Organic electro-optic chromophores

Abstract

Chromophores having large hyperpolarizabilities, electro-optically active films containing the chromophores, and electro-optical devices containing the chromophores are disclosed.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Application 62 / 911,067, filed on 4 October 2019, and U.S. Provisional Application 62 / 934,398, filed on 12 November 2019, the disclosures of which are incorporated herein by reference in their entirety.

[0002] Field of Invention This specification provides chromophores useful for inclusion in electro-optical films and electro-optical devices.

[0003] Government statement on licensing rights This invention was made with government support under Grant Gold 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 to this invention. [Background technology]

[0004] background Organic electro-optic (OEO) materials have recently seen a resurgence in interest due to the development of silicon-organic hybrid (SOH) and plasmon-organic hybrid (POH) devices, which combine the high intrinsic electro-optic activity of certain classes of organic chromophores with small device sizes and enable chip-scale integration with CMOS electronics. The size of electro-optic devices is determined by the voltage-length product. It is proportional to JPEG0007839552000001.jpg824. Here, U π n is the voltage required to cause a phase shift of π over the path length L, n is the refractive index of the electro-optic material, and r is the refractive index of the electro-optic material. 33 This is the electro-optic coefficient of the material. In OEO materials, The file is JPEG0007839552000002.jpg830, where ρ N It has a large molecular hyperpolarizability (β) and its dipole moments are non-centered. JPEG0007839552000003.jpg829 is the number density (concentration) of aligned chromophores, where θ is the angle between the dipole moment of the chromophores 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 site such as a substituted amine group and an electron-accepting site containing a strongly electron-withdrawing group such as cyano (CN) or nitro (NO2) are often linked by a π-conjugate linker containing an ene / polyene and / or heteroaromatic group. For example, a D-π-A chromophore like JRD1, shown in Figure 1, is known.

[0006] In an apparatus for any chromophore density, a higher r 33 and smaller U π There is a need for a chromophore with higher chromophore superpolarizability and desirable stability and processability to enable L. [Overview of the project]

[0007] overview This summary is provided to introduce, in a simplified form, the selection of concepts that will be further explained below in the detailed description. This summary is not intended to identify the key features of the requested subject matter, nor is it intended to be used as an aid in determining the scope of the requested subject matter.

[0008] In one embodiment, this specification uses formula A: The compound is JPEG0007839552000004.jpg1850, Here, A is a π-electron acceptor group, X is JPEG0007839552000005.jpg2627 or The filename is JPEG0007839552000006.jpg1121. L does not exist, or L is S or O. Y is H, optionally substituted C1-C 20 alkyl, optionally substituted C3-C 50 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, and n is 1, 2 or 3, and n is 1, 2, or 3, and R 5 and R 6 are each independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl, and Q is JPEG0007839552000007.jpg1247 or JPEG0007839552000008.jpg1228, and J is in each case 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 C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, optionally substituted C6-C 10 aryl, or optionally substituted C5-C 10 heteroaryl, and when Q is JPEG0007839552000009.jpg1224 or JPEG0007839552000010.jpg1019, Z 1 is optionally substituted C6-C 10 aryl, or optionally substituted C5-C 10 heteroaryl, and Z2 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 Heteroaryl, or Q is, When it is JPEG0007839552000011.jpg1228, Z 1 and Z 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl. Provides compounds.

[0009] In some embodiments, the compound is of formula A1: Represented as JPEG0007839552000012.jpg3249, Here, Z 2 Q, X, A, n, and m are as defined above, and R 1 and R 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0010] In some embodiments, the compound is of formula A2: Represented as JPEG0007839552000013.jpg3558, Here, Q, X, A, n, and m are as defined above. R 1 and R 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteralkyl, R 7 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 Cycloheteroalkyl, C1-C which may be substituted. 10 Alkyloxy, C3-C may be substituted. 10 Heteroalkyloxy, or NR 3 R 4 and R 3 and R 4 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0011] In some embodiments, the compound is of formula A3: Represented as JPEG0007839552000014.jpg3960, Here, Q, X, A, n, and m are as defined above. R 1 and R 2is independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl, and R 3 and R 4 are independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl.

[0012] In some embodiments, the compound is of formula A4: represented by JPEG0007839552000015.jpg3460, where Q, X, A, n, and m are as defined above, R 1 and R 2 are independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl, and R' is optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl.

[0013] In some embodiments, Q is JPEG0007839552000016.jpg1024.

[0014] In some embodiments, Q is JPEG0007839552000017.jpg1119, where J is iS, O, or NR 8 and R 8 is H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, optionally substituted C6-C 10 aryl, or optionally substituted C5-C 10 heteroaryl.

[0015] In some embodiments, Q is JPEG0007839552000018.jpg1228, where J is, in each case 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 C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, optionally substituted C6-C 10 aryl or optionally substituted C5-C 10 heteroaryl.

[0016] The In some embodiments, J is S.

[0017] In some embodiments, A is JPEG0007839552000019.jpg2026, where R' and R " are independently optionally substituted C1-C12 Alkyl (e.g., fluorinated alkyl) and optionally substituted C6-C 10 Selected from aryls (e.g., fluorinated aryls), and G 1 , G 2 , and G 3 It is independently selected from F, CN, CF3, and SO2CF3.

[0018] In some embodiments, A is The filename is JPEG0007839552000020.jpg1928.

