Nonlinear optical chromophores containing indoridine donor groups

Abstract

Generally, the present invention aims to provide nonlinear optical chromophores having an indidine donor group. Various embodiments of the present invention include nonlinear optical chromophores having an indidine donor group having an indidine donor linked to a π-bridge group. In various preferred embodiments of the present invention, the indidine donor group may be substituted or unsubstituted, and substituents include hydrogen and alkyl substituents, aryl substituents, and combinations thereof. In certain embodiments of the present invention, the substituent portion in the indidine donor group may be important in isolation. Isolation may reduce chromophore-chromophore interactions. Isolation may reduce intermolecular charge transfer. Isolation may lead to more optimal polarization and greater r 33 This could potentially contribute to increasing the maximum applied voltage.

Description

[Technical Field]

[0001] This invention relates to a nonlinear optical chromophore having an indoridine donor group. [Background technology]

[0002] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 524,047, filed June 29, 2023, which, by reference, forms a part in its entirety within this specification.

[0003] (Background technology) Nonlinear optical (NO) 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. Examples of electro-optic devices include external modulators in communications, RF photonics, and optical interconnects. Polymer electro-optic materials have shown enormous potential for core applications in a wide range of next-generation systems and devices. These next-generation systems and devices include electro-optic modulators, optical switches, phased array radars, satellite and fiber optic communications, cable television (CATV), optical gyroscopes for aircraft and missile guidance, electronic warfare (ECM) systems, backplane interconnects for high-speed computing, ultrafast analog-to-digital conversion, mine detection, high-frequency photonics, spatial light modulation, and all-optical (optic-switching-optic) signal processing.

[0004] Many NLO molecules (chromophores) have been synthesized and exhibit high molecular electro-optic properties. In many cases, the product of the molecular dipole moment (μ) and hyperpolarizability (β) is used as an indicator of molecular electro-optic performance due to the involvement of dipoles in material processing. See International Patent Application Publication No. 00 / 09613 by Dalton et al., titled "New Class of High Hyperpolarizability Organic Chromophores and Process for Synthesizing the Same".

[0005] However, the microscopic molecular hyperpolarizability (β) is used to express the macroscopic material hyperpolarizability (χ). 2 Extremely difficult challenges arise in the process of converting to NLO materials. Molecular subcomponents (chromophores) must be integrated into NLO materials that exhibit (i) high macroscopic nonlinearity and (ii) sufficient temporal, thermal, chemical, and photochemical stability. High electro-optic activity and stability of electro-optic activity (also called temporal stability) are important for commercially viable devices. Electro-optic activity in electro-optic polymers may be increased by increasing the concentration of nonlinear optical chromophores in the host polymer and by improving the electro-optic properties of the chromophores. However, some methods of increasing chromophore concentration may reduce polarization efficiency and temporal stability. Solving these dual problems simultaneously is considered the ultimate barrier to the widespread commercialization of electro-optic polymers in a variety of devices and systems.

[0006] Hyperpolarizability of the material (χ 2The formation of non-social dipole chromophores is limited by the poor social characteristics of NLO chromophores. In commercially viable materials, chromophores must be incorporated at high molecular density with the necessary molecular dipoles statistically oriented along a single material axis. To achieve such organization, the charge transfer (dipole) properties of NLO chromophores are generally utilized by applying an external electric field during material processing. The application of an external electric field during material processing generates local low-energy states that promote non-centrosymmetric order. Unfortunately, even at moderate chromophore densities, molecules form multimolecular dipole bond (centrosymmetric) assemblies that cannot be resolved with realistic electric field energies. To overcome this challenge, the incorporation of non-social dipole chromophores into cooperative material structures is commonly achieved by constructing physical barriers (e.g., anti-packing stereogroups) that limit near-neighbor intermolecular correlations.

[0007] Therefore, in this field, it has often been considered advantageous to manufacture nonlinear optical chromophore-containing materials that exhibit a high glass transition temperature (Tg). Materials with a high glass transition temperature exhibit improved thermal stability and maintain macroscopic electro-optic properties at a higher level than materials with a lower glass transition temperature. They also exhibit desirable macroscopic optical properties and thermal stability, and have shorter absorption maximum wavelengths (i.e., λ). max It can be advantageous to manufacture a nonlinear optical chromophore having ). [Overview of the Initiative] [Means for solving the problem]

[0008] Generally, the present invention is directed to non-linear optical chromophores having an indolizinidonor group. Various embodiments of the present invention include non-linear optical chromophores having an indolizinidonor group having an indolizinidonor linked to a π-bridge. In various embodiments of the present invention, the indolizinidonor group may be substituted or unsubstituted, and the substituents include hydrogen and alkyl substituents, aryl substituents, and combinations thereof. In certain embodiments of the present invention, the substituent portion of the indolizinidonor group may be important for isolation. Isolation may reduce chromophore-chromophore interactions. Isolation may reduce intermolecular charge transfer. Isolation may contribute to more optimal polarization and a larger r 33 that may increase the maximum applied voltage.

