Organic electro-optical chromophores

Abstract

To provide a chromophore useful for being included in a film having electro-optical activity and an electro-optical device.SOLUTION: There is provided a compound represented by formula (A).SELECTED DRAWING: Figure 6A

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 62 / 911,067, filed October 4, 2019, and U.S. Provisional Application No. 62 / 934,398, filed November 12, 2019, the disclosures of which are incorporated herein by reference in their entireties.

[0002] FIELD OF THE INVENTION The present specification provides chromophores useful for inclusion in electro-optically active films and electro-optical devices.

[0003] Government License Rights Statement This invention was made with government support under Grant No. FA9550-15-1-0319 awarded by the Air Force Office of Scientific Research and Grant No. DMR1303080 awarded by the National Science Foundation. The government has certain rights in this invention. [Background technology]

[0004] background Organic electro-optic (OEO) materials have recently seen a revival of interest due to the development of silicon-organic hybrid (SOH) and plasmonic-organic hybrid (POH) devices, which combine the high intrinsic electro-optic activity of a class of organic chromophores with small device size and enable chip-scale integration with CMOS electronics. The size of an electro-optic device is determined by the voltage-length product (VL) It is proportional to JPEG2026027285000002.jpg824, where U π is the voltage required to induce a phase shift of π over the path length L, n is the refractive index of the electro-optic material, and r 33 is the electro-optic coefficient of the material. For OEO materials, JPEG2026027285000003.jpg830, where ρ N has a large molecular hyperpolarizability (β) and the dipole moments are aligned non-centrally. JPEG2026027285000004.jpg829 is the number density (concentration) of the chromophores aligned in a direction perpendicular to the electrodes of the electro-optical device, and θ is the angle between the dipole moment of the chromophore and the axis perpendicular to the electrodes of the electro-optical device.

[0005] Highly polarizable chromophores generally have a donor-π-bridge-acceptor (D-π-A) structure, in which an electron-donating moiety, such as a substituted amine group, and an electron-accepting moiety containing a strong electron-withdrawing group, such as cyano (CN) or nitro (NO), are connected by a π-conjugate linker, often containing an ene / polyene and / or heteroaromatic group. For example, a D-π-A chromophore such as JRD1 shown in Figure 1 is known.

[0006] Higher r in the device for a given chromophore concentration 33 and smaller U π There is a need for chromophores that have higher chromophore hyperpolarizability and favorable stability and processability to enable L. Summary of the Invention

[0007] overview This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.

[0008] In one aspect, the present description provides compounds of formula A: JPEG2026027285000005.jpg1850, where: A is a π-electron acceptor group; X is JPEG2026027285000006.jpg2627 or JPEG2026027285000007.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 is cycloheteroalkyl, n is 1, 2 or 3; n is 1, 2, or 3; R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, Q is JPEG2026027285000008.jpg1247 or JPEG2026027285000009.jpg1228, J, in each occurrence, is independently S, O, or NR 8 and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 heteroaryl, and Q is, JPEG2026027285000010.jpg1224 or When JPEG2026027285000011.jpg1019, Z 1 is optionally substituted C6-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, and Z2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 heteroaryl, or Q is, JPEG2026027285000012.jpg1228, Z 1 and Z 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, A compound is provided.

[0009] In some embodiments, the compound has formula A1: It is represented as JPEG2026027285000013.jpg3249, where: Z 2 , Q, X, A, n, and m are as defined above, and R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0010] In some embodiments, the compound has formula A2: It is represented by JPEG2026027285000014.jpg3558, where: Q, X, A, n and m are as defined above; R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, R 7 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Alkyloxy, optionally substituted C3-C 10 Heteroalkyloxy, or NR 3 R 4 and R 3 and R 4 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0011] In some embodiments, the compound has formula A3: It is represented as JPEG2026027285000015.jpg3960, where: Q, X, A, n, and m are as defined above; R 1 and R 2are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 3 and R 4 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0012] In some embodiments, the compound has formula A4: It is represented as JPEG2026027285000016.jpg3460, where: Q, X, A, n, and m are as defined above; R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R' is an optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0013] In some embodiments, Q is JPEG2026027285000017.jpg1024.

[0014] In some embodiments, Q is JPEG2026027285000018.jpg1119, where: J is S, O, or NR 8 and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 It is heteroaryl.

[0015] In some embodiments, Q is JPEG2026027285000019.jpg1228, where: J, in each occurrence, is independently S, O, or NR 8 and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 It is heteroaryl.

[0016] In some embodiments, J is S.

[0017] In some embodiments, A is JPEG2026027285000020.jpg2026, where R' and R" are independently optionally substituted C-C12 Alkyl (e.g., fluorinated alkyl) and optionally substituted C-C 10 aryl (e.g., fluorinated aryl), and G 1 , G 2 , and G 3 are independently selected from F, CN, CF3, and SO2CF3.

[0018] In some embodiments, A is JPEG2026027285000021.jpg1928.

[0019] In some embodiments, m is 1. In some embodiments, n is 1.

[0020] In some embodiments, the compound has formula A5: JPEG2026027285000022.jpg3669 compound, where: Z 1 and Z 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000023.jpg2627 or JPEG2026027285000024.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0021] In some embodiments, the compound has formula A6: JPEG2026027285000025.jpg3559 compound, where: Z 1 is optionally substituted C6-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, Z 2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000026.jpg2627 or JPEG2026027285000027.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0022] In some embodiments, the compound has formula A7: JPEG2026027285000028.jpg3162 is a compound, where: Z 1 is optionally substituted C6-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, Z 2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000029.jpg2727 or JPEG2026027285000030.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0023] In some embodiments, the compound comprises one or more reactive groups capable of forming a covalent bond when reacted with a counterpart reactive group, hi some embodiments, the one or more reactive groups are groups capable of crosslinking by (4+2) cycloaddition.

[0024] In some embodiments, Z 1 and at least one of X is JPEG2026027285000031.jpg3278 and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C1-C 10 -alkyl), and R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0025] In some embodiments, LY is H, OL 1 OSiR 10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 where L 1 optionally substituted C2-C 20 Alkylene or optionally substituted C3-C 50heteroalkylene, and R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0026] In some embodiments, X is JPEG2026027285000032.jpg1627 or JPEG2026027285000033.jpg3227, where G 4 is OSiR 10 R 11 R 12 where R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 aryl or G 4 teeth, JPEG2026027285000034.jpg3140 or JPEG2026027285000035.jpg2434, where G 5 is NH, O, S, or N(C1-C 10 -alkyl).