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

[0020] In some embodiments, the compound is of formula A5: It is the compound of JPEG0007839552000021.jpg3669, Here, Z 1 and Z 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000022.jpg2627 or The filename is JPEG0007839552000023.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C10 It is a cycloheteralkyl, and R 5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0021] In some embodiments, the compound is of formula A6: It is the compound of JPEG0007839552000024.jpg3559, Here, Z 1 C6-C may be substituted. 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, Z 2 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000025.jpg2627 or The filename is JPEG0007839552000026.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10It is a cycloheteroalkyl, and R 5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0022] In some embodiments, the compound is of formula A7: It is the compound of JPEG0007839552000027.jpg3162, Here, Z 1 C6-C may be substituted. 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, Z 2 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000028.jpg2727 or The filename is JPEG0007839552000029.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and R5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0023] In some embodiments, the compound comprises one or more reactive groups that can form a covalent bond when reacted with a reactive group of a counterpart. In some embodiments, one or more reactive groups are groups that can be crosslinked by (4+2) cycloaddition.

[0024] In some embodiments, Z 1 and at least one of X is JPEG0007839552000030.jpg3278 and OSiR 10 R 11 R 12 It is substituted with a group selected from the following: Here is the G 5 is NH, O, S, or N(C1-C 10 -alkyl) and R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[0025] In some embodiments, LY is H, OL 1 OSiR 10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 And here, L 1 C2-C may be substituted. 20 C3-C may be substituted with alkylene. 50It is a heteroalkylene, and R 10 , R 11 , and R 12 Independently, H, C1-C may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[0026] In some embodiments, X is JPEG0007839552000031.jpg1627 or The filename is JPEG0007839552000032.jpg3227. Here is the G 4 OSiR 10 R 11 R 12 And here, R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is either aryl or G 4 teeth, JPEG0007839552000033.jpg3140 or The filename is JPEG0007839552000034.jpg2434. Here is the G 5 is NH, O, S, or N(C1-C 10 It is alkyl.

[0027] In some embodiments, the compound is of formula A8: It is the compound of JPEG0007839552000035.jpg4194. Here, G 6 is OR' or NR'R" where R' and R" may be substituted independently C1-C 10 It is alkyl, R 1 C1-C may be H or substituted. 10 It is alkyl, R 2 C1-C may be substituted.10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and Y may be C1-C even if it is substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and Here, R 2 , Y, and G 6 At least one of them is JPEG0007839552000036.jpg3378 and OSiR 10 R 11 R 12 It is substituted with a group selected from the following: Here is the G 5 is NH, O, S, or N(C1-C 10 -alkyl) and R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[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 embodiment, this specification provides electro-optically active films comprising one or more compounds disclosed herein. In some embodiments, the film further comprises a polymer. In some embodiments, the polymer is polymethyl methacrylate (PMMA). In some embodiments, the film has an r greater than about 100 pm / V 33 The film has a value. In some embodiments, the film has an r33 value greater than approximately 1000 pm / V. In some embodiments, the film has a Tg of approximately 105°C or higher.

[0030] In another embodiment, this specification provides a method for forming an electro-optically active film, comprising the steps of: depositing a compound or a mixture containing a compound described herein 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 lowering the temperature of the film to provide an electro-optically active film.

[0031] In another embodiment, this specification provides an electro-optical apparatus comprising a compound disclosed herein.

[0032] In another embodiment, this specification provides an electro-optical apparatus including a film disclosed herein.

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

[0034] The above-described aspects of the present invention and its many associated advantages will be better and more readily understood by referring to the following detailed description, in conjunction with the accompanying drawings.

[0035] [Figure 1] Figure 1 shows a known JRD1 chromophore with donor, π-bridge, and acceptor labeling. JRD1 includes a substituted aniline donor, a ring-lock polyene bridge, and a CF3-phenyl-substituted tricyanofuran (TCF) acceptor. [Figure 2] Figure 2 shows the synthesis of compound IV, an exemplary chromophore. [Figure 3A-3B] Figures 3A and 3B show the real (n, Figure 3A) and imaginary (k, Figure 3B) components of the refractive index of compound I, compound II, compound III, or compound IV, which are representative chromophores. [Figure 4A-4B] Figures 4A and 4B show the real (n, Figure 4A) and imaginary (k, Figure 4B) refractive index components 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] Figures 5A-5B show electro-optic measurements of exemplary compound II and exemplary compound IV thin films in PMMA obtained at 1310 nm using the Teng-Man ellipsometry method. [Figure 6A-6B] Figures 6A and 6B show the Poling efficiency (electro-optic coefficient as a function of the Poling field) of exemplary compound VI under various conditions (Figure 6A) and the real (n) and imaginary (k) components of the refractive index of exemplary compound VI (Figure 6B). [Figure 7] Figure 7 shows the synthesis of compound VI, an exemplary chromophore. Detailed description of the invention

[0036] Detailed explanation This specification provides a chromophore having a high hyperpolarizability, an electro-optically active film containing the chromophore, and an electro-optical apparatus containing the chromophore. Because the chromophore disclosed herein has a high molecular hyperpolarizability, a large electro-optic coefficient (r) is obtained in the film containing this chromophore. 33 This can be achieved.

