1H), 7.93 - 7.83 (m, 1H), 7.52 (t, J = 1.7 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 1.7 Hz, 2H), 7.37 (d, J = 2.5 Hz, 1H), 7.32 (dt, J = 4.2, 2.3 Hz, 2H), 7.30 (d, J = 1.6 Hz, 1H), 7.29 (s, 1H), 3.87 (s, 3H), 1.42 (s, 18H).

[0306]

[0307] Yield: 87%. 1 1H NMR (400 MHz, CDCl3) δ 8.13 (s, 1H), 8.10 (d, J = 0.7 Hz, 1H), 7.54 (d, J = 8.5 Hz, 1H), 7.51 (d, J = 1.7 Hz, 2H), 7.49 - 7.42 (m, 3H), 7.35 (d, J = 8.5 Hz, 1H), 7.15 (t, J = 7.4 Hz, 2H), 3.84 (s, 3H), 1.40 (s, 18H).

[0308]

[0309] Yield: 58%. 11H NMR (400 MHz, CDCl3) δ 8.14 (s, 1H), 7.64 (s, 1H), 7.53 -7.43 (m, 2H), 7.37 (d, J = 8.2 Hz, 1H), 7.21 - 7.11 (m, 5H), 7.06 (d, J = 8.3Hz, 1H), 3.86 (s, 3H), 2.07 (s, 6H).

[0310]

[0311] Yield: 88%. 1 1H NMR (400 MHz, CDCl3) δ 8.17 (s, 1H), 7.87 (d, J = 7.6 Hz,1H), 7.32 (t, J = 6.7 Hz, 3H), 7.22 - 7.15 (m, 2H), 7.13 (d, J = 7.2 Hz, 2H),3.87 (s, 3H), 2.13 (s, 6H). HRMS (ESI) [M+H] + : calculated for m / z 329.1656, found 329.1647.

[0312]

[0313] Yield: 80%. 1 1H NMR (400 MHz, CDCl3) δ 8.18 (s, 1H), 7.87 (d, J = 7.8 Hz,1H), 7.34 (dt, J = 13.2, 6.8 Hz, 3H), 7.28 (d, J = 6.9 Hz, 2H), 7.22 (d, J =7.9 Hz, 3H), 7.18 (d, J = 8.4 Hz, 1H), 3.88 (s, 3H), 2.73 (dt, J = 13.6, 6.8Hz, 2H), 1.22 - 1.06 (m, 12 H).

[0314] Scheme 3. Synthesis of L4-OMe

[0315]

[0316] In a 50 mL sealed tube, 2.89 mg (8.81 mmol, 1 equiv) of 1-(3-methoxy-2',6'-dimethyl-[1,1'-biphenyl]-4-yl)-1H-benzo[d]imidazole (4c) was dissolved in 7 mL of CH2Br2 (0.1001 mol, 11.4 equiv) to obtain a clear solution, and the mixture was stirred at 120 ºC for 72 h. Then the mixture was cooled to room temperature, 150 mL of THF was added, and the mixture was filtered. The resulting solid was washed with THF and diethyl ether and then dried under vacuum to obtain 1.81 g of an off-white solid (yield: 49%). 1 H NMR (400 MHz, DMSO) δ 10.77 (s, 1H), 8.60 (d, J = 8.2 Hz, 1H), 7.90(d, J = 7.2 Hz, 1H), 7.85 - 7.68 (m, 3H), 7.64 (s, 1H), 7.29 (s, 1H), 7.21(dd, J = 16.6, 6.6 Hz, 3H), 7.09 (d, J = 7.6 Hz, 1H), 3.85 (s, 3H), 2.09 (s,J = 8.5 Hz, 6H). HRMS (ESI) [M 2+ -2Br - : m / z calcd for 335.1648, found 335.1647.

[0317] Post-treatment method of Ln-Ome: After the reaction, an excess of diethyl ether was added to the mixture, and an off-white solid was formed. The solid was separated by centrifugation and dissolved in a small amount of DCM. Diethyl ether was added to the DCM solution to precipitate the solid, and the dissolution-precipitation process was repeated three times to obtain a white solid.

[0318]

[0319] Yield: 64%. 1 H NMR (500 MHz, DMSO) δ 10.67 (s, 1H), 8.55 (d, J = 8.5 Hz,1H), 7.87 (t, J = 7.8 Hz, 1H), 7.75 (t, J = 7.9 Hz, 2H), 7.70 (t, J = 9.4 Hz,2H), 7.59 (s, 1H), 7.51 (d, J = 8.4 Hz, 1H), 7.31 (t, J = 7.6 Hz, 1H), 3.85(s, 3H).

