Non-linear optochromic groups with indolizine donor groups

Abstract

The invention relates to a nonlinear optical chromophore having an organic indolizine electron-donating group, having the following general formula (I): D represents an indolizine electron-donating group. N represents an n-bridge between A and D, wherein the n-bridge comprises a carbon chain covalently bound to and separating A and D. A represents an organic electron accepting group having an electron affinity greater than the electron affinity of D. The organic indolizine electron-donating group D has one of the following formulae. Various embodiments of the present invention include a non-linear optochromic group having an indolizine donor group, which has an indolizine donor attached to a pi-bridge group. In various preferred embodiments of the invention, the indolizine donor groups may be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. In certain embodiments of the invention, the substituent moiety in the indolizine donor group may be important for separation. The separation may reduce chromophore-chromophore interactions. Separation may reduce charge transfer between molecules. The separation may increase the maximum applied voltage, which may contribute to better polarization and higher r33.

Description

[0001] Cross-reference with related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 524,047, filed June 29, 2023, the entire contents of which are incorporated herein by reference. Background Technology

[0003] Nonlinear optical (NLO) chromophores provide electro-optic (EO) activity in polarized, electro-optic polymer devices. Electro-optic polymers have been studied for many years as an alternative to inorganic materials such as lithium niobate in electro-optic devices. Electro-optic devices can include external modulators for applications such as telecommunications (telecommunications), data communications, RF photonics, and optical interconnects. Polymer electro-optic materials have shown great potential for core applications in a wide range of next-generation systems and devices, including electro-optic modulators, optical switches, phased array radars, satellite and fiber optic telecommunications, cable television (CATV), optical gyroscopes for aerospace and missile guidance, electronic countermeasures (ECM) systems, backplane interconnects for high-speed computing, ultrafast analog-to-digital conversion, mine detection, radio frequency photonics, spatial light modulation, and all-optical (light-controlled light) signal processing.

[0004] Many NLO molecules (chromophores) exhibiting high polymer electro-optic properties have been synthesized. The product of molecular dipole moment (μ) and hyperpolarizability (β) is often used as a measure of molecular electro-optic efficiency due to the involvement of dipoles in material processing. See Dalton et al., "New Class of High Hyperpolarizability Organic Chromophores and Process for Synthesizing the Same", WO 00 / 09613.

[0005] Then, the hyperpolarizability of microscopic molecules (β) is converted into the hyperpolarizability of macroscopic matter (χ). 2 Significant difficulties have been encountered. Molecular subcomponents (chromophores) must be integrated into NLO materials exhibiting (i) high macroscopic nonlinearity and (ii) sufficient temporal, thermal, chemical, and photochemical stability. High electro-optic activity and the stability of electro-optic activity, also known as "time stability," are important for commercially viable devices. Electro-optic activity in electro-optic polymers can be increased by increasing the concentration of nonlinear photochromophores in the host polymer and by enhancing the electro-optic properties of the chromophores. However, some techniques used to increase chromophore concentration can reduce polarization efficiency and time stability. Simultaneously addressing these dual problems is considered the ultimate obstacle to the widespread commercialization of EO polymers in many devices and systems.

[0006] High material hyperpolarizability (χ) 2The formation of anti-social dipole chromophores is limited by the poor social properties of NLO chromophores. Commercially viable materials must incorporate chromophores at high molecular densities, where the necessary molecular moments are statistically oriented along a single material axis. To achieve this organization, the charge-transfer (dipole) properties of NLO chromophores are typically utilized by applying an external electric field during material processing, creating lower energy conditions that favor localization of non-centrosymmetric order. Unfortunately, even at moderate chromophore densities, molecules form multi-molecular dipole-bound (centrosymmetric) aggregates that cannot be disintegrated by actual field energy. To overcome this difficulty, the integration of anti-social dipole chromophores into cooperative material architectures is generally achieved by constructing physical barriers that restrict intermolecular associations (e.g., anti-stabilized groups).

[0007] Therefore, it is generally considered advantageous in the art to prepare nonlinear photonic biochromatographs containing materials exhibiting high glass transition temperatures (Tg). Compared to materials with lower glass transition temperatures, materials with high glass transition temperatures exhibit improved thermal stability and retain their macroscopic electro-optic properties to a greater extent. It is also advantageous to prepare nonlinear photonic biochromatographs that exhibit desired macroscopic optical properties, thermal stability, and a lower wavelength maximum absorption, i.e., λ. max .

