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 H or a halogen;
each R 2 is independently H or a halogen, or both R 2 when taken together form CH═CH;
each R 3 is
or a first R 3 is CO 2 Y (where Y is aryl or alkyl) and a second R 3 is aryl;
each R 4 is aryl; and
each R 5 is independently H, aryl or alkyl,
and wherein the 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 or photochemical conditions.
2. The compound according to claim 1 , wherein said compound is convertible from said ring-closed isomer (II) to said ring-open isomer (I) under photochemical conditions.
3. The compound according to claim 1 , wherein the conversion from said ring-closed isomer (II) to said ring-open isomer (I) under electrochemical conditions is catalytic.
4. The compound according to claim 1 , wherein R 5 is H.
5. The compound according to claim 1 , wherein R 1 and R 2 are halogen.
6. The compound according to claim 5 , wherein R 1 and R 2 are F.
7. The compound according to claim 1 , wherein R 1 is H and both R 2 when taken together form CH═CH.
8. The compound according to claim 1 , wherein said first R 3 is CO 2 Y (where Y is aryl or alkyl) and can be polymerized by ring-opening metathesis polymerization, and said second R 3 is aryl.
9. The compound according to claim 8 , wherein the first R 3 is
10. The compound according to claim 1 , wherein each R4 is independently selected from the group consisting of:
(where X is N, O or S) and
11. The compound according to claim 1 , wherein R 3 is
12. A polymer comprising a compound reversibly convertible between a ring-open isomer (I) and a ring-closed isomer (II):
wherein;
each R 1 is independently H or a halogen;
each R 2 is independently H or a halogen;
a first R 3 is
or CO 2 Y (,here Y is aryl or alkyl) and links the compound to the main chain of the polymer and a second R 3 is aryl;
each R 4 is aryl; and
each R 5 is independently H, aryl or alkyl,
and wherein the 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 or photochemical conditions.
13. The polymer according to claim 12 , wherein said polymer is a homopolymer.
14. The polymer according to claim 12 , wherein said polymer is prepared by ring-opening metathesis polymerization.
15. The polymer according to claim 12 , wherein said compound is convertible from said ring-closed isomer (II) to said ring-open isomer (I) under photochemical conditions.
16. The polymer according to claim 12 , wherein the conversion from said ring-closed isomer (II) to said ring-open isomer (I) under electrochemical conditions is catalytic.
17. The polymer according to claim 12 , wherein R 5 is H.
18. The polymer according to claim 12 , wherein R 1 and R 2 are halogen.
19. The polymer according to claim 18 , Wherein R 1 and R 2 are F.
20. The polymer according to claim 12 , wherein R 1 and R 2 are H.
21. The polymer according to claim 12 , wherein the first R 3 is
22. The polymer according to claim 12 , wherein R 4 is selected from the group consisting of:
(where X is N, O or S) and
23. The polymer according to claim 12 , wherein R 3 is
24. A polymer comprising a compound reversibly convertible between a ring-open isomer (I) and a ring-closed isomer (II):
wherein:
each R 1 is independently H or a halogen;
each R 2 is CH═CH and forms part of the polymer backbone;
each R 3 is
each R 4 is independently aryl or alkyl; and
each R 5 is independently H, aryl or alkyl,
and wherein the 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 or photochemical conditions.
25. The polymer according to claim 24 , wherein said polymer is a homopolymer.
26. The polymer according to claim 24 , wherein said polymer is prepared by ring-opening metathesis polymerization.
27. The polymer according to claim 24 , wherein said compound is convertible from said ring-closed isomer (II) to said ring-open isomer (I) under photochemical conditions.
28. The polymer according to claim 24 , wherein the conversion from said ring-closed isomer (II) to said ring-open isomer (I) under electrochemical conditions is catalytic.
29. The polymer according to claim 24 , wherein R 5 is H.
30. The polymer according to claim 24 , wherein R 1 is halogen.
31. The polymer according to claim 24 , Wherein R 1 is H.
32. The polymer according to claim 24 , wherein R 4 is alkyl.
33. The polymer according to claim 32 , wherein R 4 is CH 3 .
34. The polymer according to claim 24 , wherein R 4 is aryl.
35. The polymer according to claim 34 , wherein R 4 is selected from the group consisting of:
(where X is N, O or S) and
36. The compound according to claim 1 , wherein said second R 3 is
37. The compound according to claim 1 , wherein said R 4 is
38. The polymer according to claim 12 , wherein said second R 3 is
39. The polymer according to claim 12 , wherein said R 4 is
40. The polymer according to claim 34 , wherein said R 4 is