[0320]

[0321] Yield: 77%. 1 H NMR (400 MHz, DMSO) δ 10.81 (s, 1H), 8.58 (d, J = 8.2 Hz, 1H), 7.90 (t, 1H), 7.79 (d, J = 7.6 Hz, 1H), 7.73 (s, 1H), 7.71 (s, 1H), 7.53 (d, J = 11.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 1H), 3.19 (s, 3H), 1.43 (s, 9H).

[0322]

[0323] Yield: 37%. 1 H NMR (500 MHz, DMSO) δ 10.79 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.5 Hz, 1H), 7.92 - 7.87 (m, 1H), 7.83 - 7.79 (m, 2H), 7.78 (s, 1H), 7.68 (s, 1H), 7.63 (s, 1H), 7.54 (t, J = 8.5 Hz, 4H), 3.98 (s, 2H), 1.39 (s, 18H).

[0324]

[0325] Yield: 84%. 1 H NMR (400 MHz, DMSO) δ 10.79 (s, 1H), 8.65 (s, 1H), 8.00 (d, J = 8.7 Hz, 1H), 7.80 (d, J = 7.8 Hz, 1H), 7.75 (d, J = 6.5 Hz, 1H), 7.73 (s, 1H), 7.70 (s, 1H), 7.47 (d, J = 3.7 Hz, 4H), 7.31 (t, 1H), 3.74 (s, 3H), 1.27 (s, 18H).

[0326]

[0327] Yield: 36%. 1¹H NMR (500 MHz, DMSO) δ 10.76 (s, 1H), 8.34 (s, 1H), 7.75 (d, J = 8.4 Hz, 3H), 7.60 (s, 1H), 7.51 (dd, J = 8.4, 3.7 Hz, 2H), 7.32 (t, J = 7.6 Hz, 1H), 7.28 - 7.21 (m, 1H), 7.15 (d, J = 7.6 Hz, 3H), 3.83 (s, 3H), 1.89 (s, 6H).

[0328]

[0329] Yield: 68%. 1 ¹H NMR (500 MHz, DMSO) δ 10.69 (s, 1H), 8.53 (d, J = 8.3 Hz, 1H), 7.88 (t, J = 7.8 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.72 (d, J = 8.6 Hz, 1H), 7.56 (dd, J = 15.1, 8.4 Hz, 4H), 7.19 (d, J = 7.7 Hz, 1H), 7.14 (d, J = 7.6 Hz, 2H), 3.88 (s, 3H), 2.07 (d, J = 12.5 Hz, 6H).

[0330]

[0331] Yield: 65%. 1 ¹H NMR (500 MHz, DMSO) δ 10.78 (s, 1H), 8.59 (t, J = 6.7 Hz, 1H), 7.86 (dd, J = 15.7, 7.8 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.69 - 7.63 (m, 2H), 7.56 (s, 1H), 7.53 (d, J = 8.9 Hz, 1H), 7.43 - 7.34 (m, 2H), 7.23 (t, J = 8.4 Hz, 3H), 3.88 (s, J = 5.4 Hz, 3H), 2.61 (dt, J = 13.7, 7.2 Hz, 2H), 1.06 (t, J = 12.6 Hz, 12 H).

[0332] Scheme 4. Synthesis of L4

[0333]

[0334] The dried 50 mL Schlenk flask equipped with a stir bar was evacuated - refilled - evacuated three times. Under argon protection, 290 mg (0.349 mmol, 1 equiv) of L4-OMe was added, and evacuated - refilled again to ensure an inert atmosphere. 30 mL of anhydrous DCM was added under argon protection to obtain a white suspension. 3 mL of BBr3 solution (6.98 mmol, 20 equiv, 2 mol / L dissolved in DCM) was added dropwise over 15 min in an ice bath, and the solution became clear. Then the mixture was stirred at room temperature for 12 h. After the reaction, methanol (5 mL) was slowly added in an ice bath to quench the reaction, and then the solvent was removed under reduced pressure. The remaining solid was washed with water, acetone, and diethyl ether to obtain 240 mg of a white solid (yield: 86%). 1 1H NMR (400 MHz, DMSO) δ 11.11 (s, 1H), 10.79 (s, 1H), 8.62 (d, J = 8.5 Hz, 1H), 7.89 (t, J = 7.6 Hz, 1H), 7.77 (dt, J = 22.1, 8.2 Hz, 3H), 7.67 (s, 1H), 7.19 (dd, J = 16.9, 6.6 Hz, 3H), 7.00 (s, 1H), 6.94 (d, J = 8.1 Hz, 1H), 2.08 (s, 6H).