[0008] Invention Summary

[0009] This invention generally relates to nonlinear photochromatographs having an indazine donor group. Various embodiments of the invention include nonlinear photochromatographs having an indazine donor group having an indazine donor attached to a π-bridge group. In various embodiments of the invention, the indazine donor group can be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. In some embodiments of the invention, the substituent portion in the indazine donor group can be important for separation. Separation can reduce chromophore-chromophore interactions. Separation can reduce charge transfer between molecules. Separation can increase the maximum applied voltage, which can contribute to better polarization and higher r. 33 .

[0010] Various embodiments of the present invention include having a C8-C junction between the donor and recipient. 20 Nonlinear photonic biochromophores with bridging groups. Various embodiments of the invention include nonlinear photonic biochromophores having C4-C6 bridging groups between the donor and acceptor, which exhibit reduced λ. max Value. In some embodiments, the nonlinear photochemical chromophore has a C4-C6 bridging group between the donor and acceptor, whose R 1 The part can represent any alkyl group, and its R 2Some can represent any aryl group. These nonlinear chromophores with C4-C6 bridging groups between the donor and acceptor exhibit reduced λ. max The value can have a narrow absorption band. In some other embodiments, nonlinear photochromophores are obtained by using chromophore analogs in nonpolar solvents based on Δλ. max λ max Characterization.

[0011] λ outside the scope described in this article max Compared to the values ​​formed, the λ of the implementation described herein max Values ​​that form a greater range of transparency at higher wavelengths. For example, various nonlinear photonic biochromophore embodiments provide transparency exceeding 800 nm, which are used in: 1) short-range local area networks, 2) free-space fiber optic communication and optical interconnects combined with LEDs or semiconductor lasers, and 3) active materials for terahertz (THz) applications. Various embodiments of the present invention include nonlinear photonic biochromophores having short-chain bridging groups between the donor and acceptor, which exhibit reduced optical loss and are capable of providing high transparency at various wavelengths. Furthermore, various embodiments of the present invention have the following optimized features: (1) at higher r values ​​at various wavelengths 33 (electro-optic coefficient), (2) higher T g (glass transition temperature), (3) exceptionally high thermal stability, and (4) high light stability.

[0012] Various embodiments of the present invention include nonlinear optical biochromosomes of general formula (I):

[0013] D-Π-A (I)

[0014] Wherein D represents an organic electron-donating group; A represents an organic electron-accepting group with an electron affinity greater than that of D; and Π represents a Π-bridge between A and D; wherein the Π-bridge comprises a carbon chain covalently bonded to and separating A and D, wherein the carbon chain between A and D is 2 to 4 carbon atoms long, and wherein the 2 to 4 carbon atom chain comprises up to 2 carbon-carbon double bonds and up to 4 side-attached substituents, wherein two or more of the side-attached substituents are capable of forming a ring structure with the 2 to 4 carbon atom chain.

[0015] In various embodiments of the present invention, the nonlinear photogenerating chromophore of general formula (I) has an indazine donor group. In various embodiments of the present invention, the nonlinear photogenerating chromophore of general formula (I) has an indazine donor group connected to a Π-bridging group.

[0016] Other aspects, features, and advantages will be apparent from the following disclosure (including the detailed description of the invention, preferred embodiments, and appended claims).

[0017] Brief description of some views in the attached diagram

[0018] The foregoing overview and the detailed description of preferred embodiments of the invention below will be better understood when read in conjunction with the accompanying drawings. The currently preferred embodiments are shown in the drawings for illustrative purposes. However, it should be understood that the invention is not limited to the precise arrangements and configurations shown.

[0019] In the attached diagram:

[0020] Figure 1 Spectrum 100 illustrates the absorption of an example indazine chromophore of general formula (I) in UV-Vis spectra in two different solvents, wherein the first curve 101 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in 1,4-dioxane solvent, while the second curve 102 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in dichloromethane (DCM) solvent.

[0021] Figure 2 Spectrum 200 illustrates the absorption of the indazine chromophore of example formula (I) in two different solvents in UV-Vis spectra, wherein the first curve 201 shows the absorption of the example short-chain bridged chromophore of formula (I) in 1,4-dioxane solvent in UV-Vis spectra, while the second curve 202 shows the absorption of the example short-chain bridged chromophore of formula (I) in dichloromethane (DCM) solvent in UV-Vis spectra.