[0027] In some embodiments, the compound has formula A8: JPEG2026027285000036.jpg4194 compound, where: G 6 is OR' or NR'R", where R' and R" are independently optionally substituted C-C 10 is alkyl, R 1 is H or optionally substituted C1-C 10 is alkyl, R 2 is optionally substituted C1-C10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and Y is an optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and where R 2 , Y, and G 6 At least one of the JPEG2026027285000037.jpg3378 and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C1-C 10 -alkyl), and R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0028] In some embodiments, the compound is Compound I, Compound II, Compound III, or Compound IV, Compound V, Compound VI, Compound VII, Compound VIII, Compound IX, Compound X, Compound XI, Compound XII, Compound XIII, Compound XIV, or Compound XV, as described below.

[0029] In another aspect, the present disclosure provides electro-optically active films comprising one or more compounds disclosed herein. In some embodiments, the films further comprise a polymer. In some embodiments, the polymer is polymethyl methacrylate (PMMA). In some embodiments, the films have an r greater than about 100 pm / V. 33 In some embodiments, the film has an r33 value greater than about 1000 pm / V. In some embodiments, the film has a Tg of about 105°C or greater.

[0030] In another aspect, the present specification provides a method of forming an electro-optically active film, the method comprising depositing a compound or a mixture including a compound as described herein on a substrate to provide a film; applying an alignment force to the film at a temperature sufficient to provide a film in which at least a portion of the compound is aligned; and reducing the temperature of the film to provide an electro-optically active film.

[0031] In another aspect, the present disclosure provides an electro-optical device comprising a compound disclosed herein.

[0032] In another aspect, the present specification provides an electro-optic device comprising the film disclosed herein.

[0033] In some embodiments, the electro-optical device further comprises one or more charge blocking layers. In some embodiments, the one or more charge blocking layers comprise poly(benzocyclobutene) (BCB), TiO2, MoO3, ZrO2, HfO2, SiO2, Al2O3, Si3N4, or a combination thereof. In some embodiments, the device is an electro-optical modulator, an antenna, a Mach-Zehnder modulator, a phase modulator, a silicon-organic hybrid modulator, a plasmonic-organic hybrid modulator, an electrical-to-optical converter, a terahertz detector, a frequency shifter, or a frequency comb source. [Brief explanation of the drawings]

[0034] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, wherein:

[0035] [Figure 1] Figure 1 shows the known JRD1 chromophore with donor, π-bridge, and acceptor labels. JRD1 contains a substituted aniline donor, a ring-locked polyene bridge, and a CF3-phenyl-substituted tricyanofuran (TCF) acceptor. [Figure 2] FIG. 2 shows the synthesis of an exemplary chromophore, Compound IV. [Figure 3A-3B] 3A and 3B show the real (n, FIG. 3A) and imaginary (k, FIG. 3B) components of the refractive index of exemplary chromophores Compound I, Compound II, Compound III, or Compound IV. [Figure 4A-4B] 4A and 4B show the real (n, FIG. 4A) and imaginary (k, FIG. 4B) components of the refractive index of exemplary Compound II at 10 wt % and 25 wt % concentrations and exemplary Compound IV at 25 wt % concentration compared to 25 wt % JRD1 in PMMA. [Figure 5A-5B] 5A-5B show electro-optic measurements of thin films of exemplary Compound II and exemplary Compound IV in PMMA obtained at 1310 nm using Teng-man ellipsometry. [Figures 6A-6B] 6A and 6B show the poling efficiency (electro-optic coefficient as a function of poling field) of an exemplary compound VI under various conditions (FIG. 6A) and the real (n) and imaginary (k) components of the refractive index of an exemplary compound VI (FIG. 6B). [Figure 7] FIG. 7 shows the synthesis of an exemplary chromophore, Compound VI. Detailed Description of the Invention

[0036] Detailed Description The present specification provides a chromophore having a large hyperpolarizability, an electro-optically active film containing the chromophore, and an electro-optic device containing the chromophore. The chromophore disclosed herein has a large molecular hyperpolarizability, which allows a large electro-optic coefficient (r 33 ) can be achieved.

[0037] The polarizable chromophore compounds or polarizable chromophores disclosed herein are second-order nonlinear optical chromophore compounds. As used herein, the term "chromophore" refers to a compound that can absorb light in the visible spectral range and is colored. The terms "polarizable chromophore compound," "polarizable chromophore," and "chromophore" are used interchangeably throughout this disclosure unless otherwise indicated. In the context of this specification, the term "nonlinear" refers to a second-order effect resulting from the nature of polarizable chromophore compounds (i.e., "push-pull" chromophore compounds) having the general structure D-π-A, where D is an electron donor, A is an electron acceptor, and π is a π-bridge that conjugates the donor to the acceptor.

[0038] A "donor" (represented by "D") is an atom or group of atoms that has a low electron affinity relative to an acceptor (defined below), such that when the donor is conjugated to the acceptor via a π-bridge, electron density is transferred from the donor to the acceptor.

[0039] The acceptor (represented by "A") is an atom or group of atoms that has a high electron affinity relative to the donor, such that when the acceptor is conjugated to the donor via a π-bridge, electron density is transferred from the acceptor to the donor.

[0040] "π-bridge" or "conjugate bridge" ("π" or "π" in chemical structure) n", where n is an integer) comprises an atom or group of atoms through which electrons can be delocalized from an electron donor (defined above) to an electron acceptor (defined above) through orbitals of atoms in the bridge. Preferably, the orbitals can be p orbitals on multiply bonded carbon atoms such as those found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. Additionally, the orbitals can be p orbitals on multiply bonded atoms such as boron or nitrogen, or organometallic orbitals. The bridge atoms containing the orbitals through which electrons can be delocalized are referred to herein as "critical atoms." The number of critical bridge atoms can be a number from 1 to about 30. Additionally, the critical atoms can be further substituted with "alkyl," as defined below, "aryl," as defined below, or "heteroalkyl," as defined below. One or more atoms, excluding hydrogen, on the alkyl, aryl, or heteroalkyl substituent of the critical bridge atom may be bonded to atoms of other alkyl, aryl, or heteroalkyl substituents to form one or more rings.

[0041] In one aspect, the present description provides compounds of formula A: JPEG2026027285000038.jpg1851, a polarizable chromophore compound where: A is a π-electron acceptor group; Z 1 and Z 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, Q is JPEG2026027285000039.jpg1249 or JPEG2026027285000040.jpg1228, J, in each occurrence, is independently S, O, or NR 8and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000041.jpg2627 or JPEG2026027285000042.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, n is 1, 2, or 3; n is 1, 2, or 3, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 6 are independently H, optionally substituted C-C 10 is heteroalkyl, however, Q is, JPEG2026027285000043.jpg1023 or JPEG2026027285000044.jpg1119, Z 1is optionally substituted C6-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, and Z 2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, and Q is, JPEG2026027285000045.jpg1228, Z 1 and Z 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, A polarizable chromophore compound is provided.

