Non-linear optical chromatography with

Abstract

The present invention relates generally to non-linear optical chromophores having a Michler's base type group. Various embodiments of the present invention include a non-linear optical chromophore having a rice alkali type group having a rice alkali donor group attached to a pi-bridge group. Various embodiments of the present invention include non-linear photochromophores with rice alkali-type groups having high photostability, which are capable of reducing the percentage of inactivation under illumination by molecular oxygen.

Description

[0001] Cross-reference with related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 525,539, filed July 7, 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), 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 phased-array radar, 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 (optically controlled optical) 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. 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 temporal stability. Simultaneously addressing these dual problems is considered the ultimate obstacle to the widespread commercialization of EO polymers in numerous 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 (hyperpolarizability) 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-bonded (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 often considered advantageous in the art to prepare nonlinear optical student chromatographs 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. However, materials with such elevated glass transition temperatures require significantly increased temperatures during the polarization process to achieve adequate alignment. The need to apply these elevated temperatures is costly, time-consuming, and results in a phenomenon known as low polarization efficiency.

[0008] Invention Summary

[0009] This invention generally relates to nonlinear photogenerated chromophores having Michler's base type groups. Various embodiments of the invention include nonlinear photogenerated chromophores having Michler's base type groups, which have Michler's base donor groups linked to Π-bridging groups. Embodiments of the invention may include nonlinear photogenerated chromophores having Michler's base type groups with high photostability, which are capable of reducing the percentage of inactivation by molecular oxygen under light irradiation.

[0010] Various embodiments of the present invention include nonlinear optical biochromosomes of general formula (I):

[0011] D-Π-A(I)

[0012] Wherein D represents an organic electron-donating group; 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 milchi alkaloid type group acts as a donor group in the nonlinear photogenerated chromophore.

[0013] The nonlinear photogenerated chromophore of formula (I) can have a michidine-type donor group. In various embodiments of the present invention, the nonlinear photogenerated chromophore of formula (I) has a michidine-type donor group connected to a Π-bridging group. In various embodiments of the present invention, the nonlinear photogenerated chromophore of formula (I) has high photostability.

[0014] The milchi alkaloid-type donor group can be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. In various embodiments, the milchi alkaloid-type donor group can be symmetrically substituted or asymmetrically substituted.

[0015] Other aspects, features, and advantages will be apparent from the following disclosure (including the detailed description of the invention, preferred embodiments, and appended claims). Brief description of some views in the attached diagram

[0016] 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.

[0017] In the attached diagram:

[0018] Figure 1 Spectrum 100 illustrates the differential scanning calorimetry (DSC) of the chromophore Pk4.2T, the chlorophyll donor of the embodiment of general formula (I). Three curves 101a-101c show the heat flow-temperature profiles of the DSC, while the midpoint temperature 102 indicates the glass transition temperature (T) of the chlorophyll donor chromophore Pk4.2T of the embodiment of general formula (I). g ).

[0019] Figure 2Various embodiments of micriticine-type donor groups according to the present invention are described, wherein 202a-202j show the skeletal structural formulas of various embodiments of micriticine-type donor groups. 202a shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2P. 202b shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2R. 202c shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2S. 202d shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2T. 202e shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2U. 202f shows the skeletal structural formula of a micriticine-type donor group in chromophore Pk4.2V. Image 202g shows the skeletal structure of the micritic alkaloid-type donor group in chromophore Pk4.2X. Image 202h shows the skeletal structure of the micritic alkaloid-type donor group in chromophore Pk4.2Z. Image 202i shows the skeletal structure of the micritic alkaloid-type donor group in chromophore Pk4.3X. Image 202j shows the skeletal structure of the micritic alkaloid-type donor group in chromophore Pk4.4I.

