Photoelectric conversion device and photoelectric conversion device dye, and compound

1. A photoelectric conversion device dye, the dye being a compound of the structure represented by the following general formula (I):

wherein:

A is selected from the group consisting of the following formulas (IV) to (VII):

wherein:

S 1 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

R 17 to R 20 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

q is 0 or 1, and the substituent —Y 1 —COOH substitutes S 1 ;

wherein:

S 2 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

S 3 is a sulfur atom or a structure represented by the following formula (Va);

R 21 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 24 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

u is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 2 and/or S 3 :

wherein:

R 25 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 27 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

R 28 to R 31 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, where R 28 and R 30 may each be eliminated to form an unsaturated bond, or R 29 and R 31 may be linked to form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

t is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 3 ; and

wherein:

R 32 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; and

R 34 to R 41 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,

B comprises a cyanine skeleton having a maximum absorption wavelength λmax of 500 to 700 nm in a methanol solution;

Z 1 is any one divalent linking group selected from —CONR—, —NRCO—, —SO 2 NR—, and —NRSO 2 —;

R in Z 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

Y 1 and Y 2 are each independently an alkylene group having 1 to 8 carbon atoms, or a single bond;

r is 1 or 2;

m and n are each independently an integer of 0 to 2; and

(m+n) is 1 or more.

2. The photoelectric conversion device dye according to claim 1 , wherein the dye is a compound of the structure represented by the following general formula (II):

wherein:

X 1 and X 2 are each independently an oxygen atom, a sulfur atom, a selenium atom, CR 3 R 4 , or NR 5 ;

R 1 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, where R 1 to R 5 may each be independently substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group, and R 3 and R 4 may be linked to form an alicyclic group having a 3- to 6-membered ring;

R 6 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, or a cyano group;

R 9 to R 16 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

in R 9 to R 16 , R 9 and R 11 may be eliminated or R 13 and R 15 may be eliminated to each form an unsaturated bond, or R 10 and R 12 may be linked or R 14 and R 16 may be linked to each form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

p is 1 or 2;

Z 1 in the formula replaces R 1 to R 16 or a hydrogen atom contained in R 1 to R 16 ;

a substituent —Y 2 —COOH in the formula replaces R 1 to R 16 or a hydrogen atom contained in R 1 to R 16 ;

An b− is a b-valent anion;

a is 1 or 2, and is a coefficient for keeping a charge of the entire dye neutral;

b is 1 or 2; and

m, n, r, Z 1 , A, Y 1 , and Y 2 are the same as described in the general formula (I).

3. The photoelectric conversion device dye according to claim 2 , wherein the dye is a compound of the structure represented by the following general formula (III):

wherein:

D 1 and D 2 are each independently a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

two substituents —Y 2 —COOH in the formula each replace R 1 to R 8 or a hydrogen atom contained in R 1 to R 8 , or substitute the benzene ring, the naphthalene ring, or the phenanthrene ring represented by D 1 and D 2 ; and

the other variables are the same as described in formula (II).

4. A compound of the structure represented by the following formula (IX):

wherein:

A is selected from the group consisting of the following formulas (IV) to (VII):

wherein:

S 1 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

R 17 to R 20 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

q is 0 or 1, and the substituent —Y 1 —COOH substitutes S 1 ;

wherein:

S 2 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

S 3 is a sulfur atom or a structure represented by the following formula (Va);

R 21 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 24 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

u is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 2 and/or S 3 :

wherein:

R 25 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 27 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

R 28 to R 31 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, where R 28 and R 30 may each be eliminated to form an unsaturated bond, or R 29 and R 31 may be linked to form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

t is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 3 ; and

wherein:

R 32 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; and

R 34 to R 41 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms;

Z 1 is any one divalent linking group selected from —CONR—, —NRCO—, —SO 2 NR—, and —NRSO 2 —;

R in Z 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

D 1 is a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, each of which may be substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group;

R 42 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, or a cyano group;

X 1 is an oxygen atom, a sulfur atom, a selenium atom, CR 3 R 4 , or NR 5 ;

R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms;

R 3 to R 5 may each be independently substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group, and R 3 and R 4 may be linked to form an alicyclic group having a 3- to 6-membered ring;

Y 1 is an alkylene group having 1 to 8 carbon atoms, or a single bond;

m is 0 to 2;

An b− is a b-valent anion;

a is 1 or 2, and is a coefficient for keeping a charge of the entire dye neutral; and

b is 1 or 2.