[0009] Various embodiments of the present invention include non-linear optical chromophores having a C8-C 20 bridge group between the donor and the acceptor. Various embodiments of the present invention include non-linear optical chromophores having a C4-C6 bridge group between the donor and the acceptor, and the chromophore exhibits a smaller λ max value. In certain embodiments, the non-linear optical chromophore has a C4-C6 bridge group between the donor and the acceptor, an R 1 group that can represent any alkyl group, and an R 2 group that can represent any aryl group. These non-linear optical chromophores having a C4-C6 bridge group between the donor and the acceptor exhibit a smaller λ max value and can have a narrower absorption band. In certain other embodiments, the non-linear optical chromophore is characterized by Δλ max based on the λ max of the chromophore analog in a non-polar solvent.

[0010] The λ max values of the embodiments described herein are λ max outside the ranges described herein.It produces a wider transparency range over wavelengths greater than the value. For example, various nonlinear optical chromophores offer transparency beyond 800 nm and have applications in 1) short-range local area networks, 2) free-space optical fiber communications 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 optical chromophores having short-chain bridge groups between donor and acceptor, which exhibit reduced optical loss and can provide high transparency over various wavelengths. In addition, various embodiments of the present invention provide (1) greater r over various wavelengths 33 It possesses optimized characteristics such as (1) a high electro-optic coefficient, (2) a higher Tg (glass transition temperature), (3) significantly higher thermal stability, and (4) high photostability.

[0011] Various embodiments of the present invention are represented by the general formula (I): D-Π-A (I) (In the formula, D represents an organoelectron-donating group, A represents an organoelectron-accepting group having a greater electron affinity than D, and PI represents a π-bridge between A and D.) The π-bridge comprises a nonlinear optical chromophore having A and D, and includes a carbon chain covalently bonded to A and D, separating A and D, the carbon chain between A and D being 2 to 4 carbon atoms long, the 2 to 4 carbon atom chain containing up to 2 carbon-carbon double bonds and up to 4 side chain substituents, and two or more side chain substituents can form a ring structure having 2 to 4 carbon atoms.

[0012] In various embodiments of the present invention, the nonlinear optical chromophore of general formula (I) has an indidine donor group. In various embodiments of the present invention, the nonlinear optical chromophore of general formula (I) has an indidine donor group linked to a π-bridge.

[0013] Other aspects, features, and advantages will become apparent from the following disclosure, including a detailed description, preferred embodiments, and appended claims.

[0014] The above summary, as well as the following detailed description of preferred embodiments of the present invention, will be better understood when read in conjunction with the accompanying drawings. For illustrative purposes of the present invention, currently preferred drawings are shown. However, it should be understood that the present invention is not limited to the illustrated detailed arrangements and means. [Brief explanation of the drawing]

[0015] [Figure 1] Spectrum 100 shows the absorption across the UV-Vis spectrum of the exemplary indoridine chromophore of general formula (I) in two solvents, the first curve 101 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in 1,4-dioxane solvent, and the second curve 102 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in dichloromethane (DCM) solvent. [Figure 2] Spectrum 200 shows the absorption across the UV-Vis spectrum of the exemplary indoridine chromophore of general formula (I) in two solvents, the first curve 201 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in 1,4-dioxane solvent, and the second curve 202 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in dichloromethane (DCM) solvent. [Figure 3] Spectrum 300 shows the absorption across the UV-Vis spectrum of the exemplary indoridine chromophore of general formula (I) in two solvents; the first curve 301 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in 1,4-dioxane solvent; and the second curve 302 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in dichloromethane (DCM) solvent. [Figure 4]Spectrum 400 shows the absorption across the UV-Vis spectrum of the exemplary indoridine chromophore of general formula (I) in two solvents; the first curve 401 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in 1,4-dioxane solvent; and the second curve 402 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in dichloromethane (DCM) solvent. [Figure 5] Spectrum 500 shows the absorption across the UV-Vis spectrum of the exemplary indoridine chromophore of general formula (I) in two solvents; the first curve 501 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in 1,4-dioxane solvent; and the second curve 502 shows the absorption across the UV-Vis spectrum of the exemplary short-chain bridge chromophore of general formula (I) in dichloromethane (DCM) solvent. [Modes for carrying out the invention]

[0016] In this specification, unless otherwise clearly indicated by context and / or circumstances, the singular forms "a" and "the" are synonymous and are interchangeable with "one or more" and "at least one." Therefore, for example, a reference to "a polymer" or "the polymer" in this specification or the appended claims may refer to a single polymer or two or more polymers. As a further example, a reference to "a solvent" or "the solvent" in this specification or the appended claims may refer to a single solvent or a mixture of two or more solvents. In addition, unless otherwise specified, all numerical values ​​are understood to be modified by the word "approximately."

