CN100377421C - Dye-sensitized photoelectric conversion device - Google Patents

Dye-sensitized photoelectric conversion device Download PDF

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CN100377421C
CN100377421C CNB2004800069266A CN200480006926A CN100377421C CN 100377421 C CN100377421 C CN 100377421C CN B2004800069266 A CNB2004800069266 A CN B2004800069266A CN 200480006926 A CN200480006926 A CN 200480006926A CN 100377421 C CN100377421 C CN 100377421C
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CN1762068A (en
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池田征明
紫垣晃一郎
井上照久
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Nippon Kayaku Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

A photoelectric conversion device sensitized with an organic dye; and a solar cell including the same. In accordance with a demand to now for the development of a photoelectric conversion device including an organic-dye-sensitized semiconductor, which photoelectric conversion device realizes high conversion efficiency and high practicability and is produced with an inexpensive dye, there is provided a photoelectric conversion device of high conversion efficiency produced by sensitizing fine semiconductor particles with the use of a methine dye of specified skeleton.

Description

Dye-sensitized electrooptical device
Technical field
The present invention relates to electrooptical device and solar cell, in detail, relate to use by dye-sensitized oxide semiconductor particulate as the electrooptical device of feature and utilize the solar cell of this device with specific skeleton by organic pigment sensitizing.
Background technology
Utilize sunlight to replace fossil fuels such as oil, coal to get most of the attention as the solar cell of the energy.Nowadays, the high efficiency of silicon solar cell that uses crystallization or amorphous silicon or the compound semiconductor solar cell that uses gallium, arsenic etc. etc. is actively developed research.But these make the required energy and expensive, are difficult to widely used problem so have.In addition, known use is by the electrooptical device of dye-sensitized semiconductive particles or use the solar cell of this device, and has disclosed material, the manufacturing technology of making these.(with reference to No. 2664194 communique of Japan Patent, B.O ' Regan and M.Graetzel Nature, the 353rd volume, 737 pages (1991), M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Graetzel, J.Am.Chem.Soc., the 115th volume, 6382 pages (1993)).This electrooptical device forms for using the cheap oxide semiconductor manufacturings of comparison such as titanium oxide, can obtain electrooptical device cheaply with the solar cell of previous use silicon etc., and obtain various solar cells and get most of the attention.But then use as sensitizing coloring matter in order to obtain the high device of conversion efficiency, so the cost height of pigment itself and supplying also is a problem with the complex compound of ruthenium system.In addition, do not reach practicability, therefore also wished to improve conversion efficiency (with reference to the WO2002011213 communique) though before used the test of organic pigment as sensitizing coloring matter, present situation to be that conversion efficiency, stability, durability are low etc.In addition, though can enumerate so far use methine be example that pigment is made electrooptical device though can to enumerate coumarin series pigment (opening the 2002-164089 communique with reference to the spy) and merocyanine (merocyanine) more be pigment (open with reference to the spy flat 8-81222 communique, spy are opened flat 11-214731 communique, the spy opens the 2001-52766 communique), expect more cost degradation, improve stability and conversion efficiency.
Total, in the semi-conductive electrooptical device that uses organic pigment sensitizing, wish to use cheap organic pigment, the exploitation of the electrooptical device that the practicality that conversion efficiency is high is high.
Summary of the invention
The inventor etc. go deep into effort in order to address the above problem, found that to use specific pigment with semiconductive particles sensitizing, make electrooptical device, can obtain the high electrooptical device of conversion efficiency thus, and finish the present invention.
That is, the present invention relates to:
(1) electrooptical device is characterized in that, using by the methine shown in the formula (1) is dye-sensitized oxide semiconductor particulate,
Figure C20048000692600151
(R in the formula (1) 1And R 2Represent hydrogen atom separately, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group.In addition, R 1And R 2Can be mutually or with phenyl ring a 1Can have substituent ring in conjunction with forming.m 1The integer of expression O to 7.n 1The integer of expression 1 to 7.X 1Expression can have substituent aromatic residue, cyano group, phosphate, sulfonic group, carboxyl, carbamoyl, alkoxy carbonyl group or acyl group.A 1And A 2Expression independently of one another can have substituent aromatic residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, can have substituent aliphatic hydrocarbon residue, carboxyl, carbamoyl, alkoxy carbonyl group or acyl group.Work as n 1Be more than 2 and A 1And A 2There is when a plurality of each A 1And each A 2Can be identical or different each other.In addition, can use and be selected from by A 1Or A 1There is each A when a plurality of 1And A 2Or A 2There is each A when a plurality of 2And X 1In a plurality of substituting groups form and can have substituent ring.Y 1Expression sulphur atom, selenium atom, tellurium be former to give, CR 3R 4Or NR 5Wherein, R 3And R 4The amino of expression hydrogen atom, halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue and maybe can have substituent aromatic residue.R 5Represent hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group.Work as m 1Be more than 2 and Y 1There is when a plurality of each Y 1Can be identical or different each other.Phenyl ring a 1Can have one or more substituting groups.This substituting group can enumerate as the amino of halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue.In addition by the phenyl ring a that mutually combines between a plurality of substituting groups 1Can form and to have substituent ring.Ring b 1Can have one or more substituting groups.This substituting group can enumerate as halogen atom, alkoxyl, acyl group, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue.In addition by mutually combining ring b between a plurality of substituting groups 1Can form and to have substituent ring.)