[0335] Work-up method for other ligands: The quenched reaction mixture was dried by rotary evaporation as shown for L4. The remaining brown solid was dissolved in DCM and washed three times with saturated NaCl solution. The DCM phase was dried over MgSO4, filtered, and concentrated. Diethyl ether was added to the DCM solution to precipitate the solid, and the dissolution - precipitation was repeated three times to obtain a white solid.

[0336]

[0337] Yield: 35%. 11H NMR (400 MHz, DMSO) δ 10.92 (s, 1H), 10.81 (s, 1H), 8.62 (d, J = 8.4 Hz, 1H), 7.85 (t, J = 7.8 Hz, 1H), 7.75 (t, J = 7.8 Hz, 1H), 7.71 (s, 1H), 7.69 - 7.63 (m, 2H), 7.61 - 7.52 (m, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H).

[0338]

[0339] Yield: 78%. 1 1H NMR (500 MHz, DMSO) δ 10.68 (s, 1H), 9.49 (s, 1H), 8.56 (d, J = 8.1 Hz, 1H), 7.88 (s, 1H), 7.77 (s, 2H), 7.56 (d, J = 8.1 Hz, 1H), 7.48 (d, J = 4.8 Hz, 1H), 7.40 (d, J = 9.7 Hz, 1H), 1.42 (s, 9H). 19 19F NMR (377 MHz, DMSO) δ -121.57 (t, J = 9.1 Hz).

[0340]

[0341] Yield: 53%. 1 1H NMR (400 MHz, DMSO) δ 11.09 (s, 1H), 10.72 (s, 1H), 8.60 (d, J = 8.3 Hz, 1H), 7.87 (d, J = 8.2 Hz, 1H), 7.77 (d, J = 6.5 Hz, 2H), 7.71 (d, J = 8.3 Hz, 1H), 7.66 (s, 1H), 7.51 (s, 1H), 7.46 (dd, J = 6.1, 4.7 Hz, 4H), 1.37 (s, 18H).

[0342]

[0343] Yield: 87%. 11H NMR (500 MHz, DMSO) δ 10.96 (s, 1H), 10.68 (s, 1H), 8.68(s, 1H), 8.01 (d, J = 8.5 Hz, 1H), 7.77 - 7.64 (m, 3H), 7.59 (t, J = 7.6 Hz,1H), 7.47 (s, 3H), 7.27 (d, J = 8.0 Hz, 1H), 7.16 (t, J = 7.5 Hz, 1H), 1.27(s, 18H).

[0344]

[0345] Yield: 99%. 1 1H NMR (400 MHz, DMSO) δ 10.97 (s, 1H), 10.69 (s, 1H), 8.41(s, 1H), 7.73 (d, J = 8.5 Hz, 1H), 7.62 (d, J = 8.3 Hz, 1H), 7.60 - 7.54 (m,2H), 7.52 (d, J = 8.5 Hz, 1H), 7.28 (d, J = 8.2 Hz, 1H), 7.24 (d, J = 7.4 Hz,1H), 7.16 (d, J = 6.8 Hz, 3H), 1.91 (s, 6H).

[0346]

[0347] Yield: 84%. 1 1H NMR (400 MHz, DMSO) δ 11.00 (s, 1H), 10.75 (s, 1H), 8.57(d, J = 8.4 Hz, 1H), 7.85 (d, J = 7.9 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.69(d, J = 8.3 Hz, 1H), 7.64 (s, 1H), 7.46 (s, 1H), 7.35 (s, 2H), 7.15 (dd, J =17.8, 6.8 Hz, 3H), 2.06 (s, 6H).

[0348]

[0349] Yield: 87%. 11H NMR (500 MHz, DMSO) δ 11.05 (s, 1H), 10.63 (s, 1H), 8.56 (d, J = 8.4 Hz, 1H), 7.86 (t, J = 7.8 Hz, 1H), 7.78 (t, J = 7.8 Hz, 1H), 7.63 (d, J = 8.3 Hz, 1H), 7.60 (s, 1H), 7.36 (ddd, J = 24.3, 11.6, 6.3 Hz, 4H), 7.21 (d, J = 7.8 Hz, 2H), 2.67 - 2.60 (m, 2H), 1.04 (dd, J = 30.4, 6.9 Hz, 12H).