[0042] As used herein, the terms "alkyl," "alkenyl," and "alkynyl" include straight-chain, branched-chain, and cyclic monovalent hydrocarbyl radicals, and combinations thereof, which, when unsubstituted, contain only C and H. Examples include methyl, ethyl, isobutyl, cyclohexyl, cyclopentylethyl, 2-propenyl, 3-butynyl, and the like. The total number of carbon atoms in each such group is also sometimes specified herein, e.g., C1-C2, as 1-10C if the group can contain up to 10 carbon atoms. 10 , C-C10, or C1-10.

[0043] As used herein, the terms "heteroalkyl," "heteroalkenyl," and "heteroalkynyl" refer to the corresponding hydrocarbon in which one or more chain carbon atoms have been replaced with a heteroatom. Exemplary heteroatoms include N, O, S, and P. When carbon atoms can be replaced with heteroatoms, such as in heteroalkyl groups, the number representing the group, whether written as C3-C10, represents the total number of carbon atoms in the cycle or chain and the number of heteroatoms included in place of carbon atoms in the cycle or chain being described.

[0044] Typically, alkyl, alkenyl, and alkynyl substituents contain 1 to 20 carbon atoms (alkyl) or 2 to 10 carbon atoms (alkenyl or alkynyl). Preferably, they contain 1 to 10 carbon atoms (alkyl) or 2 to 10 carbon atoms (alkenyl or alkynyl). A group can contain one or more types of multiple bonds, or can contain two or more types of multiple bonds. Such groups are included within the definition of the term "alkenyl" if they contain at least one carbon-carbon double bond, and are included within the term "alkynyl" if they contain at least one carbon-carbon triple bond. As used herein, the terms "cycloalkyl," "cycloalkenyl," and "cycloalkynyl" specifically refer to cyclic alkyl, alkenyl, and alkynyl, respectively.

[0045] As used herein, the terms "alkylene," "alkenylene," and "alkynylene" can include straight-chain, branched-chain, and cyclic divalent hydrocarbyl radicals, and combinations thereof. As used herein, the terms "cycloalkylene," "cycloalkenylene," and "cycloalkynylene" specifically refer to cyclic divalent hydrocarbyl radicals.

[0046] Alkyl, alkenyl, and alkynyl groups can be optionally substituted within a chemically meaningful range. Typical substituents include, but are not limited to, halogen (F, Cl, Br, I), ═O, ═N—CN, ═N—OR, ═NR, OR, NR2, SR, SO2R, SO2NR2, NRS02R, NRCONR2, NRC(O)OR, NRC(O)R, CN, C(O)OR, C(O)NR2, OC(O)R, C(O)R, and NO2, where each R is independently H, C1-C8 alkyl, C2-C8 heteroalkyl, C1-C8 acyl, C2-C8 heteroacyl, C2-C8 alkenyl, C2-C8 heteroalkenyl, C2-C8 alkynyl, C2-C8 heteroalkynyl, C6-C10 aryl ... or C5-C10 heteroaryl, and each R is optionally substituted with halogen (F, Cl, Br, I), ═O, ═N—CN, ═N—OR′, ═NR′, OR′, NR′2, SR′, S02R′, S02NR′2, NR′S02R′, NR′CONR′2, NR′C(O)OR′, NR′C(O)R′, CN, C(O)OR′, C(O)NR′2, OC(O)R′, C(O)R′, and NO2, where each R′ is independently H, C1-C8 alkyl, C2-C8 heteroalkyl, C1-C8 acyl, C2-C8 heteroacyl, C6-C10 aryl, or C5-C10 heteroaryl. Alkyl, alkenyl, and alkynyl groups can also be substituted by C1-C8 acyl, C2-C8 heteroacyl, C6-C10 aryl, or C5-C10 heteroaryl, each of which can be substituted by substituents appropriate for that particular group.

[0047] As used herein, "alkyl" includes cycloalkyl and cycloalkylalkyl groups, although the term "cycloalkyl" is used herein to describe a carbocyclic non-aromatic group linked through a ring carbon atom, and "cycloalkylalkyl" is used herein to describe a carbocyclic non-aromatic group linked within a molecule via an alkyl linker. Similarly, "heterocyclyl" is used to describe a non-aromatic cyclic group that contains at least one heteroatom as a ring member and is linked to a molecule through a ring atom that may be C or N, and "heterocyclylalkyl" may be used to describe a group that is linked to another molecule via an alkylene linker. As used herein, these terms also include rings that contain a double bond or two, as long as the ring is not aromatic.

[0048] An "aromatic" or "aryl" substituent or moiety refers to a monocyclic or fused bicyclic moiety having the well-known characteristics of aromaticity, examples of which include phenyl and naphthyl. Similarly, the terms "heteroaromatic" and "heteroaryl" refer to such monocyclic or fused bicyclic ring systems containing one or more heteroatoms as ring members. Suitable heteroatoms include N, O, and S, and the inclusion of these heteroatoms allows for aromaticity in five-membered as well as six-membered rings. Typical heteroaromatic systems include monocyclic C5-C6 aromatic groups such as pyridyl, pyrimidyl, pyrazinyl, thienyl, furanyl, pyrrolyl, pyrazolyl, thiazolyl, oxazolyl, and imidazolyl, and fused bicyclic moieties formed by fusing one of these monocyclic groups to either a phenyl ring or a heteroaromatic monocyclic group to form C8-C10 bicyclic groups such as indolyl, benzimidazolyl, indazolyl, benzotriazolyl, isoquinolyl, quinolyl, benzothiazolyl, benzofuranyl, pyrazolopyridyl, quinazolyl, quinoxaline, and cinnolinyl. Monocyclic or fused-ring bicyclic systems characterized by aromaticity in terms of electron distribution throughout the ring system are included within this definition. Also included are bicyclic groups in which at least the ring directly attached to the remainder of the molecule is characterized by aromaticity. Typically, ring systems contain 5 to 12 ring atoms. Preferably, monocyclic heteroaryls contain 5 to 6 ring members and bicyclic heteroaryls contain 8 to 10 ring members.