(2) above-mentioned (1) electrooptical device, wherein, the methine shown in the formula (1) is that pigment is, the R in the formula (1) 1And R 2For having the compound of substituent aromatic residue.
(3) above-mentioned (2) electrooptical device, wherein, the methine shown in the formula (1) is that pigment is the compound shown in the following formula (2),
Figure C20048000692600161
(in the formula (2), m 2, n 2, X 2, A 3, A 4, Y 2, a 2And b 2Separately the expression with formula (1) in corresponding m 1, n 1, X 1, A 1, A 2, Y 1, a 1And b 1The same connotation.Phenyl ring c 1Can further have one or more substituting groups.This substituting group can enumerate as the amino of halogen atom, amide groups, hydroxyl, alkoxyl, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue.In addition by the phenyl ring c that mutually combines between a plurality of substituting groups 1Can form and to have substituent ring.R 6And R 7Expression replaces or the amino of non-replacement, can have substituent aromatic residue separately.)
(4) above-mentioned (3) electrooptical device, wherein, the methine shown in the formula (2) is that pigment is the compound shown in the following formula (3),
(in the formula (3), m 3, n 3, X 3, A 5, A 6, Y 3, a 3And b 3Separately the expression with formula (1) in corresponding m 1, n 1, X 1, A 1, A 2, Y 1, a 1And b 1The same connotation.Phenyl ring c 2Can further have one or more substituting groups.This substituting group can enumerate as the amino of halogen atom, amide groups, hydroxyl, alkoxyl, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue.In addition by mutually combining phenyl ring c between a plurality of substituting groups 2Can form and to have substituent ring.R 11And R 12Expression replaces or the amino of non-replacement, can have substituent aromatic residue separately.)
(5) above-mentioned (4) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the R in the formula (3) 11And R 12For replacing or the compound of the amino of non-replacement.
(6) above-mentioned (4) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the R in the formula (3) 11And R 12For having the compound of substituent aromatic residue.
(7) above-mentioned (6) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the X in the formula (3) 3Compound for carboxyl.
(8) above-mentioned (7) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the X in the formula (3) 3Be carboxyl and and X 3Nearest A 6Be cyano group, carboxyl or acylated compound.
(9) above-mentioned (6) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the X in the formula (3) 3With with X 3Nearest A 6Formation can have the compound of substituent ring.
(10) electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (9) Xiang Zhongren, wherein, the methine shown in the formula (3) is that pigment is the m in the formula (3) 3It is 1 to 3 compound.
(11) above-mentioned (10) electrooptical device, wherein, the methine shown in the formula (3) is that pigment is the n in the formula (3) 3It is 1 to 4 compound.
(12) electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (11) Xiang Zhongren, wherein, the methine shown in the formula (3) is that pigment is the Y in the formula (3) 3Compound for sulphur atom.
(13) electrooptical device is characterized in that, using by the methine shown in the formula (1) is more than one and metal complex of pigment and/or the oxide semiconductor with organic pigment sensitizing of formula (1) structure in addition.
(14) electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (13) Xiang Zhongren, wherein, the oxide semiconductor particulate contains titanium dioxide as must composition.
(15) electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (14) Xiang Zhongren, wherein, the oxide semiconductor particulate contains as the zinc of metal ingredient or tin as must composition.
(16) electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (15) Xiang Zhongren, wherein, in the presence of inclusion compound, load pigment on the oxide semiconductor particulate.
(17) manufacture method of electrooptical device is characterized in that, the pigment shown in the load type (1) on the oxide semiconductor particulate that forms film like.
(18) solar cell is characterized in that, uses the electrooptical device of 1 of above-mentioned (1) Xiang Zhidi (16) Xiang Zhongren.
(19) oxide semiconductor particulate is a pigment institute sensitizing by the methine shown in the above-mentioned formula (1) to (3).
(20) methine is a pigment, the R in the wherein above-mentioned formula (1) 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, X 1Be carboxyl, A 1Be hydrogen atom, A 2Be cyano group.