[0017] As used herein, the term “nonlinear optical chromophore” (NLOC) refers to a molecule or part of a molecule that produces a nonlinear optical effect when irradiated with light. A chromophore is any molecular unit that causes a nonlinear optical effect through interaction with light. The desired effect is found at the resonant or non-resonant wavelength. The activity of a particular chromophore in a nonlinear optical material is described in detail as a hyperpolarizability, which is directly related to the molecular dipole moment of the chromophore. Various embodiments of the NLO chromophore of the present invention are useful structures for generating the NLO effect.

[0018] The first-order hyperpolarizability (β) is one of the most common and useful NLO properties. Higher-order hyperpolarizability is useful in other applications such as all-optical (optic-switching-optic) applications. Materials such as compounds or polymers possess first-order hyperpolarizability and a sufficient electro-optic coefficient (r). 33 To determine whether it contains a nonlinear optical chromophore having a function of β, the following tests may be performed. First, a thin film of the material is placed in an electric field to align the dipoles. This can be done, for example, by sandwiching a film of the material between electrodes such as an indium tin oxide (ITO) substrate, a gold film, or a silver film.

[0019] The nonlinear optical chromophore of the embodiments herein has an indoridine electron-donating group and a C6-C8 chain bridge group between the donor and acceptor, and the chromophore has an optimal λ max It has a value and exhibits good electro-optic properties. λ max It must be located in the optimal region to achieve a well-optimized electro-optic effect. For example, a nonlinear optical chromophore having a bridge group between an indidine donor and acceptor is located in the DCM between λ 725 nm and 900 nm. max It has.

[0020] Δλ max This is the λ of analogs in nonpolar solvents (e.g., 1,4-dioxane). max For comparison, the λ of a nonlinear optical chromophore in a standard polar solvent (e.g., DCM) maxThis is measured by calculating Δλ. Low-polarity solvents (1,4-dioxane) stabilize the chromophore in a neutral ground state, while high-polarity solvents (DCM) stabilize the charge transfer state of the chromophore. The easier charge transfer occurs, the more "highly polar" the chromophore is, and therefore the more active it is. Here, we found that larger wavelengths are directly proportional to lower energies. Therefore, Δλ between the two solvents max The larger r is, the lower the energy required to achieve the charge transfer state. In addition, r is experimentally measured and is equivalent to the response of transmitted light to an applied electric field. 33 is Δλ max It has a general correlation with, and generally, a larger Δλ max is a larger r 33 It correlates with Δλ. max This is a characteristic of the "intensity" of the electro-optic activity of the chromophore.

[0021] Referring to Figure 1, the absorption of the chromophore (IB5822) was measured in two solvents, and the λ was measured in dichloromethane (DCM). max Its wavelength is 985.7 nm, and in 1,4-dioxane, λ max It was 806.2 nm.

[0022] Referring to Figure 2, the absorption of the chromophore (IB5825) was measured in two solvents, and λ was measured in dichloromethane (DCM). max Its wavelength is 768.5 nm, and in 1,4-dioxane, λ max It was 698.7nm.

[0023] Referring to Figure 3, the absorption of the chromophore (IB5829) was measured in two solvents, and the λ was measured in dichloromethane (DCM). max Its wavelength is 861.9 nm, and in 1,4-dioxane, λ max It was 756.9nm.

[0024] Referring to Figure 4, the absorption of the chromophore (IB5831) was measured in two solvents, and λ was measured in dichloromethane (DCM). max Its wavelength is 865.6 nm, and in 1,4-dioxane, λ maxIt was 756.3 nm.

[0025] Referring to Figure 5, the absorption of the chromophore (KO5201) was measured in two solvents, and the λ was measured in dichloromethane (DCM). max Its wavelength is 726.3 nm, and in 1,4-dioxane, λ max It was 670nm.

[0026] The short-chain bridge chromophores in Figures 1-5, and the λ of other chromophores max and Δλ max The data is summarized below.

[0027] [Table 1]

[0028] Next, to generate a polarization field, a potential is applied to the electrodes while the material is heated to near its glass transition temperature (Tg). After a suitable amount of time, the temperature is gradually reduced while maintaining the polarization field. Alternatively, the material can also be polarized by corona polarization. In this method, a charging needle placed at an appropriate distance from the material film provides the polarization field. In either case, dipoles within the material tend to align along the electric field. Furthermore, various embodiments of the present invention may include, or may not include, electro-optic materials having a material glass transition temperature of 100°C or higher, 125°C or higher, or 150°C or higher.