5. The compound according to claim 4 , wherein the dye is a compound of the structure represented by the following formula (X):

wherein:

A is selected from the group consisting of the following formulas (IV) to (VII):

wherein:

S 1 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

R 17 to R 20 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

q is 0 or 1, and the substituent —Y 1 —COOH substitutes S 1 ;

wherein:

S 2 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

S 3 is a sulfur atom or a structure represented by the following formula (Va);

R 21 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 24 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

u is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 2 and/or S 3 :

wherein:

R 25 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 27 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

R 28 to R 31 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, where R 28 and R 30 may each be eliminated to form an unsaturated bond, or R 29 and R 31 may be linked to form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

t is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 3 ; and

wherein:

R 32 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; and

R 34 to R 41 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms;

Z 2 is any one divalent linking group selected from —CONR—, —NRCO, —SO 2 NR—, and —NRSO 2 —,

R in Z 2 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

D 1 is a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, each of which may be substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group,

X 1 is an oxygen atom, a sulfur atom, a selenium atom, CR 3 R 4 , or NR 5 ;

R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, where R 3 to R 5 may each be independently substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group, and R 3 and R 4 may be linked to form an alicyclic group having a 3- to 6-membered ring;

An b− is a b-valent anion;

a is 1 or 2, and is a coefficient for keeping the charge of the entire dye neutral; and

b is 1 or 2.

6. A photoelectric conversion device comprising a working electrode comprising a dye supported on a metal oxide layer, the dye being a compound of the structure represented by the following general formula (I):

wherein:

A is selected from the group consisting of the following formulas (IV) to (VII):

wherein:

S 1 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

R 17 to R 20 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

q is 0 or 1, and the substituent —Y 1 —COOH substitutes S 1 ;

wherein:

S 2 is an aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent;

S 3 is a sulfur atom or a structure represented by the following formula (Va);

R 21 to R 23 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 24 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

u is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 2 and/or S 3 :

wherein:

R 25 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a cyano group;

R 27 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an anchor group;

R 28 to R 31 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, where R 28 and R 39 may each be eliminated to form an unsaturated bond, or R 29 and R 31 may be linked to form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

t is 0 or 1; and

the substituent —Y 1 —COOH substitutes S 3 ; and

wherein:

R 32 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; and

R 34 to R 41 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms;

B comprises a cyanine skeleton having a maximum absorption wavelength λmax of 500 to 700 nm in a methanol solution;

Z 1 is a divalent linking group selected from —CONR—, —NRCO—, —SO 2 NR—, and —NRSO 2 —;

R in Z 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

Y 1 and Y 2 are each independently an alkylene group having 1 to 8 carbon atoms, or a single bond;

r is 1 or 2;

m and n are each independently an integer of 0 to 2; and

(m+n) is 1 or more.

7. The photoelectric conversion device according to claim 6 , wherein the dye is a compound of the structure represented by the following general formula (II):

wherein:

X 1 and X 2 are each independently an oxygen atom, a sulfur atom, a selenium atom, CR 3 R 4 , or NR 5 ;

R 1 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 8 carbon atoms, where R 1 to R 5 may each be independently substituted by a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, an ether group, a carbonyl group, an aromatic ring, a heterocyclic ring, or a metallocenyl group, and R 3 and R 4 may be linked to form an alicyclic group having a 3- to 6-membered ring;

R 6 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, or a cyano group;

R 9 to R 16 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

in R 9 to R 16 , R 9 and R 11 may be eliminated or R 13 and R 15 may be eliminated to each form an unsaturated bond, or R 10 and R 12 may be linked or R 14 and R 16 may be linked to each form a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

p is 1 or 2;

Z 1 in the formula replaces R 1 to R 16 or a hydrogen atom contained in R 1 to R 16 ;

the substituent —Y 2 —COOH in the formula replaces R 1 to R 16 or a hydrogen atom contained in R 1 to R 16 ;

An b− is a b-valent anion;

a is 1 or 2, and is a coefficient for keeping a charge of the entire dye neutral;

b is 1 or 2; and

m, n, r, Z 1 , A, Y 1 , and Y 2 are the same as described in formula (I).

8. The photoelectric conversion device according to claim 7 , wherein the dye is a compound of the structure represented by the following general formula (III):

wherein:

D 1 and D 2 are each independently a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a phenanthrene ring which may have a substituent;

two substituents —Y 2 —COOH in the formula each replace R 1 to R 8 or a hydrogen atom contained in R 1 to R 8 , or substitute the benzene ring, the naphthalene ring, or the phenanthrene ring represented by D 1 and D 2 ; and

the other variables are the same as described in formula (II).