[0037] The polar chromophore compounds or polar 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 “polar chromophore compound,” “polar chromophore,” and “chromophore” are used interchangeably throughout this disclosure unless otherwise specified. In the context herein, the term “nonlinear” refers to a secondary effect arising from the properties of polar chromophore compounds having a general structure D-π-A (i.e., “push-pull” chromophore compounds), 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 for an acceptor (defined below) such that when the donor is conjugated to the acceptor via a π bridge, the electron density shifts from the donor to the acceptor.

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

[0040] "π-bridge" or "conjugate bridge" (in chemical structural formulas, "π" or "π" nA bridge (represented by n, where n is an integer) contains an atom or group of atoms through which electrons can be delocalized from an electron donor (as defined above) to an electron acceptor (as defined above) via the orbitals of the atoms in the bridge. Preferably, the orbitals can be p orbitals on multiple bonded carbon atoms, as found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. Furthermore, the orbitals may be p orbitals on multiple bonded atoms such as boron or nitrogen, or organometallic orbitals. The atoms in the bridge that contain the orbitals through which electrons are delocalized are referred to here as “critical atoms”. The number of critical atoms in a bridge can be between 1 and about 30. The critical atoms can also be further substituted with “alkyl”, “aryl”, or “heteroalkyl”, as defined below. One or more atoms, excluding hydrogen, on the alkyl, aryl, or heteroalkyl substituents of the critical atoms in the bridge may bond to atoms of other alkyl, aryl, or heteroalkyl substituents to form one or more rings.

[0041] In one embodiment, this specification uses formula A: JPEG0007839552000037.jpg1851 is a polarizing chromophore compound, Here, A is a π-electron acceptor group, Z 1 and Z 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, Q is, JPEG0007839552000038.jpg1249 or The filename is JPEG0007839552000039.jpg1228. In each case, J is independently S, O, or NR 8And, R 8 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000040.jpg2627 or The filename is JPEG0007839552000041.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteralkyl, n is 1, 2, or 3. n is 1, 2, or 3, and R 5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, R 6 These are independently H, and C1-C which may be substituted. 10 It is heteroalkyl, however, Q is, JPEG0007839552000042.jpg1023 or When it is JPEG0007839552000043.jpg1119, Z 1C6-C may be substituted. 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl, and Z 2 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl, and Q is, When it is JPEG0007839552000044.jpg1228, Z 1 and Z 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl. This provides polarized chromophore compounds.

[0042] As used herein, the terms “alkyl,” “alkenyl,” and “alkynyl” include linear, branched, 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, etc. In this specification, the total number of carbon atoms in each such group may also be described, for example, if a group can contain up to 10 carbon atoms, it will be written as 1-10C, or C1-C 10 It can be represented as C-C10 or C1-10.

[0043] As used herein, the terms “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” refer to the corresponding hydrocarbons in which one or more carbon atoms in a chain are substituted with heteroatoms. Exemplary heteroatoms include N, O, S, and P. Where carbon atoms can be replaced with heteroatoms, as in heteroalkyl groups, even if written as C3-C10, the numbers representing the group represent the number of carbon atoms in the cycle or chain and the total number of heteroatoms included in place of the carbon atoms in the described cycle or chain.

[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 single group may contain one or more types of multiple bonds, or two or more types of multiple bonds. Such groups are included in the definition of the term "alkenyl" if they contain at least one carbon-carbon double bond, and in 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 “alkylynylene” may include linear, branched, and cyclic divalent hydrocarbyl radicals, as well as combinations thereof. As used herein, the terms “cycloalkylene,” “cycloalkenylene,” and “cycloalkylynylene” refer specifically to cyclic divalent hydrocarbyl radicals.

[0046] Alkyl, alkenyl, and alkynyl groups can be arbitrarily substituted within a chemically meaningful range. Typical substituents, though not limited to these, include halogens (F, Cl, Br, I), =O, =N-CN, =N-OR, =NR, OR, NR2, SR, SO2R, SO2NR2, NRSO2R, 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 independently represents 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, and C6-C10 ali. The R is a C5-C10 heteroaryl, where each R is optionally substituted with a halogen (F, Cl, Br, I), =O, =N-CN, =N-OR', =NR', OR', NR'2, SR', SO2R', SO2NR'2, NR'SO2R', 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 with C1-C8 acyls, C2-C8 heteroacyls, C6-C10 aryls, or C5-C10 heteroaryls, each of which can be substituted with substituents appropriate for the particular group.

[0047] As used herein, “alkyl” includes cycloalkyl and cycloalkylalkyl groups, but herein the term “cycloalkyl” is used to describe a carbocyclic non-aromatic group linked via a ring carbon atom, and “cycloalkylalkyl” is used 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 via a ring atom which may be C or N, and “heterocyclylalkyl” may be used to describe a group linked to another molecule via an alkylene linker. Where used herein, these terms also include rings containing a double bond or two bonds, unless the ring is aromatic.

[0048] The terms "aromatic" or "aryl" substituents or moieties refer to monocyclic or fused bicyclic moieties that possess the well-known aromatic characteristics, including phenyl and naphthyl. Similarly, the terms "heteroaromatic" and "heteroaryl" refer to such monocyclic or fused bicyclic ring systems that include one or more heteroatoms as ring members. Suitable heteroatoms include N, O, and S, and the presence of these heteroatoms allows for aromaticity of five-membered rings 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 sites formed by fusing one of these monocyclic groups with 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 cinolinyl. Monocyclic or fused bicyclic systems that exhibit aromatic characteristics in terms of the electron distribution of the entire ring system are included in this definition. Furthermore, bicyclic groups in which at least the ring directly bonded to the remainder of the molecule exhibits aromatic characteristics are also included. Typically, the ring system contains 5 to 12 ring member atoms. Preferably, a monocyclic heteroaryl contains 5 to 6 ring members, and a bicyclic heteroaryl contains 8 to 10 ring members.