[0029] Next, the nonlinear optical properties of the polarized material are tested as follows: Polarized light (often emitted from a laser) is passed through the polarized material and guided through a polarizing filter to a light intensity detector. If the intensity of the light received by the detector changes when the potential applied to the electrode is changed, the material contains a nonlinear optical chromophore with an electro-optically changing refractive index. A more detailed discussion of the technique for measuring the electro-optic constants of a polarized film containing a nonlinear optical chromophore is found in "Measuring Electro-Optic Constants of a Poled Film" by Chia-Chi Teng, Chapter 7, pp. 447-49, *Nonlinear Optics of Organic Molecules and Polymers* (edited by Hari Singh Nalwa & Seizo Miyata, 1997), which by reference constitutes part of this specification. However, in the event of any inconsistency between the disclosures or definitions of this application and those of this specification, the disclosures or definitions of this specification shall prevail.

[0030] The relationship between the change in applied potential and the change in the refractive index of a material is given by its electro-optic (OE) coefficient r 33 This is represented by [formula]. This effect is generally called the electro-optic (EO) effect. A device containing a material whose refractive index changes in response to a change in applied potential is called an electro-optic (EO) device. With regard to the compositions having short-chain bridge chromophores described herein, large EO coefficients of over 30 pm / V (e.g., measured at 980 nm) or over 20 pm / V (e.g., measured at 1310 nm) can be achieved.

[0031] Compositions having short-chain bridge chromophores as described herein can exhibit reduced optical loss. The optical loss of the various embodiments described herein can be less than 2 dB / cm. Furthermore, the compositions described herein may provide a high degree of transparency at wavelengths outside the absorption band of the various embodiments described herein. In addition, the compositions described herein can exhibit extremely high thermal stability (characterized by a decomposition temperature higher than 250°C) and high photostability (measured by the decomposition of photo-optical materials measured under broadband light and ambient conditions).

[0032] Secondary hyperpolarizability (γ) or tertiary susceptibility (χ) 3 ) is a standard measurement of tertiary NLO activity. Several methods exist for measuring these properties, but degenerate four-wave mixing (DFWM) is very common. See, by reference, CW Thiel, "Four-Wave Mixing and Its Applications" (www.physics.montana.edu.students.thiel.docs / FWMixing.pdf), which is in whole form part of this specification. A method for evaluating the tertiary NLO properties of a thin film, known in the art as degenerate four-wave mixing (DFWM), can be used, with reference to U.S. Patent Application Publication 2012 / 0267583A1, which is in whole form part of this specification. In Figure 4 of U.S. Patent Application Publication 2012 / 0267583A1, beams 1 and 2 are picosecond coherent pulses absorbed by an NLO thin film deposited on a glass substrate. Beam 3 is a weaker and slightly delayed beam with the same wavelength as beams 1 and 2. Beam 4 is the product of optical wave mixing, where beams 1 and 2 are diffracted by a transient holographic diffraction grating generated by interference within the thin film NLO material. Beam 3 can be a "control" beam in the communication wavelength band, generating a "signal" beam at a frequency not absorbed by the NLO material.

[0033] A nonlinear optical chromophore suitable for use according to various embodiments of the present invention is given by general formula (I): D-Π-A (I) (In the formula, D represents an organoelectron-donating group, A represents an organoelectron-accepting group having a greater electron affinity than D, and PI represents a π-bridge between A and D.) This includes having the following terms: “electron-donating group (donor group or “D”)”, “π-bridge (bridge or “Π”)”, and “electron-accepting group (acceptor group or “A”)”, as well as general methods for synthesizing D-π-A chromophores, are described, for example, in U.S. Patent Nos. 5,670,091, 5,679,763, 6,090,332, 6,716,995, and U.S. Patent Application No. 17 / 358,960 filed June 25, 2021, which are by reference to be part of this specification in whole.

[0034] An acceptor is an atom or group of atoms with a lower reduction potential that can accept electrons from a donor via a π-bridge. The acceptor (A) has a greater electron affinity than the donor (D). Therefore, at least in the absence of an external electric field, the chromophore is generally polarized in the ground state, and a relatively high electron density exists on the acceptor (A) side. Typically, the acceptor group contains at least one electronegative heteroatom, which is part of a π bond (double or triple bond) and can exhibit resonance structures that move electron pairs from the π bond to the heteroatom side, while simultaneously reducing the multiplicity of the π bond (i.e., a double bond is formally converted to a single bond, and a triple bond is formally converted to a double bond). This gives the heteroatom a formal negative charge. The heteroatom may also be part of a heterocycle. Typical acceptor groups include, but are not limited to, -NO2, -CN, -CHO, COR, CO2R, -PO(OR)3, -SOR, -SO2R, and -SO3R (wherein R is alkyl, aryl, or heteroaryl). The total number of heteroatoms and carbons in the acceptor group is approximately 30, and the acceptor group may be further substituted with alkyl, aryl, and / or heteroaryl groups.