[0022] Figure 3 Spectrum 300 illustrates the absorption of an example indazine chromophore of general formula (I) in UV-Vis spectra in two different solvents, wherein the first curve 301 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in 1,4-dioxane solvent, while the second curve 302 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in dichloromethane (DCM) solvent.

[0023] Figure 4 Spectrum 400 illustrates the absorption of an example indazine chromophore of general formula (I) in UV-Vis spectra in two different solvents, wherein the first curve 401 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in 1,4-dioxane solvent, while the second curve 402 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in dichloromethane (DCM) solvent.

[0024] Figure 5Spectrum 500 illustrates the absorption of an example indazine chromophore of general formula (I) in UV-Vis spectra in two different solvents, wherein the first curve 501 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in 1,4-dioxane solvent, while the second curve 502 shows the absorption of an example short-chain bridged chromophore of general formula (I) in UV-Vis spectra in dichloromethane (DCM) solvent. Invention Details

[0026] As used herein, the singular terms "an" and "a kind" are synonymous with and interchangeable with "one or more" and "at least one" unless the language and / or context clearly indicate otherwise. Accordingly, for example, reference to "polymer" or "the polymer" herein or in the appended claims can refer to a single polymer or more than one polymer. As a further example, reference to "solvent" or "the solvent" herein or in the appended claims can refer to a single solvent or a mixture of more than one solvent. Additionally, unless specifically indicated, all numerical values ​​are to be understood as being modified by "about".

[0027] As used herein, the term "nonlinear optical chromophore" (NLOC) refers to a molecule or molecular part that produces a nonlinear optical effect when exposed to light radiation. A chromophore is any molecular unit whose interaction with light produces a nonlinear optical effect. The desired effect can occur at either resonant or non-resonant wavelengths. The activity of a particular chromophore in a nonlinear optical material is described as its hyperpolarizability, which is directly related to the molecular dipole moment of that chromophore. Various embodiments of the NLO chromophores of this invention are structures useful for producing NLO effects.

[0028] First-order hyperpolarizability (β) is one of the most common and useful NLO properties. Higher orders of hyperpolarizability are used in other applications such as all-optical (light-controlled light) applications. To determine whether a substance, such as a compound or polymer, possesses first-order hyperpolarizability and a sufficient electro-optic coefficient (ro), further research is needed. 33 For a nonlinear photochromatic chromatic material (which is a function of β), the following experiment can be performed. First, the material is placed in an electric field in the form of a thin film to align the dipoles. This can be done by sandwiching the film between electrodes (such as an indium tin oxide (ITO) substrate, a gold film, or a silver film).

[0029] The nonlinear photogenerated chromophore described in this embodiment has an indazine electron-donating group and a C6-C8 bridging group between the donor and acceptor, and this chromophore has optimal λ. max It has a value and exhibits good electro-optical properties. To achieve the best electro-optical effect, λ maxIt must be within the optimal region. For example, nonlinear photochemical chromophores with bridging groups between the indazine donor and acceptor can have λ values ​​from 725 nm to 900 nm in DCM. max .

[0030] Δλ max The measurements are as follows: λ relative to the analog in a nonpolar solvent (e.g., 1,4-dioxane). max Calculate the λ of the nonlinear optical student chromophore in a standard polar solvent (e.g., DCM). max The less polar (1,4-dioxane) solvent stabilizes the neutral ground-state chromophore, while the more polar solvent (DCM) stabilizes the charge-transfer state of the chromophore. The easier the charge transfer occurs, the more "polarizable" and therefore more active the chromophore. Here, it has been found that higher wavelengths are directly proportional to lower energies. Therefore, the Δλ between the two solvents... max The higher the value, the less energy is needed to achieve the charge transfer state. Furthermore, r... 33 Its response to an applied electric field, measured experimentally and equal to that of the transmitted light, has the same characteristics as Δλ. max The overall correlation, where the larger Δλ max Generally, with larger r 33 Related. In this way, Δλ max It is a characteristic of the "intensity" of the electro-optic activity of chromophores.

[0031] Reference Figure 1 The absorption of the chromophore (IB5822) was measured in two different solvents. The λmax was 985.7 in dichloromethane (DCM) and 806.2 in 1,4-dioxane.

[0032] Reference Figure 2 The absorption of the chromophore (IB5826) was measured in two different solvents. The λmax was 768.5 in dichloromethane (DCM) and 698.7 in 1,4-dioxane.

[0033] Reference Figure 3 The absorption of the chromophore (IB5829) was measured in two different solvents. The λmax was 861.9 in dichloromethane (DCM) and 756.9 in 1,4-dioxane.