[0049] The aryl and heteroaryl moieties can be substituted with a variety of substituents, including C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C5-C12 aryl, C1-C8 acyl, and heterologs thereof, each of which can itself be further substituted; other substituents for the aryl and heteroaryl moieties are halogen (F, Cl, Br, I), OR, NR2, SR, SO2R, SO2NR2, NRSO2R, NRCONR2, NRC(O)OR, NRC(O) Examples of substituents include R, CN, C(O)OR, C(O)NR, OC(O)R, C(O)R, and NO, where each R is independently H, C-C alkyl, C-C heteroalkyl, C-C alkenyl, C-C heteroalkenyl, C-C alkynyl, C-C aryl, C-C heteroaryl, C-C arylalkyl, or C-C heteroarylalkyl, and each R is optionally substituted as described above for alkyl groups. Substituents on aryl or heteroaryl groups may, of course, be further substituted with groups described herein as appropriate for each type of such substituent or component of the substituent. Thus, for example, an arylalkyl substituent may be substituted on the aryl portion with substituents described herein as typical for aryl groups, and on the alkyl portion with substituents described herein as typical or appropriate for alkyl groups.

[0050] As used herein, "optionally substituted" indicates that the particular group being described may have one or more hydrogen substituents replaced with a non-hydrogen substituent. In some optionally substituted groups or moieties, all hydrogen substituents are replaced with a non-hydrogen substituent, such as C-C alkyl, C-C heteroalkyl, alkynyl, halogen (F, Cl, Br, I), N, OR, NR, SiR, OSiR, SR, SO, SO, NR, SO, R, NR, NR, NR, NR, NR, NR, NR, NR, CN, C(O)OR, C(O)NR, OC(O)R, C(O)R, oxo, and NO, where each R is independently H, C-C alkyl, C-C aryl, or C-C heteroalkyl. When any substituent is attached through a double bond, such as a carbonyl oxygen or oxo (=O), the group occupies two available valences and therefore the total number of substituents that can be included is reduced accordingly by the number of available valences. In some embodiments, an optional non-hydrogen substituent is OSiRR'R", where R, R', and R' are independently H, C1-C10 alkyl, or C6-C10 aryl.

[0051] In some embodiments, the optional substituents may be reactive groups such as groups capable of crosslinking by (4+2) cycloaddition, e.g., JPEG2026027285000046.jpg2028 and Contains JPEG2026027285000047.jpg1216.

[0052] In some embodiments of Formula A, Z 1 , Z 2 , Q, X, and A may be optionally substituted with one or more reactive groups, such as groups capable of crosslinking by (4+2) cycloaddition as described above.

[0053] In some embodiments of Formula A, the compound has Formula A1: It is represented as JPEG2026027285000048.jpg3249, where: Z 2 , Q, X, A, n, and m are as defined above in the compound of formula A, and R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0054] In some embodiments, the compound has formula A2: It is represented by JPEG2026027285000049.jpg3658, where: Q, X, A, n and m are as defined above; R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, R 7 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Alkyloxy, optionally substituted C3-C 10 Heteroalkyloxy, or NR 3 R 4 and R 3 and R 4 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0055] In some embodiments, the compound has formula A3: It is represented as JPEG2026027285000050.jpg3960, where: Q, X, A, n, and m are as defined above; R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 3 and R 4 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0056] In some embodiments, the compound has formula A4: It is represented as JPEG2026027285000051.jpg4069, where: Q, X, A, n, and m are as defined above for compound A; R 1 and R 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10is cycloheteroalkyl, and R' is an optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0057] In some embodiments of Formulas A1-A4, Q is JPEG2026027285000052.jpg1024.

[0058] In some embodiments of Formulas A1-A4, Q is JPEG2026027285000053.jpg1022, where J is S, O, or NR 8 Yes, and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 It is heteroaryl.

[0059] In some embodiments of Formulas A1-A4, Q is JPEG2026027285000054.jpg1228, where: J, in each occurrence, is independently S, O, or NR 8 and and R 8 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 It is heteroaryl.

[0060] In some embodiments, J is S. In some embodiments, J is O. In some embodiments, J is NR 8 is.

[0061] In some embodiments of Formulas A1-A4, A is JPEG2026027285000055.jpg2027, where R' and R" are independently optionally substituted C-C 12 Alkyl (e.g., fluorinated alkyl) and optionally substituted C-C 10 aryl (e.g., fluorinated aryl), and G 1 , G 2 , and G 3 are independently selected from electronegative groups including F, CN, CF3, and SO2CF3.

[0062] In some embodiments, R' is CF3. In other embodiments, R" is phenyl. In certain embodiments, G 1 , G 2 , and G 3 is CN.

[0063] In some embodiments, A is JPEG2026027285000056.jpg2028.

[0064] In some embodiments, m is 1. In some embodiments, n is 1.

[0065] In some embodiments, the compound has formula A5: JPEG2026027285000057.jpg3974 is a compound, where: Z 1 and Z 2 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000058.jpg2627 or JPEG2026027285000059.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0066] In some embodiments, the compound has formula A6: JPEG2026027285000060.jpg4170 is a compound, where: Z 1 is optionally substituted C6-C 10 Aryl or optionally substituted C5-C 10is heteroaryl, Z 2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000061.jpg2627 or JPEG2026027285000062.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0067] In some embodiments, the compound has formula A7: JPEG2026027285000063.jpg3771 compound, where: Z 1 is optionally substituted C6-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, Z2 is H, optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl, optionally substituted C3-C 10 Cycloheteroalkyl, optionally substituted C-C 10 Aryl or optionally substituted C5-C 10 is heteroaryl, X is JPEG2026027285000064.jpg2627 or JPEG2026027285000065.jpg1121, L is absent or L is S or O; Y is H, optionally substituted C-C 20 Alkyl, optionally substituted C3-C 50 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl.

[0068] The polarizable chromophores disclosed herein may contain one or more reactive groups capable of forming covalent bonds (i.e., crosslinks) when reacted with counterpart groups (e.g., upon exposure to elevated temperatures). Any suitable reactive group and counterpart group can be used to form films comprising the chromophores disclosed herein. In some embodiments, the reactive group and counterpart group are groups capable of crosslinking by (4+2) cycloaddition. A number of such groups are known in the art.

[0069] In some embodiments, Y, X, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In some embodiments, one or more of Y, X, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is optionally substituted with one or more reactive groups (e.g., a group crosslinkable by (4+2) cycloaddition, such as an anthracenyl group or an acrylate group). In some embodiments, the group crosslinkable by (4+2) cycloaddition has the structure: JPEG2026027285000066.jpg2936 or Represented by JPEG2026027285000067.jpg2926, where k is 0, 1, 2, 3, 4, or 5, and each Q * are independently NH, N(C1-C10-alkyl), O, or S.