[0049] The aryl and heteroaryl moieties can be substituted with various substituents including C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C5-C12 aryl, C1-C8 acyl, and heterogenes thereof, each of which can be further substituted itself. Other substituents for the aryl and heteroaryl moieties include halogens (F, Cl, Br, I), OR, NR2, SR, SO2R, SO2NR2, NRSO2R, NRCONR2, NRC(O)OR, and NRC(O). The group comprises 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, C2-C8 alkenyl, C2-C8 heteroalkenyl, C2-C8 alkynyl, C6-C10 aryl, C5-C10 heteroaryl, C7-C12 arylalkyl, or C6-C12 heteroarylalkyl, where each R is optionally substituted for alkyl groups as described above. Substituents on the aryl or heteroaryl group may, of course, be further substituted for any group described herein that is suitable for each type of substituent or for each component of the substituent. For example, an arylalkyl substituent may be substituted in the aryl portion with a substituent described herein as typical for an aryl group, and in the alkyl portion with a substituent described herein as typical or suitable for an alkyl group.

[0050] As used herein, “may be substituted” indicates that a particular group described may have one or more hydrogen substituents replaced by non-hydrogen substituents. In some may-substituted groups or parts, all hydrogen substituents are replaced by non-hydrogen substituents, e.g., C1-C6 alkyl, C2-C6 heteroalkyl, alkynyl, halogen (F, Cl, Br, I), N3, OR, NR2, SiR3, OSiR3, SR, SO2R, SO2NR2, NRSO2R, NRCONR2, NRC(O)OR, NRC(O)R, CN, C(O)OR, C(O)NR2, OC(O)R, C(O)R, oxo, and NO2, where each R is independently H, C1-C6 alkyl, C6-C10 aryl, or C2-C6 heteroalkyl. If any substituent is bonded via a double bond such as a carbonyl oxygen or oxo (=O), the group occupies two available valencies, and therefore the total number of substituents that can be included is reduced in proportion to the number of available valencies. In some embodiments, any 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, any substituent is a reactive group, such as a group that can be crosslinked by (4+2) cycloaddition, for example, JPEG0007839552000045.jpg2028 and Includes JPEG0007839552000046.jpg1216.

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

[0053] In some embodiments of formula A, the compound is of formula A1: Represented as JPEG0007839552000047.jpg3249, Here, Z 2 Q, X, A, n, and m are as defined above in the compound of formula A, and R 1 and R 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0054] In some embodiments, the compound is of formula A2: It is represented as JPEG0007839552000048.jpg3658, Here, Q, X, A, n, and m are as defined above. R 1 and R 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteralkyl, R 7 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 Cycloheteroalkyl, C1-C which may be substituted. 10 Alkyloxy, C3-C may be substituted. 10 Heteroalkyloxy, or NR 3 R 4 and R 3 and R 4 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl.

[0055] In some embodiments, the compound is of formula A3: represented by JPEG0007839552000049.jpg3960, where Q, X, A, n, and m are as defined above, R 1 and R 2 are independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl, and R 3 and R 4 are independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl.

[0056] In some embodiments, the compound is of formula A4: represented by JPEG0007839552000050.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 C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10is a cycloheteroalkyl, and R' is optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 is a cycloheteroalkyl.

[0057] In some embodiments of Formulas A1 - A4, Q is JPEG0007839552000051.jpg1024.

[0058] In some embodiments of Formulas A1 - A4, Q is JPEG0007839552000052.jpg1022, and where J is i S, O, or NR 8 and R is H, optionally substituted C1-C 8 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, optionally substituted C6-C 10 aryl, or optionally substituted C5-C 10 heteroaryl. 10 is

[0059] In some embodiments of Formulas A1 - A4, Q is JPEG0007839552000053.jpg1228, and where [[ID=�2]]J is, in each case independently, S, O, or NR 8 and R is H, optionally substituted C1-C 8 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl compound.

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

[0061] In some embodiments of formulas A1 to A4, A is The filename is JPEG0007839552000054.jpg2027. Here, R' and R'' may be substituted independently of C1-C. 12 Alkyl (e.g., fluorinated alkyl) and optionally substituted C6-C 10 Selected from aryls (e.g., fluorinated aryls), and G 1 , G 2 , and G 3 The electronegativity group is independently selected from 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 The filename is JPEG0007839552000055.jpg2028.

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

[0065] In some embodiments, the compound is of formula A5: It is the compound of JPEG0007839552000056.jpg3974, Here, Z 1 and Z 2 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl, or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000057.jpg2627 or The filename is JPEG0007839552000058.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteralkyl, and R 5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0066] In some embodiments, the compound is of formula A6: It is the compound of JPEG0007839552000059.jpg4170, Here, Z 1 C6-C may be substituted. 10 Aryl or possibly substituted C5-C 10It is a heteroaryl, Z 2 H, C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl, possibly substituted C3-C 10 Cycloheteroalkyl, possibly substituted C6-C 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, X is JPEG0007839552000060.jpg2627 or The filename is JPEG0007839552000061.jpg1121. L does not exist, or L is S or O. Y is H, and C1-C may be substituted. 20 Alkyl, possibly substituted C3-C 50 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and R 5 and R 6 These are independently H, and C1-C which may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl group.