[0034] Reference Figure 4 The absorption of the chromophore (IB5831) was measured in two different solvents. The λmax was 865.6 in dichloromethane (DCM) and 756.3 in 1,4-dioxane.

[0035] Reference Figure 5The absorption of the chromophore (KO5201) was measured in two different solvents. The λmax was 726.3 in dichloromethane (DCM) and 670 in 1,4-dioxane.

[0036] Figure 1-5 Short-chain bridged chromophores and other chromophores' λ max and Δλ max The data can be summarized as follows:

[0037]

[0038] To generate a polarizing electric field, a potential is then applied to the electrodes while the material is heated to near its glass transition (T0). g Temperature. After a suitable period of time, the temperature is gradually decreased while maintaining the polarizing electric field. Alternatively, the material can be polarized by corona polarization, wherein a charged needle at a suitable distance from the material film provides the polarizing electric field. In either case, dipoles in the material tend to align with the field. Various embodiments of the invention can include, or may further include, electro-optic materials having a glass transition temperature greater than or equal to 100°C, greater than or equal to 125°C, or greater than or equal to 150°C, or even higher.

[0039] The nonlinear optical properties of the polarized material are then tested as follows. Polarized light (often from a laser) is passed through the polarized material, then through a polarizing filter, and finally to a light intensity detector. If the light intensity received by the detector changes with the potential applied to the electrodes, the material is doped with a nonlinear photonic chromatid with an electro-optically variable refractive index. A more detailed discussion of the electro-optic constant measurement technique for polarized films doped with nonlinear photonic chromatids can be found in Chia-Chi Teng, Measuring Electro-Optic Constants of a Poled Film, in NonlinearOptics of Organic Molecules and Polymers, Chp. 7, 447-49 (Hari Singh Nalwa & Seizo Miyata eds., 1997), which is incorporated herein by reference in its entirety, except where there is any inconsistency with the disclosures or definitions herein, in which case the disclosures or definitions herein shall prevail.

[0040] The relationship between the change in applied potential and the change in the refractive index of a material can be expressed as its electro-optic (OE) coefficient (r). 33This effect is generally referred to as the electro-optic effect or EO effect. A device that includes a substance whose refractive index changes in response to a change in applied potential is called an electro-optic (EO) device. For compositions having the short-chain bridged chromophores described herein, high EO coefficients of >30 pm / V (e.g., measured at 980 nm) or >20 pm / V (e.g., measured at 1310 nm) can be achieved.

[0041] Compositions containing the short-chain bridged chromophores described herein also exhibit reduced optical loss. The optical loss of the various embodiments described herein can be < 2 dB / cm. Furthermore, the compositions described herein can provide high transparency at wavelengths outside the absorption bands of the various embodiments described herein. In addition, the compositions described herein also exhibit particularly high thermal stability (characterized by a decomposition temperature greater than 250 °C) and high photostability (measured by the degradation of photo-optical materials under broadband light and environmental conditions).

[0042] Second-order superpolarizability (γ) or third-order susceptibility (χ) (3) Third-order NLO activity is a common measure. Several methods exist for measuring these properties, among which degenerate four-wave mixing (DFWM) is very common. See CWThiel, "Four-wave Mixing and Its Applications," www.physics.montana.edu.students.thiel.docs / FWMixing.pdf, the entire contents of which are incorporated herein by reference. Referring to published US patent application No. 2012 / 0267583A1 (the entire contents of which are incorporated herein by reference), a method for evaluating the third-order NLO properties of thin films, known in the art as degenerate four-wave mixing (DFWM), can be used. In US 2012 / 0267583A1... Figure 4 In the diagram, beams 1 and 2 are picosecond coherent pulses absorbed by an NLO film deposited on a glass substrate. Beam 3 is a weaker, slightly delayed beam with the same wavelength as beams 1 and 2. Beam 4 is a product of wave mixing, diffracted from a transient holographic grating, and generated by the interference of beams 1 and 2 within the NLO material of the film. Beam 3 can serve as a "contrast" beam for communication wavelengths, generating a "signal" beam at frequencies not absorbed by the NLO material.