(21) methine is a pigment, the R in the wherein above-mentioned formula (1) 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, by X 1With A 2Form the rhodanine ring.
(22) methine is a pigment, the R in the wherein above-mentioned formula (3) 11And R 12For replacing or the amino of non-replacement maybe can have substituent aromatic residue, m 3Be 0 to 3 integer, n 3Be 1 to 2 integer, X 3Be carboxyl, A 5Be hydrogen atom, A 6Be cyano group.
Embodiment
Below, describe the present invention in detail.Electrooptical device of the present invention uses by the dye-sensitized oxide semiconductor shown in the following formula (1).
Figure C20048000692600191
R in the formula (1) 1And R 2Represent hydrogen atom separately, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue and acyl group.
Aromatic residue is meant the base of removing 1 hydrogen atom from aromatic rings, and this aromatic rings can be enumerated as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, three benzo pentaphenes aromatic hydrocarbon rings such as (テ リ レ Application); Heterocyclic type aromatic rings such as indenes, Azulene (azulene), pyridine, pyrazine, pyrimidine, pyrazoles, pyrazolidine, thiazolidine,  azoles alkane, pyrans, chromene, pyrroles, pyrrolidines, benzimidazole, imidazoline, imidazolidine, imidazoles, pyrazoles, triazole, triazine, diazole, indoline, thiophene, furans,  azoles, thiazine, thiazole, indoles, benzothiazole, aphthothiazoles, benzoxazol, naphtho- azoles, indolenine, benzo indolenine, pyrazine, quinoline, quinazoline; Condensed type such as fluorenes, carbazole aromatic rings etc., these can have a substituting group as above-mentioned.Usually preferably contain carbon number and be the aromatic residue of 5 to 16 aromatic rings (aromatic rings and contain the condensed ring of aromatic rings).
Aliphatic hydrocarbon residue can be enumerated the alkyl as saturated and unsaturated straight chain, side chain and ring-type, and wherein preferred carbon number is 1 to 36, more preferably carbon number is 1 to 20.It is cycloalkyl of 3 to 8 etc. that cyclic alkyl can be enumerated as carbon number.Specifically can enumerate as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, octyl group, octadecyl, isopropyl, cyclohexyl, acrylic, pentenyl, cyclobutenyl, hexenyl, hexadienyl, isopropenyl, dissident's thiazolinyl, cyclohexenyl group, cyclopentadienyl group, acetenyl, propinyl, pentynyl, hexin base, dissident's alkynyl, hexamethylene alkynyl etc.These can have substituting group as above-mentioned.
It is 1 to 10 alkyl-carbonyl, aryl carbonyl etc. that acyl group can be enumerated as, carbon number, and wherein preferred carbon number is 1 to 4 alkyl-carbonyl, specifically can enumerate as, acetyl group, trifluoromethyl carbonyl, propiono etc.Aryl carbonyl can enumerate as, phenylcarbamoyl, naphthalene carbonyl etc.
Can have substituent aromatic residue and can have substituting group in the substituent aliphatic hydrocarbon residue; be not particularly limited; can enumerate as, hydrogen atom; sulfonic group; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; the amino of replacement or non-replacement; can substituted sulfydryl; can substituted amide groups; can have substituent alkoxyl; can have substituent aryloxy group; carboxyl; carbamoyl; acyl group; aldehyde radical; the carbonyl that alkoxy carbonyl group etc. replace; can have substituent aromatic residue; can have substituent aliphatic hydrocarbon residue etc.Halogen atom can be enumerated the atom as fluorine, chlorine, bromine, iodine etc.Phosphate-based enumerating as phosphoric acid (carbon number is 1 or 4) alkyl ester group etc.The amino of replacement or non-replacement can be enumerated the amino that replaces as alkyl such as amino, list or dimethylamino, list or diethylamino, list or dipropyl amino; The amino that aromatic series such as list or diphenyl amino, list or dinaphthyl amino replace; Amino or benzylamino or acetamido, the phenyl-acetamides base etc. of each 1 replacement of the alkyl of monoalkyl list phenyl amino etc. and aromatic hydrocarbon residue.The sulfydryl that can replace can be enumerated as sulfydryl, alkylthio group, thiophenyl etc.The amide groups that can replace can be enumerated as amide groups, alkylamidoalkyl, aryl amido group etc.Alkoxyl is meant that by above-mentioned aliphatic hydrocarbon residue and the base that the oxygen atom combination is become can enumerate as methoxyl group, ethyoxyl, butoxy, tert-butoxy etc., in addition, aryloxy group can be enumerated as phenoxy group, naphthoxy etc.These can have a substituting group as above-mentioned.This substituting group can be identical with the substituting group described in the item that can have substituent aromatic residue.Acyl group is also same as described above.It is alkoxy carbonyl group of 1 to 10 etc. that alkoxy carbonyl group can be enumerated as carbon number.Can have substituent aromatic residue and can have substituent aliphatic hydrocarbon residue can be same as described above respectively.