[0350] Scheme 5. Synthesis of Pt-4

[0351]

[0352] In a 50 mL flame-dried two-necked flask filled with argon, 100 mg of L4 (0.125 mmol, 1 equiv) and 47 mg of Pt(COD)Cl2 (0.126 mmol, 1.01 equiv) were suspended in 8 mL of EtOH. 0.42 mL of Et3N (3.01 mmol, 24 equiv) was added and the mixture was dissolved, and the mixture was refluxed overnight under an inert atmosphere. After the reaction was completed, the mixture was cooled to room temperature, which was a white suspension. The solid was filtered and washed with cold EtOH and ether. After drying under high vacuum, the product was obtained as a white powder. (Yield: 40%) 1 1H NMR (500 MHz, CD2Cl2) δ 8.13 (d, J = 7.8 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 7.8 Hz, 1H), 7.47 (dd, J = 16.8, 8.0 Hz, 2H), 7.12 (dd, J = 16.6, 6.4 Hz, 3H), 6.92 (s, 1H), 6.70 (s, 1H), 6.49 (d, J = 8.1 Hz, 1H), 2.16 (s, 6H). HRMS (ESI) [M+H] + : m / z calcd for 834.2410, found 834.2399. C 43 H 34N4O2Pt·4C2H5OH·CH2Cl2 Anal. Calcd. for C 57.03%, H 4.79%, N 5.54%; Found: C 57.78%, H 4.37%, N 5.58%

[0353]

[0354] Yield: 15%. 1 H NMR (400 MHz, CD2Cl2) δ 8.16 (d, J = 8.2 Hz, 1H), 7.78 (d, J = 8.2 Hz, 1H), 7.71 (d, J = 8.2 Hz, 1H), 7.55 (s, 1H), 7.49 (s, 1H), 7.13 (s, 2H), 6.72 (s, 1H), 6.52 (s, 1H). HRMS (ESI) [M+H] + : m / z Calcd. 625.1180, Found 626.1141. C 27 H 18 N4O2Pt﹒H2O Anal. Calcd. for C 50.36%, H 3.33%, N 7.99%; Found: C 50.22%, H 3.29%, N 7.99%

[0355]

[0356] Yield: 10%. 1 H NMR (600 MHz, CD2Cl2) δ 8.18 (d, J = 8.2 Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.52 (t, J = 7.8 Hz, 1H), 7.48 (dd, J = 9.4, 3.1 Hz, 1H), 7.06 (dd, J = 10.5, 3.1 Hz, 1H), 6.48 (s, 1H), 1.56 (s, 9H). 19 F NMR (377 MHz, CD2Cl2) δ -131.28 (t, J = 10.1 Hz). HRMS (ESI) [M+H] + : m / z Calcd. 774.2221, Found 774.2248.

[0357]

[0358] Yield: 81%.1 1H NMR (600 MHz, CD2Cl2) δ 8.24 (d, J = 7.9 Hz, 1H), 7.88 (d, J = 8.3 Hz, 1H), 7.73 (d, J = 7.9 Hz, 1H), 7.60 - 7.48 (m, 5H), 7.45 (s, 1H), 7.01 (d, J = 8.3 Hz, 1H), 6.55 (s, 1H), 1.41 (s, 18H). C 55 H 58 N4O2Pt [M+H] + HRMS(ESI) for

[0359]

[0360] Yield: 52%. 1 1H NMR (500 MHz, CD2Cl2) δ 7.97 (d, J = 8.7 Hz, 1H), 7.87 (s, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.62 - 7.54 (m, 4H), 6.93 (d, J = 8.7 Hz, 2H), 6.71 (d, J = 7.9 Hz, 1H), 6.57 (t, 1H), 1.47 (s, 18H). HRMS (ESI) [M+H] + : calculated for m / z 1002.4288, found 1002.4248.

[0361]

[0362] Yield: 10%. 1 1H NMR (500 MHz, CD2Cl2) δ 8.19 (d, J = 8.5 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.42 (s, 1H), 7.26 (d, J = 8.5 Hz, 1H), 7.20 (d, J = 6.7 Hz, 1H), 7.14 (dd, J = 12.1, 7.4 Hz, 3H), 7.08 (s, 1H), 6.72 (s, 1H), 6.53 (s, 1H), 2.07 (s, 6H). HRMS (ESI) [M+H] +: Calculated m / z value: 834.2410, measured value: 834.2411.

[0363]

[0364] Yield: 21%. 1 H NMR (400 MHz, DMSO) δ 8.26 (d, J = 9.1 Hz, 1H), 7.96 (d, J = 9.1 Hz, 1H), 7.60 (d, J = 6.6 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.50 (s, 1H), 7.13 (s, 4H), 6.99 (s, 1H), 6.91 (d, J = 8.4 Hz, 1H), 2.10 (s, 6H). HRMS(ESI) [M+H] + : Calculated m / z value: 834.2410, measured value: 834.2380. 5C 43 H 34 N4O2Pt﹒15CH2Cl2﹒2C4H 10 Calculated elemental analysis values: C 51.13%, H 3.96%, N 5.01%, measured values: C 51.06%, H 3.69%, N 5.05%.