[0020] Figure 3 Various embodiments of chromophores having mirtinocyanine-type donor groups according to the present invention are described, wherein 302a-302j show the skeletal structural formulas of various embodiments of chromophores having mirtinocyanine-type donor groups. 302a shows the skeletal structural formula of chromophore Pk4.2P. 302b shows the skeletal structural formula of chromophore Pk4.2R. 302c shows the skeletal structural formula of chromophore Pk4.2S. 302d shows the skeletal structural formula of chromophore Pk4.2T. 302e shows the skeletal structural formula of chromophore Pk4.2U. 302f shows the skeletal structural formula of chromophore Pk4.2V. 302g shows the skeletal structural formula of chromophore Pk4.2X. 302h shows the skeletal structural formula of chromophore Pk4.2Z. 302i shows the skeletal structural formula of chromophore Pk4.3X. 302j shows the skeletal structure of the chromophore Pk4.4I. Invention Details

[0022] 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".

[0023] As used herein, the term "nonlinear optical chromophore" (NLOC) refers to a molecule or molecular unit 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 reactivity of a particular chromophore in a nonlinear optical material is called its electro-optic coefficient (r). 33 This relates to dipole moment and hyperpolarizability. Various embodiments of the NLO chromophore of this invention are structures useful for generating the NLO effect.

[0024] 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 hyperpolarizability and a sufficient electro-optic coefficient (r... 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).

[0025] 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, in which a charged needle at a suitable distance from the material film provides the polarizing electric field. In either case, the dipoles in the material tend to align with the field.

[0026] Reference Figure 1 The glass transition temperature (T) of chromophore Pk4.2T g The temperature is 169.37℃.

[0027] 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.

[0028] The relationship between the change in applied potential and the change in the refractive index of a substance can be expressed as its EO coefficient r. 33 This 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.

[0029] 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 prevalent. 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 Figure 4 of US 2012 / 0267583A1, beams 1 and 2 are picosecond coherent pulses absorbed by the NLO film deposited on the 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 in the NLO material of the film. Beam 3 can be a "contrast" beam for communication wavelengths, generated as a "signal" beam at frequencies not absorbed by the NLO material.

[0030] Photostability is one of the most useful properties of chromophores. High photostability is crucial for chromophores because it ensures they do not degrade under light in an air atmosphere. If the double bond in a chromophore reacts with molecular oxygen, the chromophore will degrade under light in air. Molecular oxygen in an air atmosphere can be triplet oxygen or singlet oxygen. Triplet oxygen is the electronic ground state of molecular oxygen, meaning it is the most stable and common allotrope of oxygen and is unreactive with double bonds. Light converts triplet oxygen molecules into singlet oxygen molecules, which are highly reactive with double bonds. Overall, singlet oxygen is the cause of chromophore degradation under light in an air atmosphere. The reaction of singlet oxygen with the chromophore's double bond inactivates the chromophore by rendering the double bond optically inactive. Therefore, if a chromophore is resistant to singlet oxygen degradation, it will possess high photostability, and fewer resources will be required to remove oxygen from the working apparatus.

[0031] Nonlinear optical student chromatids suitable for use according to various embodiments of the present invention include those having the general formula (I):

[0032] D-Π-A(I)

[0033] 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 general synthetic methods for forming the D-Π-A chromophore 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.

[0034] In nonlinear photogenerated chromophores suitable for use in various embodiments of the invention, suitable electron-donating groups can include those according to general formula (D a Those:

[0035]

[0036] (D a )

[0037] R1 and R2 each independently represent portions 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, This represents a bonding point with another part of the larger molecular structure.

[0038] Reference Figure 2 According to various embodiments of the present invention, the chromophore includes the following micriticine-type donor groups:

[0039]

[0040]

[0041] 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.

[0042] 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.

[0043] In nonlinear photogenerated chromophores suitable for use according to various embodiments of the invention, suitable electron-accepting groups can include those according to general formula (A a Those:

[0044]

[0045] Where R 4 and R 5Each 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, R 2 and R 3 One represents a halogen-substituted aromatic moiety, while the other represents an alkyl moiety. In various embodiments, the electron-accepting group can be:

[0046]

[0047] In various embodiments, the electron-accepting group can be:

[0048]

[0049] In various embodiments, the electron-accepting group can be:

[0050] .

