Photochromic and electrochromic compounds and synthesis and use thereof

• US 8,536,205 B2
• Filed: 05/25/2006
• Issued: 09/17/2013
• Est. Priority Date: 05/25/2005
• Status: Expired due to Fees

• Current Assignee: Solutia Canada, Inc. (Eastman Chemical Company)
• Original Assignee: Switch Materials, Inc.
• Inventors: Branda, Neil R., Wuestenberg, Bettina, Lemieux, Vincent, Adams, Michael, Gauthier, Simon
• Primary Examiner(s): Solola, Taofiq A
• Application Number:
  US11/915,530
• Publication Number:
  US 20100190868A1
• Time in Patent Office: 2,672 Days
• Field of Search: 514/422, 514/343, 548/517, 546/276.4
• US Class Current: 514/343
• CPC Class Codes: C07D 333/18 by sulfur atoms
• CPC Class Codes: C07D 333/22 Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
• CPC Class Codes: C07D 333/24 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 333/28 Halogen atoms
• CPC Class Codes: C07D 333/78 condensed with rings other than six-membered or with ring systems containing such rings
• CPC Class Codes: C07D 409/08 linked by a carbon chain containing alicyclic rings
• CPC Class Codes: C07D 409/14 containing three or more hetero rings
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1092 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: Y10T 436/14 Heterocyclic carbon compound [i.e. , O, S, N, Se, Te, as only ring hetero atom]
• CPC Class Codes: Y10T 436/142222 Hetero-O [e.g., ascorbic acid, etc.]

Abstract

Photochromic and electrochromic hexadiene compounds that are reversibly convertible between ring-open and ring-closed isomeric forms. The conversion between the different isomeric forms may be induced by light or electricity. The compounds may include a charge transfer moiety including electron donor and acceptor groups. The electron donor and acceptor are linearly conjugated in the ring-open form to enable electron transfer but are electrically insulated in the ring-closed form. Photoresponsive compounds may be synthesized by any of several methods disclosed, e.g., by reacting diene precursors with dienophiles in a condensation reaction. The compounds may be utilized in reactivity-gated photochromic or electrochromic applications. Compounds may be used in a method to selectively release a releasable agent, such as a small molecule.

Claims

1. A precursor for preparation of a photoactive hexatriene compound, wherein the precursor is represented by formula II:

2. The precursor of claim 1, wherein the precursor is photochemically inert.

3. The precursor of claim 1, wherein the R₇ and R₈ are each CH₂.

4. The precursor of claim 1 wherein the R₇ and R₈ taken together form a 6-membered ring according to

5. The precursor of claim 1, wherein the R₇ and R₈ when taken together form a cyclopentadiene, or an optionally substituted cyclopentadiene.

6. The precursor of claim 5, wherein the optionally substituted cyclopentadiene is a fulvene.

7. The precursor of claim 6 wherein the fulvene is

8. The precursor of claim 1, wherein R₇ and R₈ together form a 5-membered ring substituted by H or a halogen.

9. The precursor of claim 8, wherein the halogen is fluorine.

10. The precursor of claim 1, wherein R₄ and R₆ are constituents of an optionally substituted heterocycle.

11. The precursor of claim 10, wherein the optionally substituted heterocycle is an optionally substituted thiophene.

12. The precursor of claim 11 wherein the optionally substituted thiophene is

13. The precursor of claim 3, wherein:

R₁ is methyl;

R₂ is methyl;

R₃ is H; and

R₅ is methyl.

14. The precursor of claim 3, wherein:

R₁ is aryl;

R₂ is methyl;

R₃ is H; and

R₅ is methyl.

15. The precursor of claim 3, wherein:

R₁ is halogen;

R₂ is methyl;

R₃ is H; and

R₅ is methyl.

16. The precursor of claim 1 wherein the halogen is F.

17. The precursor of claim 1 wherein when R₄ is an electron donating group, R₅ and R₆ are electron accepting groups.

18. The precursor of claim 1 wherein when R₄ is an electron accepting group, R₅ and R₆ are electron donating groups.

19. The precursor of claim 1 wherein X is S.

20. The precursor of claim 1 wherein R₄ is selected from the group consisting of n-C₃H₇, C₅H₄, 4-C₆H₄OCH₃, 3,4,5-C₆H₂ (OCH₃)₃, 4-C₆H₄—

NO₂ and 4-pyridyl.

21. The precursor of claim 1, wherein the precursor is:

22. The precursor of claim 1, wherein the precursor is:

23. The precursor of claim 1, wherein the precursor is:

24. The precursor of claim 1, wherein the precursor is:

25. A method of selectively releasing a releasable agent, comprising:

a) providing a precursor compound represented by formula II;

26. The method of claim 25, wherein the releasable agent is a small molecule.

27. The method of claim 25, wherein the step of selectively converting the switching moiety comprises exposing the carrier compound to a predetermined wavelength of light.

28. The method of claim 25, wherein the carrier compound is delivered to a target location prior to the step of selectively converting the switching moiety.

29. The method of claim 28, wherein the target location is located in vivo.

30. The method of claim 25, wherein the precursor is photochemically inert.

31. The method of claim 26, wherein the small molecule is selected from the group consisting of therapeutic agents, biochemical effectors, polymer precursors and chemical reagents.

32. The method of claim 25, further comprising:

a) providing multiple releasable agents;

b) coupling each of the multiple releasable agents to the carrier compound; and

c) selectively releasing the multiple releasable agents by sequentially exposing the carrier compound to different wavelength of light, each of the wavelengths corresponding to at least one of the releasable agents.

33. A method of synthesizing a photoactive hexatriene compound, the method comprising:

a) providing a photochemically inert precursor compound represented by formula II;

34. The method of claim 33, wherein the step of chemically reacting the precursor and the reactant is reversible.

35. The method of claim 33, wherein the chemically reacting is a condensation reaction.

36. The method of claim 33, wherein the chemically reacting is a cycloaddition.