[0365]

[0366] Yield: 21%. 1 H NMR (500 MHz, CD2Cl2) δ 7.86 (d, J = 8.3 Hz, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.47 (t, J = 7.8 Hz, 1H), 7.43 (s, 1H), 7.34 - 7.26 (m, 2H), 7.19 (d, J = 7.7 Hz, 2H), 7.06 (d, J = 8.3 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.77 (s, 1H), 2.93 - 2.82 (m, 2H), 1.11 (t, J = 7.0 Hz, 12 H). HRMS (ESI) [M+H] + : Calculated m / z value: 946.3662, measured value: 946.3648.

[0367]

[0368] Yield: 18%.1 H NMR (60 MHz, CD2Cl2) δ = 8.03 (d, J = 8.4 Hz, 2H), 7.60(d, J = 2.1 Hz, 2H), 7.41 (d, J = 1.5 Hz, 2H), 7.31 (t, J = 7.7 Hz, 2H), 7.24 - 7.14 (m, 10H), 7.12 (t, J = 8.3 Hz, 4H), 6.95 (d, J = 8.1 Hz, 2H), 6.56 (s,2H), 3.04 - 2.78 (m, 4H), 2.08 - 1.93 (m, 12 H), 1.21 - 0.97 (m, 24H).

[0369]

[0370] Yield: 22%. 1 H NMR (600 MHz, DMSO-d6) δ 9.28 (dd, J = 8.3, 1.7 Hz, 2H),8.63 (dq, J = 4.9, 1.5 Hz, 4H), 7.70 (dd, J = 7.9, 4.9 Hz, 2H), 7.27 - 7.02(m, 2H), 7.03 - 6.80 (m, 4H), 6.67 (ddd, J = 8.4, 6.9, 1.6 Hz, 2H).

[0371]

[0372] Yield: 20%. 1 H NMR (600 MHz, CD2Cl2) δ 8.95 (d, J = 2.2 Hz, 2H), 8.47(dd, J = 4.8, 1.4 Hz, 2H), 8.04 (dd, J = 8.2, 1.4 Hz, 2H), 7.43 (dd, J = 8.1,4.8 Hz, 2H), 7.32 (t, J = 7.8 Hz, 2H), 7.21 (d, J= 8.0 Hz, 6H), 6.97 (dd, J =8.3, 2.1 Hz, 2H), 6.61 (s, 2H), 2.95 - 2.86 (m, 4H), 1.12 (dd, J = 6.8, 1.2Hz, 24H).

[0373] Fabrication and Characterization of OLEDs

[0374] The OLEDs were fabricated in a Kurt J. Lesker SPECTROS vacuum deposition system with a base pressure of 10 -8 mbar. Inside the vacuum chamber, the organic materials were thermally deposited sequentially at a rate of ~0.1 nm s -1 . The doping process of the emitting layer was achieved by co-deposition technique. LiF (1.2 nm) and Al (100 nm) were thermally deposited at rates of 0.03 nm s -1 and 0.2 nm s -1 respectively. The film thickness was determined in-situ by a calibrated oscillating quartz crystal sensor. EL spectra, J-L-V characteristics, CIE coordinates, EQE, CE, and PE were all measured using a Keithley 2400 source meter and an absolute external quantum efficiency measurement system (C9920-12, Hamamatsu Photonics). All the devices were characterized at room temperature without encapsulation.

[0375] Results

[0376] Photophysical Properties of Platinum(II) Complexes

[0377] A series of Pt(II)-O^C*^C*^O complexes were prepared and characterized. The Pt(II) complexes contain: (i) benzimidazole-based NHCs (e.g., Pt-1 to Pt-8); (ii) large substituted phenolates with different structures (e.g., Pt-3, Pt-4, Pt-7, and Pt-8); and (iii) in addition to the p-extension at the NHC, two types of large phenyl groups, 3,5-di-tert-butyl-phenyl (ditBuPh) and 2,6-dimethyl-phenyl (diMePh) (e.g., Pt-5 and Pt-6). Compared with the previously reported imidazole-based Pt(II)-O^C*^C*^O complexes, the structural features of the Pt(II) complexes lead to a significant increase in PLQY and radiative decay rate constants, see, for example, Chem. Commun. 2011, 47, 9075; Chem. Sci. 2013, 4, 2630. Without being bound by any theory, the improvement in the emission performance of the Pt(II) complexes can be attributed to the geometric changes of the metal complexes and the extended π-conjugation of the acceptor units.

