EP-4735533-A1 - NONLINEAR OPTICAL CHROMOPHORES WITH INDOLIZINE DONOR GROUPS

Abstract

The present invention is directed to nonlinear optical chromophores having an organic indolizine electron-donating group having the following general formula (I): D represents an indolizine electron-donating group. n represents a 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 above has one of the following formulas: Various embodiments of the present invention include nonlinear optical chromophores with indolizine donor group having an indolizine donor connected to a n-bridge group. In various preferred embodiments of the present invention, the indolizine donor groups may be substituted or unsubstituted, including hydro and alkyl substituents, aryl substituents and combination thereof. In certain embodiments of the present invention, the substituent moieties in the indolizine donor groups may be important for isolation. The isolation may reduce chromophore-chromophore interaction. The isolation may reduce charge transfer between molecules. The isolation may increase maximum applied voltage, which may contribute to more optimal poling and higher r 33 .

Inventors

• RAMANN, Ginelle A.
• JOHNSON, BARRY L.
• PECINOVSKY, CORY

Assignees

• Lightwave Logic, Inc.

Dates

Publication Date

20260506

Application Date

20240627

Claims (1)

1. Atty Docket No.: LWLG-24PCT CLAIMS What is claimed is: 1. A nonlinear optical chromophore of the general formula (I): D-Π-A (I) wherein D represents an organic indolizine electron-donating group having the following formula (D a ): 1 wherein R in the group represents a moiety selected from the group consisting of H, substituted or unsubstituted C 2 -C 10 alkyl, substituted or unsubstituted C 2 -C 10 alkenyl, and substituted or unsubstituted C 2 -C 10 alkynyl, wherein R 2 in the indolizine electron-donating group represents a moiety selected from the group consisting of substituted monocyclic aryl, substituted or unsubstituted polycyclic aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bound to and separating A and D. 2. The nonlinear optical chromophore according to claim 1, wherein the carbon chain length between A and D is 6 to 8 carbon atoms. Atty Docket No.: LWLG-24PCT 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 chromophore according to claim 1, wherein the carbon chain length between A and D is 10 carbon atoms. 5. The nonlinear optical chromophore according to claim 2, wherein the λ max value is in a range of 670 nm and 875 nm. 6. The nonlinear optical chromophore according to claim 2, wherein the Δλ max value is equal to or smaller than 130 nm. 7. The nonlinear optical chromophore according to claim 2, wherein Π represents a Π-bridge between A and D having the following formula (Π a ): wherein R 3 represents a moiety selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 represents a moiety selected from the group consisting of H, halogen molecule, substituted or unsubstituted C 2 -C 10 alkyl, substituted or unsubstituted C 2 -C 10 alkenyl, and substituted or unsubstituted C 2 -C 10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or Atty Docket No.: LWLG-24PCT unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; and wherein a is an integer of 1 or 2. 8. The nonlinear optical chromophore according to claim 1, wherein A represents an electron-accepting group of the general formula (A a ): wherein R 4 a moiety selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 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. 9. The nonlinear optical chromophore according to claim 1, wherein the nonlinear chromophore has the general formula (C’): 10. A nonlinear optical chromophore of the general formula (I): D-Π-A (I) Atty Docket No.: LWLG-24PCT wherein D represents an organic indolizine electron-donating group having the following formula: wherein R 1 , R 2 , R 3 and represents a moiety selected from the group consisting of or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 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 wherein R5 represents a moiety selected from the group consisting of H or substituted or unsubstituted aryl; wherein A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bound to and separating A and D. 11. The nonlinear optical chromophore according to claim 10, wherein R 5 represents a phenyl moiety. 12. The nonlinear optical chromophore according to claim 10, wherein Π represents a Π-bridge between A and D having the following formula (Π a ): Atty Docket No.: LWLG-24PCT 3 wherein R a the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 represents a moiety selected from the group consisting of H, halogen molecule, substituted or unsubstituted C2-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, and substituted or unsubstituted C 2 -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 chromophore according to claim 10, wherein A represents an electron-accepting group of the general formula (A a ): wherein R 4 and R 5 each independently represents a moiety selected from the group consisting of H, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 2 - C 10 alkenyl, substituted or unsubstituted C 2 -C 10 alkynyl, substituted or unsubstituted aryl, Atty Docket No.: LWLG-24PCT substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH 2 ) n -O- (CH 2 ) n where n is 1-10. 14. A nonlinear optical chromophore of the general formula (I): D-Π-A (I) wherein D represents an organic indolizine electron-donating group having one of the following formulas: wherein the group consisting of H or substituted or unsubstituted aryl; wherein A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and Π represents a Π-bridge between A and D, wherein the Π-bridge comprises a carbon chain covalently bound to and separating A and D. 15. The nonlinear optical chromophore according to claim 14, wherein R 5 represents a phenyl moiety. 16. The nonlinear optical chromophore according to claim 14, wherein Π represents a Π-bridge between A and D having the following formula (Π a ): Atty Docket No.: LWLG-24PCT 3 wherein R a the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and substituted or unsubstituted cyclohexyl; wherein R 6 represents a moiety selected from the group consisting of H, halogen molecule, substituted or unsubstituted C2-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, and substituted or unsubstituted C 2 -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 chromophore according to claim 14, wherein A represents an electron-accepting group of the general formula (A a ): wherein R 4 and R 5 each independently represents a moiety selected from the group consisting of H, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted C 2 - C 10 alkenyl, substituted or unsubstituted C 2 -C 10 alkynyl, substituted or unsubstituted aryl, Atty Docket No.: LWLG-24PCT substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, and (CH 2 ) n -O- (CH 2 ) n where n is 1-10.