[0035] 2012 / 0267583 (collectively, “Prior Publications”), U.S. Patent No. 6,584,266, U.S. Patent No. 6,3 This includes those described in U.S. Patent No. 93,190, U.S. Patent No. 6,448,416, U.S. Patent No. 6,44,830, U.S. Patent No. 6,514,434, U.S. Patent No. 5,044,725, U.S. Patent No. 4,795,664, U.S. Patent No. 5,247,042, U.S. Patent No. 5,196,509, U.S. Patent No. 4,810,338, U.S. Patent No. 4,936,645, U.S. Patent No. 4,767,169, U.S. Patent No. 5,326,661, U.S. Patent No. 5,187,234, U.S. Patent No. 5,170,461, U.S. Patent No. 5,133,037, U.S. Patent No. 5,106,211, and U.S. Patent No. 5,006,285.

[0036] In a nonlinear optical chromophore suitable for use according to various embodiments of the present invention, a suitable electron-accepting group is a general formula (A a ):

[0037] [ka]

[0038] (In the formula, R 4 and R 5 These are, independently of each other, H, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C2-C 10Alkenyl, substituted or unsubstituted C2-C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, and (CH2) n -O-(CH2) n (In the formula, n is between 1 and 10.) This represents a base selected from the group consisting of the following elements. It may include those that conform to the following. When used in this specification, the following base structure:

[0039] [ka] R represents a bonding site to another group in a larger molecular structure. In various preferred embodiments, R 4 and R 5 Either or both of these represent halogen substituents. Halogen substitution may mean monosubstituted, disubstituted, trisubstituted, and higher-level substitutions. In various embodiments, R 4 and R 5 In various embodiments, R 4 and R 5 One of them represents a halogen-substituted aromatic group, and the other represents an alkyl group. In various embodiments, the electron-accepting group can have the following structures.

[0040] [ka]

[0041] In various embodiments, the electron-accepting group can have the following structure:

[0042] [ka]

[0043] In various embodiments, the electron-accepting group can have the following structure:

[0044] [ka]

[0045] Generally, the selection of electron-accepting groups may be tailored to the strength of electron-donating groups. The combined strength between electron-donating and electron-accepting groups does not need to be too weak or too strong. If the combined strength is too weak, a smaller r 33 together with λ max It transitions to blue. If the overall intensity is too strong, a smaller r 33 and with greater loss λ max It undergoes a red transition. Also, R in the electron-accepting group 4 base and R 5 The choice of groups may depend on the volume of the acceptor groups to be isolated. Better isolation of the acceptor groups may result in better electro-optic properties.

[0046] The donor comprises an atom or group of atoms with a low oxidation potential, which donates electrons to the acceptor "A" through a π-bridge. The donor (D) has a lower electron affinity than the acceptor, and the chromophore is generally polarized, at least in the absence of an external electric field, and the donor (D) has a relatively low electron density. Typically, the donor group has at least one heteroatom, which has a lone pair of electrons that can be conjugated to the p-orbital of the atom directly bonded to the heteroatom, and can draw resonance structures that move the lone pair of electrons to the p-orbital of the atom directly bonded to the heteroatom, formally increasing the multiplicity of the bond between the heteroatom and the atom directly bonded to the heteroatom (i.e., a single bond is formally converted to a double bond, and a double bond is formally converted to a triple bond). Thereafter, the heteroatom acquires a formal positive charge. The p-orbital of the atom directly bonded to the heteroatom may be an empty orbital, or it may be part of a multiple bond with another atom other than the heteroatom. The heteroatom may be a substituent of an atom having a π bond, or it may be located within a heterocyclic ring. Exemplary donor groups are R2N- and R nX 1 -(wherein R is alkyl, aryl, or heteroaryl, X 1 The donor group may include, but is not limited to, O, S, P, Se, or Te, where n is 1 or 2. The total number of heteroatoms and carbons in the donor group is approximately 30, and the donor group may be further substituted with alkyl, aryl, and / or heteroaryl groups.

[0047] In a nonlinear optical chromophore suitable for use according to various embodiments of the present invention, a suitable electron-donating group is the following indoridine donor group (D a ):

[0048] [ka]

[0049] (R in the indoridine donor group) 1 H, substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyls, and substituted or unsubstituted C2-C 10 Represents a group selected from the group consisting of alkynyls, and R in the indoridine donor group. 2 (This represents a group selected from the group consisting of substituted or unsubstituted monocyclic aryl groups, substituted or unsubstituted polycyclic aryl groups, substituted or unsubstituted alkylaryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups.) It may include R, which isolates the nitrogen in the indoridine donor group. 1 and R 2 The selection of R on the selected indoridine donor group plays a crucial role in achieving good properties of the nonlinear optical chromophore. 1 base and R 2 The group may reduce chromophore-chromophore interaction because less chromophore-chromophore interaction contributes to better packing limitation, better conductivity, and better properties against dielectric breakdown.1 base and R 2 The group may reduce charge transfer and minimize π-bond stacking because less charge transfer and minimized π-bond stacking contribute to less adverse effects on polarization and better solubility.