[0051] 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. Such groups are well-known in the art. Generally, the orbitals are paired (sp...). 2The chromophore is a p-orbital on a carbon atom with a triple (sp) bond (such as those found in alkenes, alkynes, neutral or charged aromatic rings, and 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.

[0052] 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.

[0053] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). a Those:

[0054]

[0055] 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) a 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). b Those:

[0056]

[0057] 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. a Or II b 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.

[0058] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). c Those:

[0059]

[0060] 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 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. 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 c 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. c The isophorone group, where Y represents an aryl thioether substituent.

[0061] In various embodiments, the bridging group (Π) of the nonlinear photogenerated chromophore according to general formula (I) can include general formula (II). d Those:

[0062]

[0063] 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 d 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. d The isophorone group, wherein Y represents an aryl sulfide substituent. In various embodiments, general formula II d 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-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, halogen, halogenated alkyl (e.g., -CF3), halogenated aryl and heteroaryl (e.g., pentafluorothiophenol), and (CH2). n -O-(CH2) n , where n is 1-10.

[0064] Various preferred chromophores according to embodiments of the present invention include those of the general formula (Π) 1 ) of the Π-bridge:

[0065]

[0066] Where R 3 and R 6 Each independently represents a portion selected from the following: H, halogen, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C2-C 10 Alkenyl, substituted or unsubstituted C2-C 10Alkyne, 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.

[0067] R 3 and R 6 The choice of functional group can depend on the polarization of the substituent. If a particular substituent can increase the polarization of the chromophore, that particular substituent can bring better electro-optic properties to the chromophore. For example, the "-CF3" moiety can be a good R... 6 Group.

[0068] Various preferred chromophores according to embodiments of the present invention include those of the general formula (Π) 2 ) of the Π-bridge:

[0069]

[0070] Where R 7 The representative is selected from the following parts: H, halogen, 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. General formula (Π 2 The five-membered ring structure in the chromophore can increase the polarization of the chromophore, which can bring better electro-optic properties to the chromophore.

[0071] Various embodiments of the present invention include the following Π-bridge:

[0072]

[0073]

[0074] ;and .

[0075] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2P:

[0076]

[0077] (Pk4.2P)

[0078] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2R:

[0079]

[0080] (Pk4.2R)

[0081] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2S:

[0082]

[0083] (Pk4.2S)

[0084] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2T:

[0085]

[0086] (Pk4.2T)

[0087] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2U:

[0088]

[0089] (Pk4.2U)

[0090] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2V:

[0091]

[0092] (Pk4.2V)

[0093] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2X:

[0094]

[0095] (Pk4.2X)

[0096] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.2Z:

[0097]

[0098] (Pk4.2Z)

[0099] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.3X:

[0100]

[0101] (Pk4.3X)

[0102] Reference Figure 3 Examples of chromophores suitable for use according to various embodiments may include chromophore Pk4.4I:

[0103]

[0104] (Pk4.4I)

[0105] In addition to all chromophores disclosed in the references incorporated herein by reference, examples of chromophores suitable for use in various embodiments may also include the following:

[0106]

[0107] The nonlinear photochromophores according to various embodiments of the present invention also include michidine-type donor groups connected to the Π-bridge and acting as donors in the chromophore.

[0108] The michidine-type donor groups suitable for use in various embodiments of the invention can be substituted or unsubstituted, including hydrogen and alkyl substituents, aryl substituents, and combinations thereof. Such michidine-type groups can be symmetrically substituted or asymmetrically substituted.

