Twisted π-electron system chromophore compounds with very large molecular hyperpolarizabilities and related compositions and devices
Unconventional twisted π-electron system electro-optic (EO) chromophores/compounds, compositions and related device structures. Crystallographic analysis of several non-limiting chromophores reveals, for instance, large ring-ring dihedral twist angles and a highly charge-separated zwitterionic structure in the ground state, in both solution phase and solid-state.
1. A chromophore compound a formula
wherein X is selected from NR′, O and S; each of R′ and R 1 -R 4 is independently selected from linear alkyl, substituted linear alkyl, branched alkyl, substituted branched alkyl, cycloalkyl and substituted cycloalkyl moieties; and Y comprises a substituent comprising a moiety selected from anionic carbon and heteroatom moieties, and salts, conjugate acids and charge-transfer isomers thereof.
2. The compound of claim 1 wherein each of R 1 -R 4 is independently selected from a C n H 2n+1 moiety, where n is an integer selected from 1 and integers greater than 1, and said moieties comprising at least one electron-withdrawing substituent.
3. The compound of claim 2 wherein at least one of R 1 -R 4 comprises at least one fluoro substituent.
4. The compound of claim 2 wherein X is NR′, and R′ is Selected from linear alkyl and branched alkyl moieties.
5. The compound of claim 1 wherein Y is a substituent Selected from O − and (Ew 1 )(Ew 2 )C − moieties, where Ew 1 and Ew 2 are selected from electron withdrawing substituents.
6. The compound of claim 1 wherein Y comprises a substituent a formula
wherein z and w are independently selected from S, O, NR″ and CH═CH, and R″ is selected from linear alkyl, substituted linear alkyl, branched alkyl, substituted branched alkyl, cycloalkyl and substituted cycloalkyl moieties; m, n and 1 are independently selected from 0 and integers greater than 0, provided at least one of said m, n and 1 is at least 1; and Y′ is selected from anionic carbon and heteroatom moieties.
7. The compound of claim 6 wherein Y − is selected from O − and (Ew 1 )(Ew 2 )C moieties, where Ew 1 and Ew 2 are selected from electron withdrawing substituents.
8. The compound of claim 7 wherein X is NR′, and R′ is selected from linear alkyl and branched alkyl moieties; and Y − is (NC) 2 C − .
9. The compound of claim 1 in a composition comprising a polymeric film.
10. The compound of claim 9 incorporated into an electro-optic device.
11. A chromophore compound of a formula
wherein z and w are independently selected from S, O, NR″ and CH═CH, and where R 1 —R 4 , R′ and R″ are independently selected from linear alkyl, substituted linear alkyl, branched alkyl, substituted branched alkyl, cycloalkyl and substituted cycloalkyl moieties; m, n and 1 are independently selected from 0 and integers greater than 0, provided at least one of said m, n and 1 is at least one; and Y′ is selected from anionic carbon and heteroatom moieties, and salts, conjugate acids and charge-transfer isomers thereof.
12. The compound of claim 11 wherein each of R 1 -R 4 is independently selected from a C n H 2n+1 moiety, where n is an integer selected from 1 and integers greater than 1; and each of R′ and R″ are independently selected from linear alkyl and branched alkyl moieties.
13. The compound of claim 11 wherein Y′ is selected from O − and (Ew 1 )(Ew 2 )C − moieties, where Ew 1 and Ew 2 are selected from electron withdrawing substituents.
14. The compound of claim 13 wherein m is 0, each of n and 1 is 1, and w is CH═CH.
15. The compound of claim 14 wherein Y′ is selected from O − , and said phenoxide moiety is di-tert-butyl substituted, and (NC) 2 C − .
16. The compound of claim 11 wherein one said aryl component of said biaryl moiety is configured at an angle up to about 90° out of the plane of said other aryl component.
17. The compound of claim 16 wherein said angle varies with said selection of R 1 -R 4 .
18. The compound of claim 16 comprising a monomer of a centrosymmetric antiparallel dimer.
19. A device comprising a substrate and an electro-optic chromophore composition thereon, said chromophore composition comprising a compound of a formula
wherein X is selected from NR′, O and S; each of R′ and R 1 -R 4 is independently selected from linear alkyl, substituted linear alkyl, branched alkyl, substituted branched alkyl, cycloalkyl and substituted cycloalkyl moieties; and Y comprises a substituent comprising a moiety selected from anionic carbon and heteroatom moieties, and salts, conjugate acids and charge-transfer isomers thereof.
20. The device of claim 19 wherein Y comprises a substituent of a formula
wherein z and w are independently selected from S, O, NR″ and CH═CH, and, R″ is selected from linear alkyl, substituted linear alkyl, branched alkyl, substituted branched alkyl, cycloalkyl and substituted cycloalkyl moieties; m, n and l are independently selected from 0 and integers greater than 0, provided at least one of said m, n and l is at least one, and Y′ is selected from anionic carbon and heteroatom moieties.
21. The device of claim 20 wherein Y − is selected from O − and (Ew 1 )(Ew 2 )C − moieties; and X is NR′, and R′ is selected from linear alkyl and branched alkyl moieties.
22. The device of claim 21 wherein said composition comprises a polymeric film.
23. The device of claim 22 wherein said polymeric component comprises poly(vinylphenol).
24. The device of claim 19 wherein said substrate comprises a transparent conducting oxide.