[0378] The thermal stabilities of complexes Pt-4, Pt-7, and Pt-8 (compared with the reference complex Pt-ref1) were examined using thermogravimetric analysis (TGA). As Figure 1 and the data in Table 1 show, Pt-7 and Pt-8 have thermal stability compared to their counterparts, with decomposition temperatures T d > 400 °C.

[0379]

[0380] Figures 2A - 2C shows the X-ray single crystal structures of Pt-1 and Pt-4 (compared with the reference Pt(II) complex Pt-ref1). Tables 2-5 show the bond lengths and bond angles of Pt-1 and Pt-4 (compared with the reference complexes Pt-ref1 and Pt-ref2).

[0381]

[0382] Pt-1 and Pt-4 show a slightly distorted square planar structure with a C-Pt-O angle of ~176°, which is less than ~178° for the complex Pt-ref1. The two Pt-C and two Pt-O bonds in Pt-1 and Pt-4 are shorter compared to those in Pt-ref1, indicating stronger metal-ligand bonds in Pt-1 and Pt-4. Different from Pt-ref1 where the NHC and phenolate moieties are arranged on the same side of the coordination plane (dihedral angles between 9.08° and -5.69°), the two moieties in Pt-1 and Pt-4 are arranged on different sides of the coordination plane and are more distorted, with dihedral angles between 24.57° and -26.14° for Pt-1 between the two moieties and -21.56° and 31.20° for Pt-4. These result in a decrease in planarity and a change in orientation between the NHC and phenolate rings observed in Pt-1 and Pt-4.

[0383]

[0384]

[0385]

[0386]

[0387] The emission data of the exemplary Pt(II) blue emitters are as Figure 3A and 3B shown and summarized in Table 6. The Pt(II) complexes show blue light emission in PMMA films with a high PLQY of up to 83% and a fast radiative rate (k r >10 5 s -1 ) for Pt-1, Pt-4, Pt-7, and Pt-8. The emission bandwidths of Pt-7 and Pt-8 are narrower than those of Pt-1, Pt-4, and Pt-6. In particular, Pt-7 shows a PLQY of up to 80% with a radiative decay rate of 3.4×10 5 s -1, which is suitable as a luminescent dopant or sensitizer in blue OLEDs. Emission data for additional exemplary Pt(II) blue emitters are shown in Figure 7 and summarized in Table 9.

[0388]

[0389]

[0390] OLED Performance

[0391] OLED devices fabricated with Pt-4 were tested and the performance data are shown in Figures 4A - 4D and summarized in Table 7. OLED devices fabricated with Pt-8 were tested and the performance data are shown in Figures 5A - 5D and summarized in Table 8. OLED devices fabricated with Pt-9 were tested and the performance data are shown in Figures 8A - 8D and summarized in Table 10.

[0392]

[0393]

[0394]

[0395] 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 the claimed invention pertains. Publications and the materials cited therein are hereby specifically incorporated by reference. In addition, unless otherwise noted, the expression “wt%” refers to “wt / wt%”.

[0396] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims

1. A platinum(II) complex having the following structure: Wherein: (i) Each occurrence of X1 to X4 is independently nitrogen or CR 16 ; (ii) Each occurrence of R1 to R8 and R 16 is independently hydrogen, deuterium, a halide (such as fluoride, chloride, bromide, iodide, etc.), a hydroxyl group, an amino group, an amide group, a thiol group, a cyano group, a nitro group, an alkoxy group, a carbonyl group, a substituted or unsubstituted C1 to C 12 alkyl group, a substituted or unsubstituted C1 to C 12 alkenyl group, a substituted or unsubstituted C1 to C 12 alkynyl group, a substituted or unsubstituted aryl group (such as phenyl), a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group, or two adjacent groups among R1 to R8 and R 16 together with the carbon atom to which they are attached form a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted polyaryl group, or a substituted or unsubstituted hetero-polyaryl group; (iii) n1 is an integer from 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 or 2; (iv) R 14 and R 15 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C 12 alkenyl, or substituted or unsubstituted C1-C 12 alkynyl, or R 14 and R 15 together with the carbon atoms to which they are attached form a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl; and (v) When present, the substituents are independently unsubstituted C1-C 12 alkyl, unsubstituted C1-C 12 alkenyl, unsubstituted C1-C 12 alkynyl, unsubstituted aryl (such as phenyl), aryl (such as phenyl) substituted by one or more unsubstituted aryl (such as unsubstituted phenyl) and / or one or more unsubstituted alkyl (such as unsubstituted C1-C 12 alkyl), unsubstituted heteroaryl, heteroaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted polyaryl, polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, unsubstituted hetero-polyaryl, hetero-polyaryl substituted by one or more unsubstituted aryl and / or one or more unsubstituted alkyl, amino, or halide.