[0067] In some embodiments, the compound is of formula A7: It is the compound of JPEG0007839552000062.jpg3771, Here, Z 1 C6-C may be substituted. 10 Aryl or possibly substituted C5-C 10 It is a heteroaryl, Z2 is H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloheteroalkyl, optionally substituted C6-C 10 aryl or optionally substituted C5-C 10 heteroaryl, and X is JPEG0007839552000063.jpg2627 or JPEG0007839552000064.jpg1121, and L is absent or L is S or O, and Y is H, optionally substituted C1-C 20 alkyl, optionally substituted C3-C 50 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl, and R 5 and R 6 are independently H, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 heteroalkyl, optionally substituted C3-C 10 cycloalkyl, or optionally substituted C3-C 10 cycloheteroalkyl.

[0068] The polar chromophores disclosed herein may include one or more reactive groups that can form covalent bonds (i.e., crosslinks) when reacted with a counterpart group (e.g., when exposed to high temperatures). Films comprising the chromophores disclosed herein can be formed using any suitable reactive group and counterpart group. In some embodiments, the reactive group and the counterpart group are groups that can be crosslinked by (4+2) cycloaddition. The number of such groups is known in the art.

[0069] In some embodiments, Y, X, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 One or more of these include a reactive group. In some embodiments, Y, X, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 One or more of these groups are optionally substituted with one or more reactive groups (e.g., groups that can be crosslinked by (4+2) cycloaddition, such as anthracenyl or acrylate groups). In some embodiments, the groups that can be crosslinked by (4+2) cycloaddition are structured as follows: JPEG0007839552000065.jpg2936 or Represented by JPEG0007839552000066.jpg2926, Here, k is 0, 1, 2, 3, 4, or 5, and each Q * These 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 these may be optionally substituted with one or more functional groups or protecting functional groups, which may be present in addition to the one or more reacting groups described above. As used herein, “functional group” refers to a group, substituent, or site that is responsible for a characteristic chemical reaction of a molecule containing such a functional group. For example, a hydroxyl functional group is a group that can undergo esterification reactions, and a hydroxyl functional group can be protected with a silyl protecting group such as trimethylsilyl or tert-butyldiphenylsilyl (TBDPS).

[0071] In some embodiments of the formulas disclosed herein, LY is H, OL 1 OSiR10 R 11 R 12 , or SL 1 OSiR 10 R 11 R 12 And here, L 1 is a C2-C20 alkylene that may be substituted or a C3-C50 heteroalkylene that may be substituted, and R 10 , R 11 , and R 12 These are independently H, C1-C 10 Alkyl, or C 6- C 10 It is an aryl compound. In some embodiments, LY is H. In some embodiments, LY is -SCH2CH2OH or SCH2CH2OTBDPS.

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

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

[0074] In some embodiments of the compounds disclosed herein, Z 1 and at least one of X is JPEG0007839552000067.jpg3380 and OSiR 10 R 11 R 12 It is substituted with a group selected from the following: Here is the G 5 is NH, O, S, or N(C1-C 10 -alkyl) and R 10 , R11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[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 And here, L 1 C2-C may be substituted. 20 C3-C may be substituted with alkylene. 50 It is a heteroalkylene, and R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[0076] In some embodiments of the compounds disclosed herein, X is JPEG0007839552000068.jpg1727 or The filename is JPEG0007839552000069.jpg3327. Here is the G 4 OSiR 10 R 11 R 12 And here, R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 Is it aryl, or G 4 teeth, JPEG0007839552000070.jpg3240 or The filename is JPEG0007839552000071.jpg2434. Here is the G 5 is NH, O, S, or N(C1-C 10 It is alkyl.

[0077] In some embodiments, X is The filename is JPEG0007839552000072.jpg3337. Here, k is an integer from 1 to 20, and R 10 , R 11 , and R 12 H and C are independent of each other. 1- C 10 Alkyl, or C6-C 10 It is Ariel.

[0078] In some embodiments, X is JPEG0007839552000073.jpg1726 or The filename is JPEG0007839552000074.jpg3334. Here, TBDPS is, The filename is JPEG0007839552000075.jpg2018.

[0079] In some embodiments, the compound is of formula A8: It is the compound of JPEG0007839552000076.jpg4195, Here, G 6 is OR' or NR'R" where R' and R" may be substituted independently C1-C 10 It is alkyl, R 1 C1-C may be H or substituted. 10 It is alkyl, R 2 C1-C may be substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and Y may be C1-C even if it is substituted. 10 Alkyl, possibly substituted C3-C 10 Heteroalkyl, possibly substituted C3-C 10 Cycloalkyl or optionally substituted C3-C 10 It is a cycloheteroalkyl, and Here, R 2 , Y, and G 6 At least one of them is JPEG0007839552000077.jpg3378 and OSiR 10 R 11 R 12 It is substituted with a group selected from the following: Here is the G 5 is NH, O, S, or N(C1-C 10 -alkyl) and R 10 , R 11 , and R 12 These are independently H, and C1-C which may be substituted. 10 Alkyl or optionally substituted C6-C 10 It is Ariel.