[0050] In various embodiments, the electron-donating group may have the following structure.

[0051] [ka]

[0052] In various embodiments, the electron-donating group may include one or more substituents on the six-membered ring of the indoridine structure.

[0053] [ka]

[0054] In the formula, R1, R2, R3, and R4 are each independently H, a heteroatom, and substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, and (CH2) n -O-(CH2) n R5 represents a group selected from the group consisting of (wherein n is 1 to 10), and R5 represents a group selected from the group consisting of H and / or substituted or unsubstituted aryl groups. For example, R5 may represent a phenyl substituent.

[0055] In various embodiments, the electron-donating group may include an indoridine structure fixed with a 6-membered ring or a 5-membered ring.

[0056] [ka]

[0057] In the formula, R5 represents a group selected from the group consisting of H and / or substituted or unsubstituted aryl groups. For example, R5 may represent a phenyl substituent.

[0058] A "π-bridge" is an atom or group of atoms that can delocalize electrons from an electron donor (as defined above) to an electron acceptor (as defined above) through the orbitals of atoms within the bridge. Typically, the orbitals are those of double-bonded carbon atoms (sp) found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. 2 These are p orbitals on a carbon atom (sp) or a triple-bonded carbon atom. In addition, these orbitals may be p orbitals on atoms such as boron or nitrogen. In addition, these orbitals may be p, d, or f organometallic orbitals or hybrid organometallic orbitals. In this specification, atoms in a bridge that contain an orbital through which electrons are delocalized are referred to as “critical atoms”. The number of critical atoms in a bridge may be a number from 1 to about 30. Critical atoms may be substituted with organic or inorganic groups. Substituents may be selected in terms of improving the solubility of the chromophore in the polymer matrix, increasing the stability of the chromophore, or for other purposes.

[0059] Bridge groups (Π) suitable for nonlinear optical chromophores according to general formula (I) include those described in U.S. Patents No. 6,584,266, 6,393,190, 6,448,416, 6,44,830 and 6,514,434, which are by reference to form part of this specification in whole.

[0060] In various embodiments, the bridge group (Π) for a nonlinear optical chromophore according to general formula (I) is general formula (Π1 ):

[0061] [ka]

[0062] (In the formula, X represents a substituted or unsubstituted, branched or unbranched C2-C4 diyl group, a and b each independently represent an integer from 0 to 3, and z represents an integer from 1 to 3.) It may include those having the following: General formula (Π 1 In various embodiments where a or b in ) is 1, the carbon-carbon double bond in the formula can be replaced with a carbon-carbon triple bond. Alternatively, in various embodiments, the bridge (Π) of a nonlinear optical chromophore following general formula (I) is general formula (Π 2 ):

[0063] [ka]

[0064] (In the formula, X represents a substituted or unsubstituted, branched or unbranched C2-C4 diyl group.) It may include those having the following characteristics: General formula Π 1 or Π 2 In various embodiments in which one or more diamondoid groups are covalently bonded to a crosslinking group, one or more diamondoid groups may, for example, be bonded to a sulfur atom or oxygen atom of a thiophene group, or to one or more carbon atoms in X via an ether linking group or a thioether linking group.

[0065] In various embodiments, the bridge group (Π) for a nonlinear optical chromophore according to general formula (I) is general formula (Π 3 ):

[0066] [ka]

[0067] (Wherein, Y each independently represents a diamondoid-containing group covalently bonded to the bridge group by any of various linking groups (including, but not limited to, ether linking groups and thioether linking groups) described hereinafter in this specification, or each Y represents hydrogen, an alkyl group, an aryl group, an alkyl or aryl group to which sulfur or oxygen is bonded, or a branched or unbranched C1-C4 substituent optionally containing a heteroatom; a and b each independently represent an integer from 0 to 3; z represents an integer from 1 to 3; Each arc A independently represents a substituted or unsubstituted C2-C4 alkyl group, and these together with the carbon atom having a Y substituent and the two adjacent carbon atoms form a cyclic group: The substituted or unsubstituted C2-C4 alkyl group constituting arc A may contain 1 to 4 hydrogen substituents, and the hydrogen substituents are substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkylaryl group, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted cyclohexyl, and (CH2) n -O-(CH2) n (wherein n is from 1 to 10).) selected from the group consisting of. ) Those having can be included. In various embodiments, z represents 1. In various embodiments, the electron-donating group or the electron-accepting group can include one or more covalently bonded diamondoid groups. General formula Π 3 Y in can represent any of the above substituents. In various embodiments, the chromophore includes an electron-donating group containing one or more covalently bonded diamondoid groups, preferably adamantyl, and the bridge group is of the general formula Π 3It may contain an isophorone group according to (where Y represents an aryl thioether substituent).