[0070] In some embodiments, Y, X, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 One or more of the following may be optionally substituted with one or more functional groups or protective functional groups, which may be present in addition to the one or more reactive groups described above. As used herein, a "functional group" is a group, substituent, or site responsible for a characteristic chemical reaction of a molecule containing such a functional group. For example, a hydroxyl functional group is a group capable of undergoing an esterification reaction, and the hydroxyl functional group may be protected with a silyl protecting group such as trimethylsilyl or tert-butyldiphenylsilyl (TBDPS).

[0071] In some embodiments of the formulae disclosed herein, LY is H, OL 1 OSiR10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 where L 1 is an optionally substituted C2 to C20 alkylene or an optionally substituted C3 to C50 heteroalkylene, and R 10 , R 11 , and R 12 are independently H, C1-C 10 Alkyl or C 6- C 10 In some embodiments, LY is —SCH 2 CH 2 OH or —SCH 2 CH 2 OTBDPS.

[0072] In some embodiments, R 1 is methyl or optionally substituted ethyl. In some embodiments, R 2 is methyl or optionally substituted ethyl. In some embodiments, R 3 is methyl or optionally substituted ethyl. In some embodiments, R 4 is methyl or optionally substituted ethyl.

[0073] In some embodiments, R 5 is CH3 and R 6 is CH3.

[0074] In some embodiments of the compounds disclosed herein, Z 1 and at least one of X is JPEG2026027285000068.jpg3380 and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C1-C 10 -alkyl), and R 10 , R11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0075] In some embodiments of the compounds disclosed herein, LY is H, OL 1 OSiR 10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 where L 1 optionally substituted C2-C 20 Alkylene or optionally substituted C3-C 50 heteroalkylene, and R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0076] In some embodiments of the compounds disclosed herein, X is JPEG2026027285000069.jpg1727 or JPEG2026027285000070.jpg3327, where G 4 is OSiR 10 R 11 R 12 where R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 aryl or G 4 teeth, JPEG2026027285000071.jpg3240 or JPEG2026027285000072.jpg2434, where G 5 is NH, O, S, or N(C1-C 10 -alkyl).

[0077] In some embodiments, X is JPEG2026027285000073.jpg3337, where k is an integer from 1 to 20, and R 10 , R 11 , and R 12 are independently H, C 1- C 10 Alkyl, or C6-C 10 It is aryl.

[0078] In some embodiments, X is JPEG2026027285000074.jpg1726 or JPEG2026027285000075.jpg3334, Where TBDPS is: JPEG2026027285000076.jpg2018.

[0079] In some embodiments, the compound has formula A8: JPEG2026027285000077.jpg4195 is a compound, where: G 6 is OR' or NR'R", where R' and R" are independently optionally substituted C-C 10 is alkyl, R 1 is H or optionally substituted C1-C 10 is alkyl, R 2 is optionally substituted C1-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and Y is an optionally substituted C-C 10 Alkyl, optionally substituted C3-C 10 Heteroalkyl, optionally substituted C-C 10 Cycloalkyl or optionally substituted C3-C 10 is cycloheteroalkyl, and where R 2 , Y, and G 6 At least one of the JPEG2026027285000078.jpg3378 and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C1-C 10 -alkyl), and R 10 , R 11 , and R 12 are independently H, optionally substituted C-C 10 Alkyl or optionally substituted C-C 10 It is aryl.

[0080] In some embodiments, the compound is Compound I, Compound II, Compound III, or Compound IV, Compound V, Compound VI, Compound VII, Compound VIII, Compound IX, Compound X, Compound XI, Compound XII, Compound XIII, Compound XIV, or Compound XV: JPEG2026027285000079.jpg247152JPEG2026027285000080.jpg251152, Where TBDPS is: JPEG2026027285000081.jpg2118.

[0081] The chromophores disclosed herein, e.g., compounds of Formulae A, A1, A2, A3, A4, A5, A6, A7, A8, I, II, III, IV, V, VI, VII, VIII, IX, XI, XII, XIII, XIV, and XV, can be produced by standard organic synthesis methods known to those skilled in the art using common intermediates for many known OEO chromophores, including substituted thioether-substituted isophorones and CF3-phenyl-substituted tricyanofuran (TCF) acceptors (e.g., Dalton, LR; Sullivan, PA; Bale, DH, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects. Chemical Reviews 2010, 110 (1), 25-55, the disclosure of which is incorporated herein by reference in its entirety). The synthesis of exemplary chromophores is shown in Figures 2 and 7.

[0082] In one embodiment, the chromophores disclosed herein have a large static hyperpolarizability. In certain embodiments, the chromophores disclosed herein have a static hyperpolarizability between about 1.5 and about 3 times that of the reference chromophore JRD1 (FIG. 1), as measured, for example, by hyper-Rayleigh scattering at 1300 nm in chloroform solution and extrapolated to zero frequency using a damped two-level model. In some embodiments, the chromophores disclosed herein have a static hyperpolarizability greater than about 1.5 to about 3 times that of the reference chromophore JRD1.

[0083] In another aspect, the present disclosure provides polymer compositions comprising the chromophores disclosed herein. In certain embodiments, the chromophores are blended with polymers to form processable and durable films that can exhibit electro-optical activity induced by electric field poling (a process in which a strong DC electric field is applied to a film, the film is heated to near its glass transition temperature (Tg) to reorient the chromophore dipole moments into net alignment with the electric field, and then cooled in the presence of the electric field to retain the poling order). Electro-optical activity can be measured by Teng-Man ellipsometry, an attenuated total reflectance (ATR) technique known to those skilled in the art.

[0084] In certain embodiments, films comprising the chromophores disclosed herein blended with polymethyl methyl acrylate (PMMA) have a luminance of from about 70 pm / V to about 300 pm / V, from about 40 pm / V to about 140 pm / V, from about 30 pm / V to about 250 pm / V, from about 75 pm / V to about 300 pm / V, from about 80 pm / V to about 250 pm / V, from about 50 pm / V to 200 pm / V, from about 15 to about 105 pm / V, from about 105 to about 405 pm / V, from about 125 to about 1100 pm / V, from about 125 to about 1200 pm / V, from about 125 to about 1300 pm / V, from about 125 to about 1500 pm / V, greater than about 350 pm / V, greater than about 500 pm / V, greater than 750 pm / V, or greater than about 1000 pm / V as measured by Teng-Man ellipsometry. pm / V 33 It has a value.