[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: JPEG0007839552000078.jpg247152JPEG0007839552000079.jpg251152, Here, TBDPS is, The filename is JPEG0007839552000080.jpg2118.

[0081] The chromophores disclosed herein, for example, compounds of formulas 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 intermediates common to a number of 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 entirety of which is incorporated herein by reference). Exemplary synthesis of chromophores is shown in Figures 2 and 7.

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

[0083] In another embodiment, this specification provides polymer compositions comprising a chromophore disclosed herein. In certain embodiments, the chromophore is blended with a polymer to form a processable and durable film that may have electro-optic activity induced by 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 so that its dipole moment aligns perfectly with the electric field, and then the film is cooled in the presence of the electric field to maintain the order induced by poling). The electro-optic activity can be measured by Teng-Man ellipsometry, the attenuated total internal reflection (ATR) method, which is known to those skilled in the art.

[0084] In certain embodiments, a film comprising a chromophore disclosed herein blended with polymethylmethyl acrylate (PMMA) is measured by Teng-Man ellipsometry in the following ranges: approximately 70 pm / V to approximately 300 pm / V, approximately 40 pm / V to approximately 140 pm / V, approximately 30 pm / V to approximately 250 pm / V, approximately 75 pm / V to approximately 300 pm / V, approximately 80 pm / V to approximately 250 pm / V, approximately 50 pm / V to approximately 200 pm / V, approximately 15 to approximately 105 pm / V, approximately 105 to approximately 405 pm / V, approximately 125 to approximately 1100 pm / V, approximately 125 to approximately 1200 pm / V, approximately 125 to approximately 1300 pm / V, approximately 125 to approximately 1500 pm / V, above approximately 350 pm / V, above approximately 500 pm / V, above 750 pm / V, or approximately 1000 pm / V. r exceeding pm / V 33 It has a value.

[0085] In some embodiments, the film containing the chromophore described herein can be combined with a film of a dielectric material or a wide-bandgap semiconductor as a charge-blocking layer (for example, to minimize conductivity during poling of the film). Such a film may be poly(benzocyclobutene)(BCB, Cyclotene) TMThe materials may include organic materials such as ) or inorganic materials, but not limited to TiO2, MoO3, ZrO2, HfO2, SiO2, Al2O3, Si3N4, or combinations 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, for example, a layer described 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 embodiment, this specification 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, plasmon-organic hybrid modulators, electro-optic converters, terahertz detectors, frequency shifters, or frequency comb sources. In some embodiments, the electro-optical devices comprising the films disclosed herein further include one or more charge-blocking layers as described above.

[0087] Certain components of optical communication systems can be fabricated, in whole or in part, from the films disclosed herein. Exemplary components include, but are not limited to, linear 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., birefringent modulators, Mach-Zehnder interferometers, and directional and evanescent couplers), arrays (including long, high-density waveguide arrays), optical interconnects, optochips, single-mode DWDM components, photonic crystal apparatuses, and resonant apparatuses (e.g., photonic crystals, ring or disk resonators, and diffraction gratings). The films described herein may be used, for example, in wafer-level processing, applicable in vertical-cavity surface-emitting lasers (VCSELs) and CMOS technologies.

[0088] In many applications, the films described herein can be used as substitutes for lithium niobate, gallium arsenide, and other inorganic materials currently found to be used as light-transmitting materials in optical communication systems.

[0089] Unless otherwise defined herein, all terms used herein shall have the same meaning for those skilled in the art in the field of the present invention.

[0090] As used herein, the term "about" indicates that the disclosed embodiments may be included even if the subject matter values ​​are modified by plus or minus 5%.

[0091] In the claims, the term “or” is used to mean “and / or” unless expressly indicated to refer only to substitutes, or unless the substitutes are mutually exclusive, and this specification supports definitions that refer only to substitutes and “and / or”. In the claims or specification, the words “a” and “an” refer to one or more unless otherwise specified when used with the word “including”.

[0092] Unless otherwise clearly required by context, throughout this specification and the claims, the words “comprise,” “comprising,” etc., are to be interpreted in a comprehensive sense, as opposed to an exclusive or exhaustive sense; that is, they are to be interpreted as “including but not limited to.” Also, words using singular or plural include plural and singular, respectively. In this specification, terms of the form “A / B” or “A and / or B” mean (A), (B), or (A and B). In this specification, terms of the form “at least one of A, B, and C” mean (A), (B), (C), (A and B), (A and C), (B and C), or (A, B and C). In this specification, terms of the form “(A)B” mean (B) or (AB), that is, A is an optional element. Furthermore, when used in this Application, the terms “Specified," “Above,” and “Below,” and similar inclusive terms, refer to the Application as a whole and not to any particular part thereof.

[0093] All publications cited herein and the subjects from which they are cited are incorporated herein by reference in their entirety.