[0043] Nonlinear optical student chromatids suitable for use according to various embodiments of the present invention include those having the general formula (I):

[0044] D-Π-A (I)

[0045] Wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than that of D; and Π represents a Π-bridge between A and D. The terms electron-donating group (donor or "D"), Π-bridge (bridging group or "Π"), and electron-accepting group (acceptor or "A"), and the general synthetic methods for forming D-Π-A chromophores according to the various embodiments described herein are known in the art, for example described in US Patent Nos. 5,670,091, 5,679,763, 6,090,332, and 6,716,995, and US Patent Application No. 17 / 358,960, filed June 25, 2021, the entire contents of which are incorporated herein by reference.

[0046] An acceptor is an atom or group of atoms with a low reduction potential, which can accept electrons from a donor via a π-bridge. The acceptor (A) has a higher electron affinity than the donor (D), so that, at least in the absence of an external electric field, the chromophore is generally polarized in the ground state and has a relatively larger electron density on the acceptor (D). Generally, the acceptor group contains at least one electronegative heteroatom (which is part of a pi bond (double or triple bond)) that allows for the drawing of resonance structures that move electron pairs from the pi bond to the heteroatom while simultaneously reducing the multiplicity of the pi bond (i.e., a double bond formally transforms into a single bond or a triple bond formally transforms into a double bond), thereby giving the heteroatom a formal negative charge. The heteroatom can be part of a heterocycle. Exemplary acceptor groups include, but are not limited to, -NO2, -CN, -CHO, COR, CO2R, --PO(OR)3, --SOR, --SO2R, and --SO3R, where R is an alkyl, aryl, or heteroaryl group. The total number of heteroatoms and carbons in the acceptor group is about 30, and the acceptor group can be further substituted with alkyl, aryl and / or heteroaryl groups.

[0047] Suitable electron-accepting groups "A" (also referred to in the literature as electron-withdrawing groups) of nonlinear photogenerable chromophores that can be used according to various embodiments of the present invention include those described below: published US patent applications: US2007 / 0260062; US2007 / 0260063; US2008 / 0009620; US2008 / 0139812; US2009 / 0005561; US2012 / 0267583A1 (collectively, the “prior disclosures”), each of which is incorporated herein by reference in its entirety; and US Patent Nos. 6,584,266; 6,393,190; 6,448,416; 6,44,830; 6,514,434; 5,044,725; 4,795,664; 5,247,042; 5,196,509; 4,810,338; 4,936,645; 4,767,169; 5,326,661; 5,187,234; 5,170,461; 5,133,037; 5,106,211; and 5,006,285; each of which is incorporated herein by reference in its entirety.

[0048] In nonlinear photogenerated chromophores suitable for use in various embodiments of the invention, suitable electron-accepting groups can include those according to general formula (A a Those:

[0049]

[0050] Where R 4 and R 5 Each independently represents a portion selected from the following: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10. As used in this article, Represents a bonding site with another part of the larger molecular structure. In various preferred embodiments, R 4 and R 5 One or both represent the halogen-substituted portion. Halogen-substituted can refer to mono-, di-, tri-, and higher degrees of substitution. In various embodiments, R 4 and R 5 One represents a halogen-substituted alkyl moiety, while the other represents an aromatic moiety. In various embodiments, R4 and R 5 One represents a halogen-substituted aromatic moiety, while the other represents an alkyl moiety. In various embodiments, the electron-accepting group can be:

[0051]

[0052] In various embodiments, the electron-accepting group can be:

[0053]

[0054] In various embodiments, the electron-accepting group can be:

[0055] .

[0056] Typically, the choice of electron-accepting group can be matched to the strength of the electron-donating group. The overall strength between the electron-donating and electron-accepting groups can be neither too weak nor too strong. If the overall strength is too weak, λ... max It can blueshift, thus having a lower r 33 If the total strength is too high, λ max It can be redshifted, thus having a lower r 33 And the losses are even greater. In the electron-accepting group, R... 4 and R 5 The choice of functional groups can also depend on the volume of the acceptor moiety to be separated. Better separation of the acceptor moiety can lead to better electro-optic properties.

