EP-4740066-A1 - NON-LINEAR OPTICAL CHROMOPHORES WITH MICHLER'S BASE-TYPE DONORS

Abstract

The present invention is directed, in general, to nonlinear optical chromophores having a Michler's base-type group. Various embodiments of the present invention include nonlinear optical chromophores with Michler's base-type group having a Michler's base donor group connected to a Π-bridge group. Various embodiments of the present invention include nonlinear optical chromophores with Michler's base-type group having high photostability, which chromophores can reduce the percentage of being deactivated by molecular oxygen under illumination.

Inventors

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

Assignees

• Lightwave Logic, Inc.

Dates

Publication Date

20260513

Application Date

20240702

Claims (1)

1. Atty Docket No.: LWLG-25PCT CLAIMS What is claimed is: 1. A nonlinear optical chromophore of the general formula (I): D-Π-A (I) wherein 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 bound to and separating A and D; wherein D comprises one Michler’s base-type donor group, wherein the Michler’s base-type donor group comprises a symmetric Michler’s base-type donor, wherein the Michler’s base-type donor group represents the symmetric Michler’s base-type donor of the general formula (D a ): wherein R1 and R2 selected from the group consisting of H, unsubstituted C3-C10 alkyl, substituted 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. 2. The nonlinear optical chromophore according to claim 1, wherein A represents an electron-accepting group of the general formula (A a ): Atty Docket No.: LWLG-25PCT wherein R 4 and R 5 each 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. 3. The nonlinear optical chromophore according to claim 1, wherein Π represents bridge of the gener 1 al formula (Π ): wherein R 3 and R 6 each independently represents a moiety selected from the group consisting of H, halogen, 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. Atty Docket No.: LWLG-25PCT 4. The nonlinear optical chromophore according to claim 3, wherein R 6 represents a moiety of -CF 3 . 5. The nonlinear optical chromophore according to claim 1, wherein Π represents a Π-bridge of the general formula (Π 2 ): wherein R 7 represents a consisting of H, halogen, 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, 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. Atty Docket No.: LWLG-25PCT 6. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has the general formula (C’): 7. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a photostability greater than or equal to about 70%. 8. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a photostability greater than or equal to about 75%. Atty Docket No.: LWLG-25PCT 9. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a photostability greater than or equal to about 80%. 10. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a photostability greater than or equal to about 90%.

Description

Atty Docket No.: LWLG-25PCT TITLE Non-Linear Optical Chromophores with Michler’s Base-Type Donors CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of United States Provisional Application No.63/525,539 filed on July 7, 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, 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 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., “New Class of High Hyperpolarizability Organic Chromophores and Process for Synthesizing the Same”, WO 00/09613. Atty Docket No.: LWLG-25PCT [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. 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 (hyperpolarizability) 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, at even 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 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 Atty Docket No.: LWLG-25PCT thermal stability and maintain their macroscopic electro-optic properties to a greater degree than materials with lower glass transition temperatures. However, materials with such elevated glass transition temperatures require significantly increased temperatures during poling processes to achieve adequate alignment. The necessity of employing such elevated temperatures is costly, time-consuming and results in what is referred to as poling inefficiency. BRIEF SUMMARY [0007] The present invention is directed, in general, to nonlinear optical chromophores having a Michler’s base-type group. Various embodiments of the present invention include nonlinear optical chromophores with Michler’s base-type group having a Michler’s base donor group connected to a Π-bridge group. Embodiments of the present invention may include nonlinear optical chromophores with Michler’s base-type group having high photostability, which chromophores can reduce the percentage of being