[0109] The nonlinear photochromophores described in this embodiment have a micritic alkaloid-type donor group connected to a Π-bridge, exhibiting high photostability. For example, nonlinear photochromophores with micritic alkaloid-type donor groups can have 70% or higher photostability. The photostability percentage is measured as follows: after exposing the chromophore to light for 20 hours, the amount of chromophore that remains unchanged and undegraded via UV-Vis absorption is calculated. For example, 75% photostability means that 75% of the chromophore remains unchanged after 20 hours of light exposure, while only 25% of the chromophore is inactivated by light and / or singlet oxygen. Therefore, a higher photostability percentage indicates high photostability of the chromophore.

[0110] The photostability percentage data for various embodiments of nonlinear photogeneronic chromophores with michidine-type donor groups are summarized below:

[0111]

[0112] According to certain embodiments, chromophores having milch-type donor groups as described herein can be incorporated into electro-optic (EO) materials. For example, an EO material can comprise one or more nonlinear optical chromophores incorporated into a matrix material. For instance, an EO material can be a pure film of a single type of chromophore having milch-type donor groups. In another example, an EO material can be a film containing a blend of two or more chromophores, wherein at least one chromophore has a milch-type donor group. Suitable matrix materials can include polymers such as: poly(methyl methacrylate) (PMMA); polyimide; polyamic acid; polystyrene; poly(urethane) (PU); and amorphous polycarbonate (APC). In some examples, the matrix material can comprise poly(methyl methacrylate) having, for example, a molecular weight of about 120,000 and a glass transition temperature Tg of about 85-165°C, or APC having a Tg of about 150-220°C.

[0113] According to certain embodiments, the EO materials described herein can be used in electro-optic (EO) devices. In one example, the EO device is a Mach-Zehnder (MZ) modulator or other waveguide-type devices for telematics applications. Another example of an EO device is an all-optical device. These devices can be used for, for example, optical switches, parametric amplification, and other all-optical applications with third-order hyperpolarization.

Claims

1. Nonlinear optical student chromatographs of general formula (I): D-Π-A(I) Where D represents an organic electron-donating group; A represents an organic electron-accepting group; 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 D contains a micriticine-type donor group, wherein the micriticine-type donor group comprises a symmetrical micriticine-type donor, wherein the micriticine-type donor group represents the general formula (D). a Symmetrical miltiorrhiza-type donors: (D a ) R1 and R2 each independently represent portions selected from the following: H, unsubstituted C3-C 10 Alkyl, substituted C1-C 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 (CH2). n -O-(CH2) n , where n is 1-10.

2. 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 Alkynyl, 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.

3. The nonlinear optical student chromaticity according to claim 1, wherein Π represents the general formula (Π 1 ) of the Π-bridge: Where R 3 and R 6 Each independently represents a portion selected from the following: H, halogen, substituted or unsubstituted C1-C. 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 (CH2). n -O-(CH2) n , where n is 1-10.

4. The nonlinear optical student chromaticity according to claim 3, wherein R 6 Representative -CF3 section.

5. The nonlinear optical student chromaticity according to claim 1, wherein Π represents the general formula (Π 2 ) of the Π-bridge: Where R 7 The representative is selected from the following parts: H, halogen, substituted or unsubstituted C1-C. 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 (CH2). n -O-(CH2) n , where n is 1-10.

6. The nonlinear optical student chromaticity according to claim 1, wherein the nonlinear optical student chromaticity has the general formula (C'): (C’)。 7. The nonlinear photogenerated chromatograph according to claim 1, wherein the nonlinear photogenerated chromatograph has a photostability of more than or equal to about 70%.

8. The nonlinear photogenerated chromatograph according to claim 1, wherein the nonlinear photogenerated chromatograph has a photostability of more than or equal to about 75%.

9. The nonlinear photogenerated chromatograph according to claim 1, wherein the nonlinear photogenerated chromatograph has a photostability of more than or equal to about 80%.

10. The nonlinear photogenerated chromatograph of claim 1, wherein the nonlinear photogenerated chromatograph has a photostability of more than or equal to about 90%.

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