[0057] The donor comprises an atom or group of atoms with a low oxidation potential, which can donate electrons to the acceptor "A" via a π-bridge. The donor (D) has a lower electron affinity than the acceptor (A), so that, at least in the absence of an external electric field, the chromophore is generally polarized, and the donor (D) has a relatively lower electron density. Generally, the donor group contains at least one heteroatom with a lone pair of electrons conjugated with the p-orbitals of the atom directly attached to the heteroatom, thereby enabling the construction of a resonance structure (where the shifted lone pair of electrons bonds with the p-orbitals of the atom directly attached to the heteroatom) to formally increase the multiplicity of the bond between the heteroatom and the atom directly attached to it (i.e., a single bond formally transforms into a double bond, or a double bond formally transforms into a triple bond), thus giving the heteroatom a formal positive charge. The p-orbitals of the atom directly attached to the heteroatom can be empty or part of a multiple bond connecting another atom different from the heteroatom. The heteroatom can be a substituent of an atom with a pi bond or can be located in a heterocycle. Exemplary donor groups include, but are not limited to, R2N- and R n X 1 --, where R is an alkyl, aryl, or heteroaryl group, and X 1It is O, S, P, Se, or Te, and n is 1 or 2. The total number of heteroatoms and carbons in the donor group can be about 30, and the donor group can be further substituted with alkyl, aryl, or heteroaryl groups.

[0058] In nonlinear photogenerated chromophores suitable for use according to various embodiments of the invention, suitable electron-donating groups can include the following indazine donor groups (D a ):

[0059]

[0060] R in the electron-donating group of indazine 1 The representative is selected from the following parts: H, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C groups 10 Alkyne group, wherein the R in the electron-donating group of indazine 2 The term represents a subset selected from the following: substituted monocyclic or unsubstituted aryl groups, substituted or unsubstituted polycyclic aryl groups, substituted or unsubstituted alkyl aryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups. Option R 1 and R 2 The use of groups to separate nitrogen in the indazine donor moiety plays a crucial role in achieving desirable properties in nonlinear photogenerated chromatographs. The selected R group on the indazine donor moiety... 1 and R 2 The group can reduce chromophore-chromophore interactions because lower chromophore-chromophore interactions contribute to better loading confinement, better conductivity, and better dielectric breakdown resistance. The selected R group on the indazine donor group... 1 and R 2 Groups can reduce charge transfer and minimize π-bond stacking because lower charge transfer and minimized π-bond stacking contribute to less reaction to polarization and better solubility.

[0061] In various embodiments, the electron-donating group can be:

[0062]

[0063] In various embodiments, the electron-donating group can include one or more substituents on the six-membered ring of the indazine structure:

[0064]

[0065] R1, R2, R3, and R4 each independently represent a subset selected from the following: H, heteroatoms, substituted or unsubstituted C1-C atoms. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and / or (CH2). n -O-(CH2) n , where n is 1-10, and where R5 represents a portion selected from: H and / or substituted or unsubstituted aryl groups. For example, R5 may represent a phenyl substituent.

[0066] In various instances, the electron-donating group can include a five- or six-membered ring-locked indazine structure:

[0067]

[0068] R5 represents a subset selected from H and / or a substituted or unsubstituted aryl group. For example, R5 can represent a phenyl substituent.

[0069] A "π-bridge" comprises 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. Generally, the orbitals are paired (sp...). 2 The chromophore is a p-orbital on a carbon atom with a triple (sp) bond (such as in alkenes, alkynes, neutral or charged aromatic rings, and those found in neutral or charged heteroaromatic ring systems). Alternatively, the orbital can be a p-orbital on an atom such as boron or nitrogen. Additionally, the orbital can be a p, d, or f organometallic orbital or a hybrid organometallic orbital. A bridging atom containing an electron through its delocalized orbital is referred to herein as a "key atom." The number of key atoms in the bridge can be from 1 to approximately 30. Key atoms can be substituted with organic or inorganic groups. Substituents can be selected to improve the solubility of the chromophore in the polymer matrix, enhance the stability of the chromophore, or for other purposes.

[0070] Suitable bridging groups (Π) of nonlinear photochemical student chromophores according to general formula (I) can include those described in US Patent Nos. 6,584,266; 6,393,190; 6,448,416; 6,44,830; 6,514,434; all of which are incorporated herein by reference.

[0071] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). a Those:

[0072] (II 1 )

[0073] Where X represents a substituted or unsubstituted, branched or unbranched C2-C4 cross moiety; where each a and b independently represents an integer from 0 to 3; and z represents an integer from 1 to 3. In general formula (II) 1 In various embodiments where a or b in formula (I) is 1, the carbon-carbon double bond in the formula can be replaced by a carbon-carbon triple bond. Alternatively, in various embodiments, the bridging group (Π) of the nonlinear photochemical chromophore according to general formula (I) can include general formula (II). 2 Those:

[0074] (II 2 )

[0075] Where X represents a substituted or unsubstituted, branched or unbranched C2-C4 alkyl group. One or more adamantyl groups are covalently linked to a group according to general formula II. 1 Or II 2 In various embodiments of the bridging group, the one or more adamantyl groups may be connected to, for example, sulfur or oxygen atoms bound to a thiophene group or to one or more carbon atoms in X via ethers or thioethers.

