COMPOUND, PHOTOELECTRIC CONVERTER AND PHOTOELECTROCHEMICAL CELL

• US 20100101643A1
• Filed: 03/27/2008
• Published: 04/29/2010
• Est. Priority Date: 03/29/2007
• Status: Abandoned Application

• Current Assignee: Sumitomo Chemical Company Limited
• Original Assignee: Sumitomo Chemical Company Limited
• Inventors: Tanaka, Akio, Shintaku, Tetsuya, Kawata, Tetsuo, Takahashi, Toshiya, Miyake, Kunihito, Higo, Mutsuko
• Application Number:
  US12/593,539
• Publication Number:
  US 20100101643A1
• Time in Patent Office: Days
• US Class Current: 136/256
• CPC Class Codes: C07D 213/22 containing two or more pyridine rings directly linked together, e.g. bipyridyl
• CPC Class Codes: C07D 213/79 Acids; Esters
• CPC Class Codes: C07D 401/14 containing three or more hetero rings
• CPC Class Codes: C07D 409/06 linked by a carbon chain containing only aliphatic carbon atoms
• CPC Class Codes: C07D 409/14 containing three or more hetero rings
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• CPC Class Codes: C09B 57/10 Metal complexes of organic compounds not being dyes in uncomplexed form
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H10K 85/331 Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
• CPC Class Codes: H10K 85/344 comprising ruthenium
• CPC Class Codes: H10K 85/348 comprising osmium

Abstract

A complex compound (I) obtained by coordinating a compound represented by the following formula (II), hereinafter abbreviated as compound (II), to a metal atom. In the formula, R¹, R² and R³ each independently represent a substituent represented by the following formula (III), formula (IV), formula (V) or formula (VI) and at least one of them is a substituent represented by the formula (III); a, b and c each independently represent an integer of 0 to 2 and a+b+c≧1; here, L represents a linking group represented by the following formula (VII) or formula (VIII); Ar represents an aryl group which may have a substituent; A represents an acidic group or a salt thereof; Y represents a halogen atom or a substituent; Q¹ and Q² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a cyano group; and p and q each represent an integer of 1 to 3.

Claims

1. A complex compound (I), wherein a compound represented by the following formula (II), abbreviated as compound (II), is coordinated to a metal atom:

2. The complex compound (I) according to claim 1, wherein L in the formula (III) comprises a substituent represented by the formula (VII), wherein, R¹, R², R³, a, b, c, A, L, Ar, Y, p, Q¹ and Q² represent the same meanings as in claim 1.

3. The complex compound (I) according to claim 1, wherein L in the fowl:

lila (III) comprises a substituent represented by the formula (VIII), wherein, R¹, R², R³, a, b, c, A, L, Ar, Y and q represent the same meanings as in claim 1.

4. The complex compound (I) according to claim 1, wherein the acidic group is at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a squaric acid group, a phosphoric acid group and a boric acid group.

5. The complex compound (I) according to claim 4, wherein the acidic group is a carboxylic group.

6. The complex compound (I) according to claim 1, wherein the salt of the acidic group is a salt with an organic base.

7. The complex compound (I) according to claim 1, wherein at least one of R¹, R² and R³ is a substituent represented by the formula (III) according to claim 1;

the linking group L is represented by the formula (VII);

Q¹ and Q² are hydrogen atoms;

p is 1;

Ar is a thiophene ring which may have a substituent; and

A is a carboxyl group.

8. The complex compound (I) according to claim 1, wherein a+b+c is an integer of 1 to 3.

9. The complex compound (I) according to claim 1, wherein the metal atom is Fe, Ru or Os.

10. A compound represented by the formula (II):

11. The compound (II) represented by the formula (II) according to claim 10, wherein L in the formula (III) is a compound comprising a substituent represented by the formula (VII).

12. The compound (II) represented by the formula (II) according to claim 10, wherein L in the formula (III) is a compound comprising a substituent represented by the formula (VIII).

13. The compound (II) according to claim 10, wherein the acidic group is at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a squaric acid group, a phosphoric acid group and a boric acid group.

14. The compound (II) according to claim 13, wherein the acidic group is a carboxyl group.

15. The compound (II) according to claim 10, wherein the salt of the acidic group is a salt with an organic base.

16. The compound (II) according to claim 10, wherein at least one of R¹, R² and R³ is a substituent represented by the formula (III) according to claim 1;

the linking group L is represented by the formula (VII);

Q¹ and Q² are hydrogen atoms and p is 1;

Ar is a thiophene ring which may have a substituent; and

A is a carboxyl group.

17. The compound (II) according to claim 10, wherein a+b+c is an integer of 1 to 3.

18. A photosensitizing dye comprising a complex compound (I) according to claim 1.

19. A photoelectric converter comprising a conductive substrate and a layer of semiconductor fine particles on which a photosensitizing dye according to claim 18 is adsorbed.