[0085] In some embodiments, films containing the chromophores described herein can be combined with films of dielectric materials or wide bandgap semiconductors as charge blocking layers (e.g., to minimize conductivity during poling of the film). Such films include poly(benzocyclobutene) (BCB, Cyclotene) TMThe charge blocking layer may comprise an organic material such as SiO 2 , MoO 3 , ZrO 2 , HfO 2 , SiO 2 , Al 2 O 3 , Si 3 N 4 , or an inorganic material including, but not limited to, TiO 2 , MoO 3 , ZrO 2 , HfO 2 , SiO 2 , Al 2 O 3 , Si 3 N 4 , or a combination thereof. In some embodiments, the film comprises poly(benzocyclobutene). In some embodiments, the BCB layer has a thickness of about 40 nm to about 150 nm, or about 60 nm to about 100 nm. In some embodiments, the charge blocking layer is a layer described, for example, in "Benzocyclobutene barrier layer for suppressing conductance in nonlinear optical devices during electric field poling," Applied Physics Letters 104, 243304 (2014).

[0086] In yet another aspect, the present disclosure provides electro-optical devices comprising the films disclosed herein or films formed by the methods disclosed herein. Exemplary devices incorporating the films disclosed herein include electro-optical modulators, antennas, Mach-Zehnder modulators, phase modulators, silicon-organic hybrid modulators, plasmonic-organic hybrid modulators, electro-optical converters, terahertz detectors, frequency shifters, or frequency comb sources. In some embodiments, electro-optical devices comprising the films disclosed herein further comprise one or more charge-blocking layers, as described above.

[0087] Certain components of optical communication systems can be fabricated, in whole or in part, with the films disclosed herein. Exemplary components include, but are not limited to, straight waveguides, bends, single-mode splitters, couplers (including directional couplers, MMI couplers, and star couplers), routers, filters (including wavelength filters), switches, modulators (optical and electro-optical, e.g., birefringence modulators, Mach-Zehnder interferometers, and directional and evanescent couplers), arrays (including long, dense waveguide arrays), optical interconnects, optochips, single-mode DWDM components, photonic crystal devices, resonator devices (e.g., photonic crystals, ring or disk resonators, and diffraction gratings). The films described herein may be used, for example, in wafer-level processing, for example, in applications in vertical-cavity surface-emitting laser (VCSEL) and CMOS technologies.

[0088] In many applications, the films described herein can be used in place of lithium niobate, gallium arsenide, and other inorganic materials currently finding use as optically transparent materials in optical communication systems.

[0089] Unless otherwise defined herein, all terms used herein have the same meaning to one skilled in the art of the present invention.

[0090] As used herein, the term "about" indicates that the subject value can be modified by plus or minus 5% and still fall within the disclosed embodiments.

[0091] The use of the term "or" in the claims is intended to mean "and / or," unless expressly indicated to refer to alternatives only or where the alternatives are mutually exclusive, and this specification supports a definition that refers to alternatives only and "and / or." In the claims or specification, the words "a" and "an," when used in conjunction with the word "comprising," indicate one or more, unless otherwise specified.

[0092] Unless the context clearly requires otherwise, throughout this specification and claims, the words "comprise," "comprising," and the like are to be construed in an inclusive sense, i.e., "including but not limited to," as opposed to an exclusive or exhaustive sense. Also, words using the singular or plural include the plural and the singular, respectively. As used herein, a term in the form "A / B" or "A and / or B" means (A), (B), or (A and B). As used herein, a term in the form "at least one of A, B, and C" means (A), (B), (C), (A and B), (A and C), (B and C), or (A, B, and C). As used herein, a term in the form "(A)B" means (B) or (AB), i.e., A is an optional element. Furthermore, the words "herein," "above," and "below," and similar inclusive terms, when used in this application, shall refer to this application as a whole and shall not refer to particular portions of this application.

[0093] All publications cited herein and the subject matter for which they are cited are specifically incorporated herein by reference in their entirety.

[0094] The following examples are provided to illustrate particular features and / or embodiments of the present disclosure and should not be construed as limiting the present disclosure to the particular features or embodiments described. [Example]

[0095] Example Using density functional theory (DFT) calculations performed using well-validated methods, we have found that the chromophores disclosed herein, such as compounds I and II, can possess large hyperpolarizabilities. Calculations were performed at the M062X / 6-31+G(d) level of theory in a chloroform negative solvent environment (PCM), and hyperpolarizabilities were calculated using analytical differential calculus (CPHF). Similar calculations were also performed using a truncated model of JRD1 as a standard. The OTBDPS group on the donor of JRD1 was replaced with hydrogen for computational efficiency, and the donor was modeled as diethylaniline. Based on this model, we report the results of the hyperpolarizability calculations. Exemplary compounds I-XV were synthesized using standard organic synthesis methods familiar to those skilled in the art, and the proton ( 1 The composition was confirmed by H NMR and electrospray ionization mass spectrometry (ESI-MS). UV / visible absorption spectra were measured in both chloroform and thin films using methods well known to those skilled in the art.

[0096] The hyperpolarizabilities of exemplary compounds I, II, III, IV, V, VI, and VII in chloroform solution were measured by hyper-Rayleigh scattering (HRS) using light generated by a high-repetition-rate (80 MHz), broadband (680-1300 nm) femtosecond pulsed laser (InsightDS+, Spectra-Physics) tuned to 1300 nm, as previously described (Campo, J.; Desmet, F.; Wenseleers, W.; Goovaerts, E., Highly sensitive setup for tunable wavelength hyper-Rayleigh scattering with parallel detection and calibration data for various solvents. Optics Express 2009, 17 (6), the disclosure of which is incorporated herein by reference). Measurements were performed relative to a pure chloroform standard, and data were extrapolated to zero frequency using a damped two-level model and a linewidth of 0.1 eV. To eliminate the dependency on the chloroform standard and to clarify the comparison with the state of the art, the state-of-the-art chromophore JRD1 was also measured in the same set of experiments, and the data are reported relative to JRD1. The data from the DFT, UV / Vis, and HRS measurements are summarized in Table 1.

[0097] JPEG2026027285000082.jpg93165

[0098] Exemplary thin films containing exemplary compounds I, II, III, IV, VI, and VII were cast onto glass slides and / or glass slides where half of the slide was coated with a conductive layer of indium tin oxide (ITO). ITO slides were produced by Thin Film Devices (Anaheim, CA). Chromophores were deposited by spin coating from trichloroethane (TCE) solutions containing the chromophores (neat or mixed with PMMA). Films were dried in a vacuum oven at 65°C before use.