2. The platinum(II) complex according to claim 1, wherein the platinum(II) has the following structure:

3. The platinum(II) complex according to claim 1, wherein X1 and X4 are independently nitrogen or CR 16 ; X2 and X3 are CR 16 ; R 16 is hydrogen, deuterium, a halide, an unsubstituted C1-C 12 alkyl, an unsubstituted aryl, or an aryl substituted by one or more unsubstituted C1-C 12 alkyl; R2 to R5 are independently hydrogen, deuterium, an amino group, an unsubstituted C1-C 12 alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted hetero-polyaryl, or R2 and R3, R3 and R4, or R4 and R5 together with the carbon atoms to which they are attached form a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, or a substituted or unsubstituted hetero-polyaryl; and the substituents, when present, are independently an unsubstituted C1-C 12 alkyl, an unsubstituted aryl (e.g., phenyl), an aryl (e.g., phenyl) substituted by one or more unsubstituted aryls (e.g., phenyl) and / or one or more unsubstituted alkyls, an unsubstituted heteroaryl, a heteroaryl substituted by one or more unsubstituted aryls and / or one or more unsubstituted alkyls, an unsubstituted polyaryl, a polyaryl substituted by one or more unsubstituted aryls and / or one or more unsubstituted alkyls, an unsubstituted hetero-polyaryl, a hetero-polyaryl substituted by one or more unsubstituted aryls and / or one or more unsubstituted alkyls, or an amino group.

4. The platinum(II) complex according to claim 1, wherein each occurrence of R1 to R8 is independently hydrogen, deuterium, halide, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C1-C 12 alkenyl, substituted or unsubstituted C1-C 12 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted polyaryl, or substituted or unsubstituted hetero-polyaryl.

5. The platinum(II) complex according to claim 4, wherein each occurrence of R1 to R8 is independently hydrogen, deuterium, a halide, a substituted or unsubstituted C1 to C 12 alkyl group, or a substituted or unsubstituted aryl group.

6. The platinum(II) complex according to claim 4, wherein each occurrence of R1 to R8 is independently hydrogen, deuterium, a halide (e.g., fluoride, chloride or bromide), an unsubstituted C1-C 12 alkyl (e.g., unsubstituted C1-C6 alkyl, unsubstituted C1-C4 alkyl or unsubstituted C1-C3 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), or , and wherein R9 to R 13 are independently hydrogen, deuterium, an unsubstituted C1-C 12 alkyl, an unsubstituted phenyl, an unsubstituted heteroaryl, or an amino group, Optionally, wherein R9 to R 13 are independently hydrogen, deuterium or unsubstituted C1-C6 alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.).

7. The platinum(II) complex according to claim 1, wherein the platinum(II) complex has any one of the following structures: 。 8. The platinum(II) complex according to claim 1, wherein the maximum emission wavelength (λ max ) of the platinum(II) complex is in the range of 420 nm to 490 nm, 430 nm to 490 nm, 440 nm to 490 nm, 450 nm to 490 nm, 460 nm to 490 nm, 430 nm to 465 nm, or 440 nm to 470 nm, such as 441 nm to 454 nm, etc.

9. The platinum(II) complex according to claim 1, wherein the emission quantum yield (Ф em ) is at least 30%, at least 35%, at least 45%, at least 50%, at least 60%, at least 70%, in the range of 30% to 90%, in the range of 30% to 85%, in the range of 30% to 80%, in the range of 35% to 85%, in the range of 35% to 80%, in the range of 45% to 85%, in the range of 45% to 80%, in the range of 50% to 85%, or in the range of 50% to 80%, as measured in a film at room temperature.

10. The platinum(II) complex according to claim 1, wherein the emission lifetime (τ em ) is ≤ 5.5 μs, ≤ 5 μs, ≤ 4 μs, ≤ 3 μs, ≤ 2 μs, ≤ 1 μs, in the range of 0.5 μs to 5 μs, in the range of 1 μs to 5 μs, or in the range of 2 μs to 5 μs, such as about 2.25 μs, etc., as measured in a film at room temperature.

11. The platinum(II) complex according to claim 1, wherein the radiation decay rate (k r ) of the platinum(II) complex is at least 1.0 × 10 5 s -1 , at least 1.5 × 10 5 s -1 , at least 2.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 5.0 × 10 5 s -1 , in the range of 1.0 × 10 5 s -1 to 4.0 × 10 5 s -1 , in the range of 1.5 × 10 5 s -1 to 4.0 × 10 5 s -1 , in the range of 2.0 × 10 5 s -1 to 4.0 × 10 5 s -1 , or in the range of 3.0 × 10 5 s -1 to 6.0 × 10 5 s -1 , such as about 3.4 × 10 5 s -1 etc. The above were measured in the film at room temperature.