Description

Atty Docket No.: LWLG-24PCT TITLE Nonlinear Optical Chromophores with Indolizine Donor Groups CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of United States Provisional Application No.63/524,047 filed on June 29, 2023, the entire contents of which is incorporated herein by reference. BACKGROUND [0002] Nonlinear optical (NLO) chromophores provide the electro-optic (EO) activity in poled, electro-optic polymer devices. Electro-optic polymers have been investigated for many years as an alternative to inorganic materials such as lithium niobate in electro-optic devices. Electro-optic devices may include, for example, external modulators for telecom, datacom, RF photonics, and optical interconnects and so forth. Polymeric electro-optic materials have demonstrated enormous potential for core application in a broad range of next-generation systems and devices, including electro- optic modulators, optical switches, phased array radar, satellite and fiber telecommunications, cable television (CATV), optical gyroscopes for application in aerial and missile guidance, electronic counter measure (ECM) systems, backplane interconnects for high-speed computation, ultraquick analog-to-digital conversion, land mine detection, radio frequency photonics, spatial light modulation and all-optical (light- switching-light) signal processing. [0003] Many NLO molecules (chromophores) have been synthesized that exhibit high molecular electro-optic properties. The product of the molecular dipole moment (μ) and hyperpolarizability (β) is often used as a measure of molecular electro-optic performance due to the dipole’s involvement in material processing. See Dalton et al., Atty Docket No.: LWLG-24PCT “New Class of High Hyperpolarizability Organic Chromophores and Process for Synthesizing the Same”, WO 00/09613. [0004] Nevertheless, extreme difficulties have been encountered translating microscopic molecular hyperpolarizabilities (β) into macroscopic material hyperpolarizabilities (χ2). Molecular subcomponents (chromophores) must be integrated into NLO materials that exhibit (i) a high degree of macroscopic nonlinearity and (ii) sufficient temporal, thermal, chemical and photochemical stability. High electro-optic activity and the stability of electro-optic activity, which is also referred to as “temporal stability,” are important for commercially viable devices. Electro-optic activity may be increased in electro-optic polymers by increasing the concentration of nonlinear optical chromophores in a host polymer and by increasing of the electro-optic property of chromophores. However, some techniques for increasing chromophore concentration may decrease poling efficiency and temporal stability. Simultaneous solution of these dual issues is regarded as the final impediment in the broad commercialization of EO polymers in numerous devices and systems. [0005] The production of high material hyperpolarizabilities (χ2) is limited by the poor social character of NLO chromophores. Commercially viable materials must incorporate chromophores at large molecular densities with the requisite molecular moment statistically oriented along a single material axis. In order to achieve such an organization, the charge transfer (dipole) character of NLO chromophores is commonly exploited through the application of an external electric field during material processing that creates a localized lower-energy condition favoring noncentrosymmetric order. Unfortunately, even at moderate chromophore densities, molecules form multi-molecular dipolarly-bound (centrosymmetric) aggregates that cannot be dismantled via realistic field energies. To overcome this difficulty, integration of anti-social dipolar chromophores into a cooperative material architecture is commonly achieved through the Atty Docket No.: LWLG-24PCT construction of physical barriers (e.g., anti-packing steric groups) that limit proximal intermolecular relations. [0006] Thus, it has often been considered advantageous in the art to produce 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 their macroscopic electro-optic properties to a greater degree than materials with lower glass transition temperatures. It can also be advantageous to produce nonlinear optical chromophores which exhibit desirable macroscopic optical properties, thermal stability and have lower wavelength maximum absorption, i.e., λmax. BRIEF SUMMARY [0007] The present invention is directed, in general, to nonlinear optical chromophores having an indolizine donor group. Various embodiments of the present invention include nonlinear optical chromophores with indolizine donor group having an indolizine donor connected to a Π-bridge group. In various embodiments of the present invention, the indolizine donor groups may be substituted or unsu