[0099] The complex refractive index (n and k) of thin films containing exemplary compounds I, II, III, and IV on glass substrates was measured using a Woollam MC2000 spectroscopic ellipsometer at the UW Molecular Analysis Facility using JA Variable Angle Spectroscopic Ellipsometry (VASE) and a previously described method (Benight, SJ; Johnson, LE; Barnes, R.; Olbricht, BC; Bale, DH; Reid, PJ; Eichinger, BE; Dalton, LR; Sullivan, PA; Robinson, BH, Reduced Dimensionality in Organic Electro-Optic Materials: Theory and Defined Order. The Journal of Physical Chemistry B 2010, 114 (37), 11949-11956, the disclosure of which is incorporated herein by reference). The data for exemplary compounds I, II, III, and IV as neat films are shown in Figure 3. Data for films of Compound II in PMMA and compared to neat JRD1 are shown in Figure 4. The data in Figure 4 are representative of the behavior of compounds disclosed herein when incorporated into dilute polymer films.

[0100] For electro-optical measurements, gold electrodes were sputter-coated onto thin films of exemplary compounds I, II, III, IV, VI, and VII, and wires were attached using commercially available silver paste. Electro-optical measurements were performed with E values ​​ranging from 15 V / μm to 110 V / μm. PThe materials were prepared by poling at a temperature appropriate for the Tg of the material using a poling field of 1000 Hz, cooling to <35°C, and measuring the electro-optical activity at 1310 nm using previously reported methods and equipment (Dalton, LR; Sullivan, PA; Bale, DH, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects. Chemical Reviews 2010, 110 (1), 25-55, the disclosure of which is incorporated herein by reference). Representative poling results for exemplary compounds II and III are shown in Figure 5. The poling efficiency r 33 / Ep is the electro-optical activity (pm / V) vs. E p was determined by linear fitting.

[0101] In addition to the data shown in FIG. 5, exemplary Compound I at a 10 wt. % concentration in PMMA exhibited a 1.77 nm 2 / V 2 Compound III at a concentration of 25% by mass in PMMA demonstrated a poling efficiency of 2.87 nm. 2 / V 2 This poling efficiency is comparable to that of 25% JRD1 (~1 nm) in PMMA. 2 / V 2 ) compares very favorably with the poling efficiency of exemplary compounds II and IV at low concentrations, which is particularly exceptional for their number densities. Exemplary compound II at 10% concentration in PMMA (2.82 nm 2 / V 2 ) and exemplified compound IV (2.86 nm) at 10% concentration in PMMA 2 / V 2) competed with neat JRD1 (Jin, W.; Johnston, PV; Elder, DL; Tillack, AF; Olbricht, BC; Song, J.; Reid, PJ; Xu, R.; Robinson, BH; Dalton, LR, Benzocyclobutene barrier layer for suppressing conductance in nonlinear optical devices during electric field poling. Applied Physics Letters 2014, 104 (24), 243304, the disclosure of which is incorporated herein by reference, and demonstrated a poling efficiency of 3.43 ± 0.2 nm with a BCB charge blocking layer between the ITO and OEO materials. 2 / V 2 , with and without a charge-blocking layer has 3.1 ± 0.1). The over 2.5-fold improvement in EO activity at a given concentration in a polymer host demonstrates the utility of exemplary chromophores, including novel thienothiophene-derived donors such as exemplary compounds I, II, III, and IV, in electro-optical devices, enabling high device performance while providing substantial flexibility in blending with chromophores.

[0102] Exemplary compounds V, VI, and VII demonstrated the range of structural variations of the present invention utilizing different aromatic groups and side chain substitutions in the electron-donating region of the molecule, allowing for the desired tuning of substitution and optical properties, while exhibiting improved hyperpolarizability over the state-of-the-art compound JRD1, as shown in Table 1. Exemplary compound VI was synthesized at a 10% concentration (0.90 nm) in PMMA. 2 / V 2) to 25% JRD1 in PMMA, and exhibits exceptional poling efficiency as a neat material (100% concentration, no polymer) when combined with a charge-blocking layer to reduce the current during poling. A poling efficiency of 7.98 was obtained when combined with MoO3 (20 nm thick, evaporated) as a charge-blocking layer. A poling efficiency of 15.98 was obtained with a sol-gel TiO2 charge-blocking layer. The latter exhibited a r of over 600 pm / V. 33 values ​​significantly exceeding the recorded values ​​of JRD1 and exceeding the poling efficiency of JRD1 by nearly five times. Additionally, the real component of the refractive index of exemplary compound VI was improved to 2.02 at 1310 nm and 1.90 at 1550 nm, demonstrating exceptional n 3 r 33 The refractive index and poling data for Compound VI are shown in Figure 6. An exemplary Compound VII exhibits a refractive index of 0.94 nm at a 10% concentration in PMMA. 2 / V 2 , slightly exceeding that of exemplary Compound VI at 10% in PMMA.

[0103] While exemplary embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.

Claims

1. Formula A below: A compound of the formula: where: A is a π-electron acceptor group; X is or and L is absent or L is S or O; Y is H, optionally substituted C 1 -C 20 Alkyl, optionally substituted C 3 -C 50 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 is cycloheteroalkyl, n is 1, 2 or 3; n is 1, 2 or 3, and R 5 and R 6 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, Q is or and J, in each occurrence, is independently S, O, or NR 8 and R 8 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 heteroaryl, and Q is, or When Z 1 may be substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 is heteroaryl, and Z 2 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 is heteroaryl, or Q is, When Z 1 and Z 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 is heteroaryl, compound.

2. 10. The compound of claim 1, wherein the compound has the following formula A1: is expressed as where: Z 2 , Q, X, A, n, and m are as defined in claim 1; and R 1 and R 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

3. 3. The compound according to claim 1 or 2, wherein the compound has the following formula A2: is expressed as where: Q, X, A, n and m are as defined in claim 1; R 1 and R 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, R 7 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 1 -C 10 Alkyloxy, optionally substituted C 3 -C 10 Heteroalkyloxy, or NR 3 R 4 and R 3 and R 4 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

4. The compound according to any one of claims 1 to 3, wherein the compound has the following formula A3: is expressed as where: Q, X, A, n, and m are as defined in claim 1; R 1 and R 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and R 3 and R 4 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

5. The compound according to any one of claims 1 to 3, wherein the compound has the following formula A4: is expressed as where: Q, X, A, n, and m are as defined in claim 1; R 1 and R 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and R' is an optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

6. 6. The compound according to any one of claims 1 to 5, wherein Q is A compound.