[0076] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). 3 Those:

[0077] (II 3 )

[0078] Each Y independently represents: an adamantane-containing group covalently bonded to a bridging group via any of the various linkages described below (including, but not limited to, ether and thioether linkages); or each Y may represent a hydrogen-, alkyl, aryl, sulfur-, or oxygen-linked alkyl or aryl group, or a branched or unbranched, optionally heteroatom-containing C1-C4 substituent; each a and b independently represents an integer from 0 to 3; z represents an integer from 1 to 3; and each arc A independently represents a substituted or unsubstituted C2-C4 alkyl group that forms a cyclic group together with the carbon carrying the Y substituent and its two adjacent carbon atoms. The substituted or unsubstituted C2-C4 alkyl group constituting arc A may include 1 to 4 hydrogen substituents, each comprising a portion selected from: substituted or unsubstituted C1-C 10Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n Where n is 1-10. In various embodiments, z represents 1. In various embodiments, the electron-donating or electron-accepting group can include one or more covalently bonded adamantyl groups, and the general formula II 3 The Y in the formula can represent any of the substituents described above. In various embodiments, the chromophore can include an electron-donating group comprising one or more covalently linked adamantyl groups, preferably adamantyl, and the bridging group can include those according to general formula II. 3 The isophorone group, where Y represents an aryl thioether substituent.

[0079] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). 4 Those:

[0080] (II 4 )

[0081] Each Y independently represents: an adamantyl-containing group covalently bonded to a bridging group via any of the various linkages described below (including, but not limited to, ether and thioether linkages); or each Y may represent a hydrogen, alkyl, aryl, sulfur or oxygen-linked alkyl or aryl group, an aryl group directly linked by a carbon-carbon bond (optionally carrying an adamantyl group) (e.g., adamantyl anisole), a halogen, a halogenated alkyl group, a halogenated aryl group, or a branched or unbranched, optionally heteroatom-containing C1-C4 substituent; wherein each a and b independently represents an integer from 0 to 3; and z represents an integer from 1 to 3. In various embodiments, the electron-donating or electron-accepting group can include one or more covalently bonded adamantyl groups, and general formula II 4 The Y in the formula can represent any of the substituents described above. In various embodiments, the chromophore can include an electron-donating group comprising one or more covalently linked adamantyl groups, preferably adamantyl, and the bridging group can include those according to general formula II. 4 The isophorone group, wherein Y represents an aryl sulfide substituent. In various embodiments, general formula II 4 Each methyl group at the isophorone bridge can independently represent a moiety selected from: substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, halogen, halogenated alkyl (e.g., -CF3), halogenated aryl and heteroaryl (e.g., pentafluorothiophenol), and (CH2). n -O-(CH2) n , where n is 1-10.

[0082] In nonlinear photogenerated chromophores suitable for use according to various embodiments of the invention, a suitable bridging group (Π) can include the following structure (Π). a ):

[0083]

[0084] Where R 3 The symbol is selected from the following: substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 The representative is selected from the following parts: H, halogen molecule, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C groups 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; and wherein a is an integer of 1 or 2.

[0085] R 3 and R 6 The choice of bridging groups can depend on their thermal and optical stability. In other words, bridging groups without good thermal and optical stability cannot achieve the desired electro-optic effect.

[0086] For example, the bridging group (Π) of a nonlinear photogenerated chromophore according to general formula (I) can include:

[0087]

[0088]

[0089] For example, the bridging group (Π) of a nonlinear photogenerated chromophore according to general formula (I) can include:

[0090] ;

[0091] ;and .

[0092] In various embodiments, the nonlinear photogenerated chromophore having an indazine donor group may include, for example:

[0093]

[0094] The indazine donor group suitable for use in various embodiments of the invention can be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. The substituent moiety in the nonlinear photochromophore having the indazine donor group can be important for separation. Separation can reduce chromophore-chromophore interactions. Separation can reduce intermolecular charge transfer. Separation can increase the maximum applied voltage, which can contribute to better polarization and higher r. 33 .