12. An organic light-emitting device comprising a light-emitting layer or two or more light-emitting layers, wherein each light-emitting layer in the light-emitting layer or the two or more light-emitting layers contains one or more platinum(II) complexes of claim 1, optionally wherein the organic light-emitting device emits light in the blue spectral region.

13. The organic light-emitting device according to claim 12, wherein the total concentration of the one or more platinum(II) complexes in each light-emitting layer of the light-emitting layer or the two or more light-emitting layers is at most 20 wt%, at most 10 wt%, at least 1 wt%, in the range of about 1 wt% to about 20 wt%, in the range of about 1 wt% to about 10 wt%, in the range of about 2 wt% to about 20 wt%, or in the range of about 2 wt% to about 10 wt%, such as about 2 wt%, about 6 wt% or about 10 wt%, etc.

14. The organic light-emitting device according to claim 12, further comprising an anode, a cathode, a hole transport region, and an electron transport region, wherein the hole transport region comprises a hole injection layer and / or a hole transport layer and optionally an electron blocking layer, wherein the electron transport region comprises an electron transport layer and / or an electron injection layer and optionally a hole blocking layer, wherein the light-emitting layer is located between the anode and the cathode, wherein the hole transport region is located between the anode and the light-emitting layer, and wherein the electron transport region is located between the cathode and the light-emitting layer.

15. The organic light-emitting device according to claim 12, wherein the organic light-emitting device emits light in the blue region, optionally with λ max in the range of 420 nm to 490 nm, such as in the range of 440 nm to 490 nm, in the range of 450 nm to 490 nm, in the range of 460 nm to 490 nm, in the range of 430 nm to 480 nm, in the range of 440 nm to 480 nm, in the range of 450 nm to 480 nm, in the range of 460 nm to 480 nm, or in the range of 470 nm to 480 nm.

16. The organic light-emitting device according to claim 12, wherein the maximum luminance (L) of the organic light-emitting device is at least 3000 cd m -2 , at least 4000 cd m -2 , at least 5000 cd m -2 , at least 6000 cd m -2 , at least 8000 cd m -2 , between 3000 cd m -2 and 50000 cd m -2 , between 3000 cd m -2 and 40000 cd m -2 , between 3000 cd m -2 and 30000 cd m -2 , between 3000 cd m -2 and 25000 cd m -2 , or between 3000 cd m -2 and 15000 cd m -2 .

17. The organic light-emitting element according to claim 12, wherein the current efficiency (CE) of the organic light-emitting element at 1000 cd / m 2 is at least 20 cd A -1 , at least 25 cd / A, in the range of 20 cd / A to 50 cd / A, or in the range of 20 cd / A to 45 cd / A.

18. The organic light-emitting device according to claim 12, wherein the power efficiency (PE) of the organic light-emitting device at 1000 cd / m 2 is at least 20 lm / W, in the range of 20 lm / W to 50 lm / W, or in the range of 20 lm / W to 45 lm / W.

19. The organic light-emitting element according to claim 12, wherein the external quantum efficiency (EQE) of the organic light-emitting element at 1000 cd / m 2 is at least 10%, at least 15%, in the range of 10% to 35%, in the range of 10% to 30%, in the range of 10% to 25%, in the range of 15% to 35%, in the range of 15% to 30%, in the range of 15% to 25%, in the range of 20% to 30%, or in the range of 15% to 20%, such as about 20%, etc.

20. The organic light-emitting device according to claim 12, wherein the organic light-emitting device is an organic light-emitting diode ("OLED") or a light-emitting electrochemical cell ("LEEC").

21. The organic light-emitting device according to claim 12, wherein each light-emitting layer of the light-emitting layer or the two or more light-emitting layers further comprises an organic dye, and wherein the one or more platinum(II) complexes act as sensitizers to transfer energy to the organic dye.

22. The organic light-emitting device according to claim 12, wherein each light-emitting layer of the light-emitting layer or the two or more light-emitting layers further comprises an organic dye, and wherein the one or more platinum(II) complexes have a higher singlet state than the organic dye.

23. The organic light-emitting device according to claim 12, wherein each light-emitting layer of the light-emitting layer or the two or more light-emitting layers is formed by vacuum evaporation deposition, spin coating, ink printing, or roll-to-roll printing.

24. A device comprising one or more organic light-emitting elements as claimed in claim 12, wherein the device is a stationary visual display unit, a mobile visual display unit, a lighting device, a wearable device, a light therapy device or a medical monitoring device.

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