[0094] The following examples are provided to illustrate specific features and / or embodiments of the disclosure herein. The examples should not be construed as limiting the disclosed herein to the specific features or embodiments described herein. [Examples]

[0095] Examples Using density functional theory (DFT) calculations performed with well-validated methods, the inventors found that the chromophores of the disclosure herein, such as compounds I and II, may have high hyperpolarizability. The calculations were performed at the M062X / 6-31+G(d) level theory in a chloroform anal solvent environment (PCM), and the hyperpolarizability was calculated by analytical differential (CPHF). Similar calculations were also performed using the JRD1 cleavage model as a standard. For computational efficiency, the OTBDPS group on the donor of JRD1 was replaced with hydrogen, and the donor was modeled as diethylaniline. Based on this model, the calculation results of hyperpolarizability are reported. Exemplary compounds I-XV were synthesized using standard organic synthesis methods well known to those skilled in the art, and protons ( 1 The composition was confirmed by 1H NMR and electrospray ionization mass spectrometry (ESI-MS). UV / visible absorption spectra were measured using methods well known to those skilled in the art, for both chloroform and thin film.

[0096] The hyperpolarizability of exemplary compounds I, II, III, IV, V, VI, and VII in chloroform solutions was 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 in comparison to a pure chloroform standard, and data were extrapolated to zero frequency using a two-level attenuation model and a linewidth of 0.1 eV. To eliminate dependence on chloroform reference values ​​and to clearly compare with the level of technology, the state-of-the-art chromophore JRD1 was also measured using the same experimental setup, and the data is reported in comparison with JRD1. The DFT, UV / Vis, and HRS measurement data are summarized in Table 1.

[0097] JPEG0007839552000081.jpg93165

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

[0099] The complex refractive indices (n and k) of thin films containing exemplary compounds I, II, III, and IV on a glass substrate were obtained using a Woollam MC2000 spectroscopic ellipsometer at the UW Molecular Analysis Facility using JA Variable Angle Spectroscopic Ellipsometry (VASE) and previously described methods (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 contents of which are incorporated herein by reference). Data for exemplary compounds I, II, III, and IV as neat films are shown in Figure 3. Figure 4 shows data on the film of compound II in PMMA, and data compared with neat JRD1. The data in Figure 4 are representative of the behavior of the compounds disclosed herein when incorporated into dilute polymer films.

[0100] The films for electro-optical measurements are prepared by sputter-coating gold electrodes onto thin films of exemplary compounds I, II, III, IV, VI, and VII, attaching wires using commercially available silver paste, and applying electro-optical measurements at an intensity in the range of 15V / μm to 110V / μm. PThe materials were prepared by polling them at a temperature suitable for their Tg using a polling field, cooling them to < 35°C, and measuring the electro-optic activity at 1310 nm using previously reported methods and apparatus (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 contents of which are incorporated herein by reference). Representative polling results for exemplary compounds II and III are shown in Figure 5. Polling efficiency r 33 / Ep represents the electro-optic activity (pm / V) versus E p This was determined by linear fitting.

[0101] In addition to the data shown in Figure 5, the exemplary compound I at a 10% by mass concentration in PMMA is 1.77 nm 2 / V 2 The poling efficiency was demonstrated, and compound III at a concentration of 25% by mass in PMMA was 2.87 nm. 2 / V 2 The polling efficiency was demonstrated. This polling efficiency is 25% JRD1 (~1nm) in PMMA. 2 / V 2 ) is compared very well. The poling efficiency of exemplary compounds II and IV at low concentrations is particularly exceptional for their number density. Exemplary compound II (2.82 nm) at a 10% concentration in PMMA. 2 / V 2 ) and exemplary compound IV (2.86 nm) at a concentration of 10% 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 (this disclosure is incorporated herein by reference) and showed a polling efficiency of 3.43 ± 0.2 nm when there is a BCB charge blocking layer between ITO and OEO materials. 2 / V 2 (Without a charge blocking layer, the value is 3.1 ± 0.1). The more than 2.5-fold improvement in EO activity at a given concentration in the polymer host demonstrates the usefulness of exemplary chromophores, including novel thienothiophene-derived donors such as exemplary compounds I, II, III, and IV, for electro-optical devices, enabling high device performance while providing substantial flexibility in blending with chromophores.

[0102] Exemplary compounds V, VI, and VII, as shown in Table 1, demonstrate a range of structural variations of the present invention utilizing different aromatic groups and side-chain substitutions in the electron-donating region of the molecule, enabling desired substitutions and tuning of optical properties while showing improved hyperpolarizability compared to the state-of-the-art compound JRD1. Exemplary compound VI is found at a concentration of 10% in PMMA (0.90 nm 2 / V 2It exhibits competitive polling efficiency from 25% JRD1 in PMMA, and when combined with a charge blocking layer to reduce current during polling, it shows exceptional polling efficiency as a neat material (100% concentration, no polymer). When combined with MoO3 (20 nm thick, deposited) as the charge blocking layer, a polling efficiency of 7.98 was obtained. With a sol-gel TiO2 charge blocking layer, a polling efficiency of 15.98 was obtained. The latter shows performance at r above 600 pm / V. 33 This yielded a value that significantly exceeded the recorded value of JRD1, and nearly five times the polling efficiency of JRD1. In addition, the real component of the refractive index of the example compound VI improved to 2.02 at 1310 nm and 1.90 at 1550 nm, showing exceptional n 3 r 33 This makes the value possible. The refractive index and poling data for compound VI are shown in Figure 6. Exemplary compound VII is 0.94 nm at a 10% concentration in PMMA. 2 / V 2 It demonstrated a polling efficiency that slightly surpassed that of 10% of exemplary compound VI in PMMA.

