Bis-anthracenyl chiroptical compositions
AssigneeCalifornia Molecular Electronics Corporation
InventorsRobert R. Schumaker, James J. Marek, Jr., James Parakka
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Abstract
Optoelectronic materials are provided that are bistable organic tautomeric compositions that intraconvert dithio or diseleno carbamate esters and cyclic 1,3-dithia- or -diselena-2-iminium salts of π-conjugated bis-anthracenyl compounds. Specifically disclosed are compounds having the formula: where X is sulfur or selenium; where the R and R1 groups are alkyl or alkyl that together form a ring of carbon atoms; where An is the anion of a strong acid; and where the Z element is a chiral ring-completing system of atoms that changes chirality on tautomerization. These molecules are in themselves molecular-sized optoelectronic switching devices.
Claims33
Asymmetric narcissistic molecules comprising polyene-linked bis-anthracenyl compounds that are optically active, have two terminal positions, and bear a dichalcogenide carbamate ester on one terminal position and a dichalcogenide iminium salt on the other terminal position, capable of undergoing valence tautomerization between degenerate cationic forms that are enantiomeric to each other, wherein the asymmetric narcissistic molecules comprise conjugated bis-anthracenyl derivatives having the structure:
- wherein:
- An is the anion of a strong acid;
- X is independently selected from the group consisting of sulfur, selenium, and oxygen;
- the R and R1 groups are independently selected from the group consisting of alkyls and cycloalkyls and derivatives thereof;
- n is 1;
- D is hydrogen or an auxochrome substituted on the molecular chromophore;
- W1, W2, W3, and W4 are independently hydrogen or electron-withdrawing substituents;
- and
- Z is a six-membered chiral ring system of atoms that changes chirality on tautomerization.
A method of forming asymmetric narcissistic molecules that comprise polyene-linked bis-anthracenyl compounds that are optically active, have two terminal positions, and bear a dichalcogenide carbamate ester on one terminal position and a dichalcogenide iminium salt on the other terminal position, capable of undergoing valence tautomerization between degenerate cationic forms that are enantiomeric to each other, wherein the asymmetric narcissistic molecules comprise conjugated bis-anthracenyl derivatives having the structure:
- wherein:
- An is the anion of a strong acid;
- X is independently selected from the group consisting of sulfur, selenium, and oxygen;
- the R and R1 groups are selected from the group consisting of alkyls and cycloalkyls and derivatives thereof;
- n is 1;
- D is hydrogen or an auxochrome substituted on the molecular chromophore;
- W1, W2, W3, and W4 are independently hydrogen or electron-withdrawing substituents;
- and
- Z is a six-membered chiral ring system of atoms that changes chirality on tautomerization,
- the method comprising:
- providing an aldehyde;
- providing an organo-lithium compound;
- reacting together the aldehyde and the organo-lithium compounds to form a keto-alcohol via an organo-metallic aldehyde condensation reaction;
- reacting the keto-alcohol with trifluoroacetic acid and then a strong acid anion to form the anion salt of a cyclic iminium ketone;
- providing a methylenetriphenylphosphorane;
- and
- by reacting the cyclic iminium ketone with the methylenetriphenylphosphorane to form the asymmetric narcissistic composition.
A molecular optoelectronic switching device comprising asymmetric narcissistic molecules comprising optically active, polyene-linked bis-anthracenyl molecules coupled with electric field directed tautomerism and a mechanism for detecting specific optical states by their chiroptical effect on polarized light, wherein the asymmetric narcissistic molecules have two terminal positions and bear a dichalcogenide carbamate ester on one terminal position and a dichalcogenide iminium salt on the other terminal position, capable of undergoing valence tautomerization between degenerate cationic forms that are enantiomeric to each other, wherein the asymmetric narcissistic molecules comprise conjugated bis-anthracenyl derivative molecules having the structure:
- wherein:
- An is the anion of a strong acid;
- X is independently selected from the group consisting of sulfur, selenium, and oxygen;
- the R and R1 groups are selected from the group consisting of alkyls and cycloalkyls and derivatives thereof;
- n is 1;
- D is hydrogen or an auxochrome substituted on the molecular chromophore;
- W1, W2, W3, and W4 are independently hydrogen or electron-withdrawing substituents;
- and
- Z is a six-membered chiral ring system of atoms that changes chirality on tautomerization,
- the molecule having a molecular dipole moment and an optical axis.
Dependencies are inferred from the claim text.