[0068] In various embodiments, the bridge group (Π) for the non-linear optical chromophore according to general formula (I) is of general formula (Π 4 ):

[0069]

Chemical formula

[0070] (where Y each independently represents a diamondoid-containing group covalently bonded to the bridge group by any of various linking groups (including, but not limited to, ether linking groups and thioether linking groups) described later in this specification, or each Y is hydrogen, an alkyl group, an aryl group, an alkyl or aryl group bonded to sulfur or oxygen, an aryl group directly bonded by a carbon-carbon bond (optionally having a diamondoid group) (for example, adamantly anisole), a halogen, a halogenated alkyl group, a halogenated aryl group, or a branched or unbranched C1-C4 substituent optionally containing a heteroatom; a and b each independently represent an integer from 0 to 3; z represents an integer from 1 to 3.) Those having can be included. In various embodiments, the electron-donating group or electron-withdrawing group can include one or more covalently bonded diamondoid groups, and Y in general formula Π 4 may represent any of the above substituents. In various embodiments, the chromophore includes an electron-donating group containing one or more covalently linked diamondoid groups (preferably adamantyl), and the bridge group includes an isophorone group according to general formula Π 4 (where Y represents an aryl thioether substituent). Alternatively, in various embodiments, general formula Π 4The methyl groups at the geminal position on the isophorone bridge are, independently, substituted or unsubstituted C1-C1. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, halogens, halogenated alkyl groups (e.g., -CF3), halogenated aryl and heteroaryl groups (e.g., pentafluorothiophenol), and (CH2) n -O-(CH2) n This can represent a base selected from the group consisting of (where n is between 1 and 10).

[0071] In a nonlinear optical chromophore suitable for use according to various embodiments of the present invention, a suitable bridge group (Π) has the following structure (Π a ) includes.

[0072] [ka]

[0073] In the formula, R 3 R represents a group selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted alkylaryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups. 6 H, halogen molecules, substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10 This represents a group selected from the group consisting of alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyls, where a is an integer of 1 or 2.

[0074] R 3base and R 6 The selection of the bridge group is based on its thermal and photostable properties. In other words, a bridge group that does not possess good thermal and photostable properties may not be able to achieve the desired electro-optic effect.

[0075] For example, a bridge group (Π) for a nonlinear optical chromophore following general formula (I) may include the following structure:

[0076] [ka]

[0077] For example, a bridge group (Π) for a nonlinear optical chromophore following general formula (I) may include the following structure:

[0078] [ka]

[0079] In various embodiments, the nonlinear optical chromophore having an indoridine donor group may include, for example, the following structure.

[0080] [ka]

[0081] The indidine donor group suitable for use in various embodiments of the present invention may be substituted or unsubstituted, and the substituents include hydrogen and alkyl substituents, aryl substituents, and combinations thereof. The substituent portion of the nonlinear optical chromophore having the indidine donor group may be important for isolation. Isolation reduces chromophore-chromophore interaction. Isolation may reduce intermolecular charge transfer. Isolation leads to more optimal polarization and greater r 33 This could potentially contribute to increasing the maximum applied voltage.

[0082] On the other hand, a nonlinear optical chromophore having an indidine donor group according to various embodiments of the present invention may be a short chromophore having an indidine donor, or a long chromophore having an indidine donor. A short chromophore having an indidine donor may have three conjugated double bonds as a π-bridge between the acceptor and the donor. The short chromophore has a red-transitioned absorption maximum (λ max This is only feasible if a strong donor (e.g., an indidine donor) is available that provides ). Therefore, a short chromophore is narrow λ max This may provide a reduction in light loss in the device. On the other hand, a nonlinear optical chromophore having an indidine donor group according to various embodiments of the present invention may be a long chromophore having an indidine donor. A long chromophore having an indidine donor may have four or more conjugated double bonds as a π-bridge between the acceptor and the donor.

Claims

1. General formula (I): D-Pi-A (I) (In the formula, D is the following formula (D a ): 【Chemistry 1】 (In the formula, R in the indolizine donor group 1 represents a group selected from the group consisting of H, substituted or unsubstituted C 2 to C 10 alkyl, substituted or unsubstituted C 2 to C 10 alkenyl, and substituted or unsubstituted C 2 to C 10 alkynyl, and R in the indolizine donor group 2 represents a group selected from the group consisting of substituted monocyclic aryl, substituted or unsubstituted polycyclic aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, and substituted or unsubstituted cyclohexyl.) (An organodidine electron-donating group is represented, where A represents an organoelectron-accepting group having a greater electron affinity than D, and PI represents a π-bridge between A and D, the π-bridge containing a carbon chain that covalently bonds to A and D and separates A and D.) A nonlinear optical chromophore characterized by having the following features.

2. The nonlinear optical chromophore according to claim 1, characterized in that the carbon chain length between A and D is 6 to 8 carbon atoms.