7. 6. The compound according to any one of claims 1 to 5, wherein Q is and where: J is S, O, or NR 8 and R 8 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 is heteroaryl, compound.

8. 6. The compound according to any one of claims 1 to 5, wherein Q is and where: J, in each occurrence, is independently S, O, or NR 8 and R 8 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl or optionally substituted C 5 -C 10 is heteroaryl, compound.

9. 9. The compound of claim 7 or claim 8, wherein J is S.

10. A compound according to any one of claims 1 to 9, wherein A is and wherein R′ and R″ are independently optionally substituted C 1 -C 12 Alkyl (e.g., fluorinated alkyl) and optionally substituted C 6 -C 10 aryl (e.g., fluorinated aryl), and G 1 , G 2 , and G 3 are independently F, CN, and CF 3 , SO 2 CF 3 Selected from compound.

11. A compound according to any one of claims 1 to 10, wherein A is A compound.

12. 12. The compound of claim 1, wherein m is 1.

13. 13. The compound of any one of claims 1 to 12, wherein n is 1.

14. 10. The compound of claim 1, wherein the compound has formula A5: is a compound of where: Z 1 and Z 2 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 aryl or optionally substituted C 5 -C 10 is heteroaryl, X is or and L is absent or L is S or O; Y is H, optionally substituted C 1 -C 20 Alkyl, optionally substituted C 3 -C 50 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

15. 10. The compound of claim 1, wherein the compound has the following formula A6: is a compound of where: Z 1 may be substituted C 6 -C 10 Aryl or optionally substituted C 5 -C 10 is heteroaryl, Z 2 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl or optionally substituted C 5 -C 10 is heteroaryl, X is or and L is absent or L is S or O; Y is H, optionally substituted C 1 -C 20 Alkyl, optionally substituted C 3 -C 50 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

16. 10. The compound of claim 1, wherein the compound has formula A7: is a compound of where: Z 1 may be substituted C 6 -C 10 Aryl or optionally substituted C 5 -C 10 is heteroaryl, Z 2 is H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 Cycloalkyl, optionally substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl or optionally substituted C 5 -C 10 is heteroaryl, X is or and L is absent or L is S or O; Y is H, optionally substituted C 1 -C 20 Alkyl, optionally substituted C 3 -C 50 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, compound.

17. 17. The compound according to any one of claims 1 to 16, wherein the compound comprises one or more reactive groups capable of forming a covalent bond when reacted with a reactive group of a counterpart.

18. 18. The compound of claim 17, wherein the one or more reactive groups are groups capable of crosslinking by (4+2) cycloaddition.

19. 17. The compound according to claim 1, wherein Z 1 and at least one of X is and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C 1 -C 10 -alkyl), and R 10 , R 11 , and R 12 are independently H, optionally substituted C 1 -C 10 Alkyl or optionally substituted C 6 -C 10 is aryl, compound.

20. LY is H, OL 1 OSiR 10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 where L 1 optionally substituted C 2 -C 20 Alkylene or optionally substituted C 3 -C 50 heteroalkylene, and R 10 , R 11 , and R 12 are independently H, optionally substituted C 1 -C 10 Alkyl or optionally substituted C 6 -C 10 20. The compound of any one of claims 1 to 19, which is aryl.

21. 21. The compound according to any one of claims 1 to 20, wherein X is or and where G 4 is OSiR 10 R 11 R 12 where R 10 , R 11 , and R 12 are independently H, optionally substituted C 1 -C 10 Alkyl or optionally substituted C 6 -C 10 aryl or G 4 teeth, or and where G 5 is NH, O, S, or N(C 1 -C 10 -alkyl), compound.

22. 10. The compound of claim 1, wherein the compound has the following formula A8: is a compound of where: G 6 is OR' or NR'R", where R' and R" are independently optionally substituted C 1 -C 10 is alkyl, R 1 is H or optionally substituted C 1 -C 10 is alkyl, R 2 may be substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and Y is an optionally substituted C 1 -C 10 Alkyl, optionally substituted C 3 -C 10 Heteroalkyl, optionally substituted C 3 -C 10 cycloalkyl or optionally substituted C 3 -C 10 is cycloheteroalkyl, and where R 2 , Y, and G 6 At least one of the and OSiR 10 R 11 R 12 and is substituted with a group selected from where G 5 is NH, O, S, or N(C 1 -C 10 -alkyl), and R 10 , R 11 , and R 12 are independently H, optionally substituted C 1 -C 10 Alkyl or optionally substituted C 6 -C 10 is aryl, compound.

23. 23. The compound according to any one of claims 1 to 22, wherein the compound is Compound I, Compound II, Compound III, or Compound IV, Compound V, Compound VI, Compound VII, Compound VIII, Compound IX, Compound X, Compound XI, Compound XII, Compound XIII, Compound XIV, or Compound XV: and Where TBDPS is: A compound.

24. Electro-optically active film comprising one or more compounds according to claims 1 to 23.

25. 25. The film of claim 24, wherein the film further comprises a polymer.

26. 26. The film of claim 25, wherein the polymer is polymethyl methacrylate (PMMA).

27. The film has an r greater than about 100 pm / V 33 27. The film of any one of claims 24 to 26, having a value.

28. The film has an r greater than about 1000 pm / V 33 28. The film of any one of claims 24 to 27, having a value.

29. 29. The film of any one of claims 24 to 28, wherein the film has a Tg of about 105°C or greater.

30. 24. A method of forming an electro-optically active film, comprising the steps of depositing a compound or a mixture comprising the compound of any one of claims 1 to 23 onto a substrate to provide a film, applying an alignment force to the film at a temperature sufficient to provide a film in which at least a portion of the compound is aligned, and reducing the temperature of the film to provide an electro-optically active film.

31. 24. An electro-optical device comprising a compound according to any one of claims 1 to 23.

32. An electro-optical device comprising the film of any one of claims 24 to 29.

33. 33. An electro-optical device according to claim 31 or claim 32, further comprising one or more charge blocking layers.

34. The one or more charge blocking layers may be selected from the group consisting of poly(benzocyclobutene) (BCB), TiO 2 , MoO 3 , ZrO 2 , HfO 2 , SiO 2 , Al 2 O 3 , Si 3 N 4 32. The electro-optical device of claim 31, comprising:

34. 35. The electro-optical device according to any one of claims 31 to 34, wherein the device is an electro-optical modulator, an antenna, a Mach-Zehnder modulator, a phase modulator, a silicon-organic hybrid modulator, a plasmonic-organic hybrid modulator, an electro-optical converter, a terahertz detector, a frequency shifter or a frequency comb source.

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