20. A photoelectrochemical cell comprising a photoelectric converter according to claim 19, a charge transport layer and a counter electrode.

21. A method for manufacturing a tin compound represented by the following formula (A) or (B), wherein a halogenated compound (IX) or (X) described in the following formula is reacted with a tin reagent represented by the following formula (XI) in the presence of a metal catalyst:

22. A method for manufacturing the compound represented by the (II)

23. A method for manufacturing the compound (II),

24. A complex compound (I′

), wherein a compound represented by the following formula (II′

), abbreviated as compound (II′

), is coordinated to a metal atom;

25. The complex compound (I′

) according to claim 24, wherein the acidic group is a group selected from the group consisting of a carboxyl group, a sulfonic acid group, a squaric acid group, a phosphoric acid group and a boric acid group.

26. The complex compound (I′

) according to claim 25, wherein the acidic group is a carboxyl group.

27. The complex compound (I′

) according to claim 24, wherein the salt of the acidic group is a salt with an organic base.

28. The complex compound (I′

) according to claim 24, wherein the number of the acidic groups or the salts thereof are two or more.

29. The complex compound (I′

) according to claim 24, wherein, in the formula (III′

), b′

=1 and R⁵′

is an alkoxy group.

30. The complex compound (I) according to claim 24, wherein, in the formula (III′

), b′

=1 and R⁵′

is a carboxyl group or a salt thereof.

31. The complex compound (I) according to claim 24, wherein, in the formula (III′

), L′

represents the formula (IV′

);

Q¹′ and

Q²′

represent hydrogen atoms;

p′

=1 and b′

=1; and

Ar represents a benzene ring or a benzene ring having a substituent.

32. The complex compound (I′

) according to claim 24, wherein, in the formula (III), L′

represents the formula (IV′

);

Q¹′ and

Q²′

represent hydrogen atoms;

p′

=1 and b′

=1; and

Ar represents a thiophene ring or a thiophene ring having a substituent.

33. A compound represented by the formula (II′

);

34. The compound (II′

) according to claim 33, wherein the acidic group is a group selected from the group consisting of a carboxyl group, a sulfonic acid group, a squaric acid group, a phosphoric acid group and a boric acid group.

35. The compound (II′

) according to claim 34, wherein the acidic group is a carboxyl group.

36. The compound (II′

) according to claim 33, wherein the salt of the acidic group is a salt with an organic base.

37. The compound (II′

) according to claim 33, wherein the number of the acidic groups or the salts thereof are two or more.

38. The compound (II′

) according to claim 33, wherein, in the formula (III′

), b′

=1 and R⁵′

is an alkoxy group.

39. The compound (II′

) according to claim 33, wherein, in the formula (III′

), b′

=1 and R⁵′

is a carboxyl group or a salt thereof.

40. The compound (II′

) according to claim 33, wherein, in the formula (III′

), L′

represents the formula (IV);

Q¹′ and

Q²′

are hydrogen atoms;

p′

=1 and b′

1; and

Ar is a benzene ring or a benzene ring having a substituent.

41. The complex compound (II′

) according to claim 33, wherein, in the formula (III′

), L′

represents the formula (IV′

);

Q1′ and

Q2′

are hydrogen atoms;

p′

=1 and b′

=1; and

Ar is a thiophene ring or a thiophene ring having a substituent.

42. A method for manufacturing the compound (II′

) according to claim 33, comprising the following processes (A) to (C) or processes (A) and (B);

[Process A];

a process wherein a compound represented by the formula (1% hereinafter abbreviated as compound (1);

43. The method for manufacturing the compound (II'"'"') according to claim 42, wherein X is a bromine atom, R⁶′

is a methyl group or an n-butyl group and the protected acidic group is a methyl ester or an ethyl ester.

44. The method for manufacturing the compound (II′

) according to claim 42, wherein the metal catalyst is Pd(PPh₃)₄ or Pd(PPh₃)₂Cl₂.

45. The method for manufacturing the compound (II′

) according to claim 42, wherein a base is used in removing the protecting group which has been introduced, the base is lithium hydroxide or triethylamine, and the solvent is methanol or ethanol.

46. The complex compound (I′

) according to claim 24, wherein the metal atom is Fe, Ru or Os.

47. A photosensitizing dye, comprising the complex compound (I′

) according to claim 24.

48. A photoelectric converter comprising a conductive substrate and a layer of semiconductor fine particles on which the photosensitizing dye according to claim 47 is adsorbed.

49. A photoelectrochemical cell comprising the photoelectric converter according claim 48, a charge transport layer and a counter electrode.