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

4. The nonlinear optical chromophore according to claim 1, characterized in that the carbon chain length between A and D is 10 carbon atoms.

5. λ max The nonlinear optical chromophore according to claim 2, characterized in that the value is within the range of 670 nm to 875 nm.

6. Δλ max The nonlinear optical chromophore according to claim 2, characterized in that the value is 130 nm or less.

7. Π is given by the following equation (Π a ): 【Chemistry 2】 (In the formula, R 3 R represents a group selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted alkylaryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups. 6 H, halogen molecules, substituted or unsubstituted C 2 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 (This represents a group selected from the group consisting of alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyls, where a is an integer of 1 or 2.) The nonlinear optical chromophore according to claim 2, characterized in that it represents a π-bridge between A and D.

8. A is the general formula (A a ): 【Transformation 3】 (In the formula, R 4 and R 5 These are, independently, H, substituted or unsubstituted C. 1 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, and (CH 2 ) n -O-(CH 2 ) n (In the formula, n is between 1 and 10.) This represents a group selected from the group consisting of these elements. The nonlinear optical chromophore according to claim 1, characterized in that it represents an electron-accepting group having the above.

9. The general formula for a nonlinear optical chromophore is (C'): 【Chemistry 4】 The nonlinear optical chromophore according to claim 1, characterized by having the above.

10. General formula (I): D-Pi-A (I) (In the formula, D is the following formula: 【Transformation 5】 (In the formula, R 1 , R 2 , R 3 and R 4 These are, independently, heteroatoms, substituted or unsubstituted C 1 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, and (CH 2 ) n -O-(CH 2 ) n R represents a group selected from the group consisting of (wherein n is 1 to 10), 5 (This represents a group selected from the group consisting of H, or substituted or unsubstituted aryl groups.) (An organodidine electron-donating group is represented, where A represents an organoelectron-accepting group having a greater electron affinity than D, and PI represents a π-bridge between A and D, the π-bridge containing a carbon chain that covalently bonds to A and D and separates A and D.) A nonlinear optical chromophore characterized by having the following features.

11. R 5 The nonlinear optical chromophore according to claim 10, characterized in that represents a phenyl group.

12. Π is given by the following equation (Π a ): 【Transformation 6】 (In the formula, R 3 R represents a group selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted alkylaryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups. 6 H, halogen molecules, substituted or unsubstituted C 2 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 (This represents a group selected from the group consisting of alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyls, where a is an integer of 1 or 2.) The nonlinear optical chromophore according to claim 10, characterized in that it has a π-bridge between A and D.

13. A is the general formula (A a ): 【Transformation 7】 (In the formula, R 4 and R 5 These are, independently, H, substituted or unsubstituted C. 1 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 Alkynnyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted cyclohexyls, and (CH 2 ) n -O-(CH 2 ) n (In the formula, n is between 1 and 10.) This represents a group selected from the group consisting of these elements. The nonlinear optical chromophore according to claim 10, characterized in that it represents an electron-accepting group having the above.

14. General formula (I): D-Pi-A (I) (In the formula, D is the following formula: 【Transformation 8】 (In the formula, R 5 (This represents a group selected from the group consisting of H, or substituted or unsubstituted aryl groups.) (An organodidine electron-donating group having one of the following characteristics: A represents an organoelectron-accepting group having a greater electron affinity than D; PI represents a π-bridge between A and D, the π-bridge containing a carbon chain covalently bonded to A and D and separating A and D.) A nonlinear optical chromophore characterized by having the following features.

15. R 5 The nonlinear optical chromophore according to claim 14, characterized in that represents a phenyl group.

16. Π is given by the following equation (Π a ): 【Chemistry 9】 (In the formula, R 3 R represents a group selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted alkylaryl groups, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyl groups. 6 H, halogen molecules, substituted or unsubstituted C 2 ~C 10 Alkyl, substituted, or unsubstituted C 2 ~C 10 Alkenyl, substituted or unsubstituted C 2 ~C 10 (This represents a group selected from the group consisting of alkynyls, substituted or unsubstituted aryls, substituted or unsubstituted alkylaryls, substituted or unsubstituted carbocyclic groups, substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted cyclohexyls, where a is an integer of 1 or 2.) The nonlinear optical chromophore according to claim 14, characterized in that it represents a π-bridge between A and D having

17. A is the general formula (A a ): 【Chemistry 10】 (wherein, R 4 and R 5 each independently represents H, a substituted or unsubstituted C 1 - C 10 alkyl, a substituted or unsubstituted C 2 - C 10 alkenyl, a substituted or unsubstituted C 2 - C 10 alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted cyclohexyl, and (CH 2 ) n - O - (CH 2 ) n (wherein, n is 1 to 10). represents a group selected from the group consisting of.) The nonlinear optical chromophore according to claim 14, characterized in that it represents an electron-accepting group having the above.

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