Photochromic and electrochromic compounds and methods of synthesizing and using same
This invention relates to novel photochromic and electrochromic monomers and polymers based on 1,2-dithienylcyclopentene derivatives and method of using and synthesizing same. The compounds are reversibly interconvertible between different isomeric forms under suitable photochromic or electrochromic conditions. The electrochromic conversion may be catalytic. The application also relates to ultra-high density homopolymers prepared using ring-opening methathesis polymerization (ROMP) where the central ring of the 1,2-bis(3-thienyl)-cyclopentene is incorporated directly into the polymer backbone. The monomer units may be readily functionalized to enable the synthesis of polymers with diverse structural and electronic properties. The compounds have many potential applications including high-density optical information storage systems, photoregulated molecular switches, reversible holographic systems, ophthalmic lenses, actinometry and molecular sensors, photochromic inks, paints and fibers and optoelectronic systems such as optical waveguides, Bragg reflectors and dielectric mirrors.
1. A compound reversibly convertible between a ring-open isomer (I) and a ring-closed isomer (II):
wherein:
each R 1 is independently selected from the group consisting of H and a halogen;
each R 2 is independently H, a halogen, or both
R 2 when taken together form CH═CH, or R 2 is CH═CH and forms part of a polymer backbone;
each R 3 is independently selected from the group consisting of H, a halogen, CO 2 Y (Y═H, Na, alkyl, aryl),
and
(X═N,O,S);
R 4 is aryl; and
each R 5 is independently selected from the group consisting of H, alkyl and aryl, and wherein compound is convertible from said ring-open isomer (I) to said ring-closed isomer (II) under photochemical conditions and from said ring-closed isomer (II) to said ring-open isomer (I) under electrochemical conditions.
2. The compound as defined in claim 1 , wherein said compound is also convertible from said ring-closed isomer (II) to ring-open isomer (I) under photochemical conditions and from said ring-open isomer (I) to said ring-closed isomer (II) under electrochemical conditions.
3. The compound as defined in claim 1 , wherein said compound is also convertible from said ring-closed isomer (II) to said ring-open isomer (I) under photochemical conditions.
4. The compound as defined in claim 1 , wherein said compound is also convertible from said ring-open isomer (I) to said ring-closed isomer (II) under electrochemical conditions.
5. The compound as defined in claim 1 , wherein the electrochemical conversion between said isomers (II) and (I) is catalytic.
6. The compound as defined in claim 1 , wherein R 1 is F.
7. The compound as defined in claim 1 , wherein R 1 and R 2 are F, R 3 and R 4 are
(X═S) and R 5 iS H.
8. The compound as defined in claim 1 , wherein R 1 and R 2 are F, each R 3 is independently selected from the group consisting of aryl and
and R 5 is H.
9. The compound as defined in claim 1 , wherein R 1 and R 2 are F, R 3 is H, R 4 is
(X═S) and R 5 is H.
10. The compound as defined in claim 1 , wherein R 1 and R 2 are F, R 3 and R 4 are
and R 5 is H.
11. The compound as defined in claim 1 , wherein R 1 is H, R 2 is HC═CH and forms part of the polymer backbone, R 3 is Cl and R 5 is H.
12. The compound as defined in claim 1 , wherein R 1 is H, R 2 is HC═CH and forms part of the polymer backbone, R 3 is CO 2 CH 3 and R 5 is H.
13. The compound as defined in claim 1 , wherein R 1 is H, R 2 is HC═CH and forms part of the polymer backbone, R 3 is CO 2 H and R 5 is H.
14. A polymer comprising the compound of claim 1 , wherein R 2 is CH═CH and forms part of the polymer backbone.
15. The polymer as defined in claim 14 , wherein said polymer is a homopolymer.
16. The polymer as defined in claim 15 , prepared by ring-opening methathesis polymerization.
17. A method of preparing a compound according to claim 1 , comprising carrying out the reaction steps set forth in any one of:
18. A method of using a compound according to claim 1 in an electrochromic and/or photochromic device.
19. The method according to claim 18 , wherein said electrochromic and/or photochromic device is:
(1) opthalmic lenses-eyeglasses that change color depending on the ambient light;
(2) an actinometric device;
(3) a molecular sensor;
(4) photochromic ink;
(5) photochromic paint;
(6) photochromic fibers;
(7) a variable transmission filter;
(8) a high-density optical information storage system;
(9) photo-regulated molecular switches that can be incorporated into molecular scale machinery;
(10) an optoelectronic system;
(11) a reversible holographic system; or
(12) molecular switches in molecule-based wires and circuitry.
20. A polymer comprising a compound interconvertible between a ring-open isomer (III) and a ring-closed isomer (IV):
wherein each R 3 is independently selected from the group consisting of H, a halogen, CO 2 Y (Y═H, Na, alkyl, aryl),
and
(X═N,O,S) and n is between 10 and 100.
21. The polymer as defined in claim 20 , wherein each R 3 is independently selected from the group consisting of Cl, CO 2 CH 3 and CO 2 H.
22. The compound as defined in claim 1 , wherein:
each R 2 is independently H or a halogen, and
each R 3 is independently selected from the group consisting of H, a halogen, CO 2 Y (Y═aryl),
and
(X═N,O,S).
23. The compound as defined in claim 1 , wherein:
each R 2 is independently H or F;
each R 3 is independently selected from the group consisting of H, a halogen
and
(X═N,O,S), and
R 5 is H.
24. The compound as defined in claim 1 , wherein:
R 1 and R 2 are F;
each R 3 is independently selected from the group consisting of H and
(X═N,O,S), and
R 5 is H.
25. A method of preparing a polymer having electrochromic and photochromic properties, comprising utilizing a compound as defined in claim 1 , wherein each R 2 is independently H or F, or both R 2 when taken together form CH═CH.
26. The polymer as defined in claim 14 , wherein:
R 1 is F;
each R 3 is independently selected from the group consisting of H, a halogen,
and
(X═N,O,S); and
R 5 is H.
27. The polymer as defined in claim 14 , wherein R 1 is F.
28. The polymer as defined in claim 14 , wherein R 1 is F, R 3 and R 4 are
(X═S) and R 5 is H.
29. The polymer as defined in claim 14 , wherein R 1 is F, R 3 is aryl and R 5 is H.
30. The polymer as defined in claim 14 , wherein R 1 is F, R 3 is H, R 4 is
(X═S) and R 5 is H.
31. The polymer as defined in claim 14 , wherein R 1 is F, R 3 and R 4 are
and R 5 is H.
32. A polymer comprising a main chain and the compound of claim 1 , wherein each R 2 is independently selected from the group consisting of H and F; and each R 3 is independently selected from the group consisting of H, a halogen, CO 2 Y (Y═H, Na, alkyl, aryl),
and
(X═N,O,S), wherein at least one R 3 is CO 2 Y (Y=aryl) and links the compound to the main chain of the polymer.
33. A method of preparing a film, sheet, fiber or bead having electrochromic and photochromic properties, comprising utilizing a polymer as defined in claim 14 .
34. A method of preparing a film, sheet, fiber or bead having electrochromic and photochromic properties, comprising utilizing a polymer as defined in claim 32 .
35. A method of using a polymer according to claim 14 in an electrochromic and/or photochromic device.
36. A method of using a polymer according to claim 32 in an electrochromic and/or photochromic device.