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

Claims

1. Formula A2 below: A compound of, Here, A is And, Here, R' and R" are independently optionally substituted C 1 -C 12 alkyl and optionally substituted C 6 -C 10 aryl, and G 1 , G 2 , and G 3 are independently F, CN, CF 3 , SO 2 CF 3 selected from, X is And, L does not exist, or L is S or O. Y is H, and C may be substituted. 1 -C 20 Alkyl, possibly substituted C 3 -C 50 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl, may be substituted C 3 -C 10 It is a cycloheteralkyl, n is 1, m is 1, and R 5 and R 6 These are H and C, which may be substituted, independently. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteralkyl, R 1 and R 2 These are H and C, which may be substituted, independently. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteralkyl, R 7 , NR 3 R 4 OR 9 And, R 3 and R 4 These are H and C, which may be substituted, independently. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteralkyl, R 9 C may be substituted. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteralkyl, R 7 is OR 9 If that is the case, Q is, And, R 7 NR 3 R 4 If that is the case, Q is, And, In each case, J is independently S, O, or NR 8 And, R 8 H, and C may be substituted. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl, may be substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl, or possibly substituted C 5 -C 10 It is a heteroaryl. compound.

2. The compound according to claim 1, wherein the compound is of the following formula A3: It is represented as, Here, 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 -cycloheteroalkyl, and R 3 and R 4 are each, 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 cycloheteroalkyl. compound.

3. The compound according to claim 1, wherein the compound is of the following formula A4: It is represented as, Here, Q, X, A, n, and m are as defined in claim 1, R 1 and R 2 These are H and C, which may be substituted, independently. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteroalkyl, and R 9 may be substituted with C 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteroalkyl, compound.

4. A compound according to claim 1 or 3, wherein Q is It is a compound.

5. A compound according to any one of claims 1 to 3, wherein Q is And, Here, J is S, O, or NR 8 and R 8 H, and C may be substituted. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl, may be substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl, or possibly substituted C 5 -C 10 It is a heteroaryl. compound.

6. A compound according to any one of claims 1 to 3, wherein Q is And, Here, In each case, J is independently S, O, or NR 8 and R 8 H, and C may be substituted. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl, may be substituted C 3 -C 10 Cycloheteroalkyl, optionally substituted C 6 -C 10 Aryl or possibly substituted C 5 -C 10 It is a heteroaryl. compound.

7. The compound according to claim 5 or claim 6, wherein J is S.

8. A compound according to any one of claims 1 to 7, wherein A is It is a compound.

9. The compound according to claim 1, wherein the compound is of the following formula A8: It is a compound of, Here, G 6 This is OR 9, where R 9 may be substituted with C. 1 -C 10 It is alkyl, R 1 is H or possibly substituted C 1 -C 10 It is alkyl, R 2 C may be substituted. 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteroalkyl, and Y may be substituted for C 1 -C 10 Alkyl, possibly substituted C 3 -C 10 Heteroalkyl, possibly substituted C 3 -C 10 Cycloalkyl or optionally substituted C 3 -C 10 It is a cycloheteroalkyl, and Here, R 2 , Y, and G 6 At least one of them is It is substituted with a group selected from the following: Here is the G 5 is NH, O, S, or N(C) 1 -C 10 -alkyl) and R 10 , R 11 , and R 12 These are H and C, which may be substituted, independently. 1 -C 10 Alkyl or optionally substituted C 6 -C 10 It is Ariel. compound.

10. A compound according to any one of claims 1 to 9, wherein the compound is one of the following compounds: Compound I, Compound II, Compound IV, Compound V, Compound VII, Compound XI, Compound XIV, or Compound XV: And, Here, TBDPS is, It is a compound.

11. A film having electro-optical activity, comprising one or more of the compounds described in claims 1 to 10.

12. The film according to claim 11, wherein the film further comprises a polymer.

13. The film according to claim 12, wherein the polymer is polymethyl methacrylate (PMMA).

14. The aforementioned film has a voltage greater than approximately 100 pm / V. 33 A film according to any one of claims 11 to 13, having a value.

15. The aforementioned film has a voltage greater than approximately 1000 pm / V. 33 A film according to any one of claims 11 to 14, having a value.

16. The film according to any one of claims 11 to 15, wherein the film has a Tg of approximately 105°C or higher.

17. A method for forming an electro-optically active film, comprising the steps of: depositing a compound or a mixture containing a compound according to any one of claims 1 to 10 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 lowering the temperature of the film to provide an electro-optically active film.

18. An electro-optical apparatus comprising a compound according to any one of claims 1 to 10.

19. An electro-optical apparatus comprising a film according to any one of claims 11 to 16.

20. The electro-optic apparatus according to claim 18 or 19, further comprising one or more charge blocking layers.

21. The one or more charge blocking layers are poly(benzocyclobutene) (BCB), TiO 2 MoO 3 , ZrO 2 , HfO 2 SiO 2 , Al 2 O 3 Si 3 N 4 The electro-optical apparatus according to claim 20, including, or a combination thereof.

22. An electro-optical apparatus according to any one of claims 18 to 21, wherein the apparatus is an electro-optical modulator, an antenna, a Mach-Zehnder modulator, a phase modulator, a silicon-organic hybrid modulator, a plasmon-organic hybrid modulator, an electro-optic converter, a terahertz detector, a frequency shifter, or a frequency comb source.

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