[0095] On one hand, the nonlinear photochromic group with an indazine donor group according to various embodiments of the present invention can be a short-lived chromophore with an indazine donor or a long-lived chromophore with an indazine donor group. A short-lived chromophore with an indazine donor can have three conjugated double bonds as a Π-bridge between the acceptor and the donor. The short-lived chromophore can provide maximum redshift absorption (λ) only in the presence of a strong donor (e.g., an indazine donor). max This is only feasible under certain conditions. Short chromophores can therefore provide a narrow λ range. max Furthermore, it reduces optical loss in the device. On the other hand, the nonlinear photogenerated chromophore with an indazine donor group according to various embodiments of the present invention can be an elongated chromophore with an indazine donor group. An elongated chromophore with an indazine donor can have four or more conjugated double bonds as a Π-bridge between the acceptor and the donor.

Claims

1. Nonlinear optical student chromatographs of general formula (I): D-Π-A(I) Where D represents the expression (D) a The organoindazine electron-donating group: R in the electron-donating group of indazine 1 The representative is selected from the following parts: H, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C 10 Alkyne group, wherein the R in the electron-donating group of indazine 2 The term is selected from the following: substituted monocyclic aryl, substituted or unsubstituted polycyclic aryl, substituted or unsubstituted alkyl aryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl. Where A represents an organic electron-accepting group with a greater electron affinity than D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bonded to and separating A and D.

2. The nonlinear optical chromophore of claim 1, wherein the carbon chain length between A and D is 6 to 8 carbon atoms.

3. The nonlinear optical chromophore according to claim 1, wherein the carbon chain length between A and D is 4 carbon atoms.

4. The nonlinear optical chromosome according to claim 1, wherein the carbon chain length between A and D is 10 carbon atoms.

5. The nonlinear optical student chromaticity according to claim 2, wherein λ max The values ​​are in the range of 670 nm and 875 nm.

6. The nonlinear optical student chromaticity according to claim 2, wherein Δλ max The value is equal to or less than 130 nm.

7. The nonlinear optical student chromaticity according to claim 2, wherein Π represents having the following formula (Π a The Π-bridge between A and D: Where R 3 The symbol is selected from the following: substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 The representative is selected from the following parts: H, halogen molecule, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; and wherein a is an integer of 1 or 2.

8. The nonlinear optical student chromaticity according to claim 1, wherein A represents the general formula (A a Electron-accepting groups: Where R 4 and R 5 Each independently represents a portion selected from the following: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n , where n is 1-10.

9. The nonlinear optical chromophore according to claim 1, wherein the nonlinear chromophore has the general formula (C'): (C’)。 10. Nonlinear optical biochromosomes of general formula (I): D-Π-A(I) Where D represents an organoindazine electron-donating group having the following formula: R1, R2, R3, and R4 each independently represent a subset selected from the following: heteroatoms, substituted or unsubstituted C1-C atoms. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, or (CH2). n -O-(CH2) n , where n is 1-10, and where R5 represents a portion selected from: H or substituted or unsubstituted aryl; Where A represents an organic electron-accepting group with a greater electron affinity than D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bonded to and separating A and D.

11. The nonlinear photochromosome of claim 10, wherein R5 represents the phenyl moiety.

12. The nonlinear optical student chromaticity of claim 10, wherein Π represents having the following formula (Π a The Π-bridge between A and D: Where R 3 The symbol is selected from the following: substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 The representative is selected from the following parts: H, halogen molecule, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; and wherein a is an integer of 1 or 2.

13. The nonlinear optical student chromaticity according to claim 10, wherein A represents the general formula (A a Electron-accepting groups: Where R 4 and R 5 Each independently represents a portion selected from the following: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n , where n is 1-10.

14. Nonlinear optical student chromatographs of general formula (I): D-Π-A(I) Where D represents an organoindazine electron-donating group having one of the following formulas: R5 represents a subset selected from the following: H or a substituted or unsubstituted aryl group; Where A represents an organic electron-accepting group with a greater electron affinity than D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bonded to and separating A and D.

15. The nonlinear photochromosome of claim 14, wherein R5 represents the phenyl moiety.

16. The nonlinear optical student chromaticity of claim 14, wherein Π represents having the following formula (Π a The Π-bridge between A and D: Where R 3 The symbol is selected from the following: substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 The representative is selected from the following parts: H, halogen molecule, substituted or unsubstituted C2-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl groups, and substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; and wherein a is an integer of 1 or 2.

17. The nonlinear optical student chromaticity according to claim 14, wherein A represents the general formula (A a Electron-accepting groups: Where R 4 and R 5 Each independently represents a portion selected from the following: H, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkyne, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH2). n -O-(CH2) n , where n is 1-10.

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