In addition, R 1And R 2Can be mutually or with phenyl ring a 1Can have substituent ring in conjunction with forming.R 1And R 2The formed ring that mutually combines can be enumerated as morpholine ring, piperidine ring, piperazine ring, pyrrolidine ring, carbazole ring, indole ring etc.In addition, R 1And R 2With phenyl ring a 1In conjunction with formed ring, can enumerate as julolidine (julolidine) ring etc.These can have a substituting group as above-mentioned.This substituting group, can with above-mentioned can have substituent aromatic residue and can have a substituting group described in the replacement ground term of substituent aliphatic hydrocarbon residue identical.
The R of formula (1) 1And R 2Preferably can have substituent aromatic residue.
This substituting group can have substituent aromatic residue and can have a substituting group described in the replacement ground term of substituent aliphatic hydrocarbon residue identical with above-mentioned, wherein preferably replaces or the amino of non-replacement, can have substituent aromatic residue.
m 1Expression 0 to 7 integer, wherein preferred 0 to 6 integer, more preferably 1 to 3 integer.n 1Expression 1 to 7 integer, wherein preferred 1 to 6 integer, more preferably 1 to 4 integer.As m 1With n 1Combination, preferred especially m 1Be 1 to 3 integer and n 1It is 1 to 4 integer.
The X of formula (1) 1Expression can have the base that substituent aromatic residue, cyano group, phosphate, sulfonic group or carboxyl, carbamoyl, alkoxy carbonyl group and acyl group etc. contain substituted carbonyl.Aromatic residue can be same as described above, as the substituting group that can have, and can be identical with the substituting group described in the item that can have substituent aromatic residue.Alkoxy carbonyl group and acyl group are also same as described above separately.Wherein preferred X 1For having substituent aromatic residue or carboxyl, the residue of the preferred salicylic acid of aromatic residue, catechol.In addition, X described later 1Can with A 1Or A 1Form ring.Formed ring preferably can have substituent heterocycle residue.Specifically can enumerate as pyridine, quinoline, pyrans, chromene, pyrimidine, the pyrroles, thiazole, benzothiazole, the  azoles, benzoxazol, selenazoles, the benzo selenazoles, imidazoles, benzimidazole, pyrazoles, thiophene, residues such as furans, each heterocycle residue all can be increased ring or hydrogenation, in addition, these can have a substituting group as above-mentioned, in addition, preferred these substituting group combinations form the rhodanine ring,  oxazolidone ring, sulfo- oxazolidone ring, the hydantoins ring, the thio-hydantoin ring, the indandione ring, the benzo-thiophene ring, pyrazolone ring, the barbital ring, sulfo-barbital ring, the structure of pyridone ring etc.
A in the formula (1) 1And A 2Expression independently of one another can have substituent aromatic residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, can have the base that substituent aliphatic hydrocarbon residue or carboxyl, carbamoyl, alkoxy carbonyl group and acyl group etc. contain carbonyl.Aromatic residue, halogen atom, aliphatic hydrocarbon residue, alkoxy carbonyl group and acyl group are same as described above separately.Work as n 1Be more than 2, A 1And A 2When a plurality of, each A 1And each A 2Can be identical or different independently of each other.Preferred A 1And A 2Be that hydrogen atom, cyano group, aliphatic hydrocarbon residue, halogen atom are or/and carboxyl etc. independently of one another.As combination, work as n 1Be 1 o'clock, preferred A 1, A 2Be all cyano group, A 1Be hydrogen atom A 2Be hydrogen atom, cyano group or carboxyl; Perhaps work as n 1Be 2 when above, preferred A 1, A 2All be cyano group, A 1It all is hydrogen atom and from X 1Nearest A 2Be cyano group or carboxyl, other A 2Be hydrogen atom.In addition, the A in the formula (1) 1, n particularly 1Be 2 when above from X 1A farthest 1Preferably can have substituent aromatic residue.This aromatic residue is same as described above, preferred benzene, naphthalene, anthracene, thiophene, pyrroles, furans etc.These aromatic residues can have a substituting group as above-mentioned.Substituting group is not particularly limited, can be identical with the substituting group described in the above-mentioned item that can have a substituent aromatic residue, preferably replace or the amino of non-replacement and can have substituent aromatic residue.
In addition, can use from A 1Or A 1Each A when a plurality of 1, A 2Or A 2Each A when a plurality of 2And X 1Middle a plurality of substituting groups of selecting, formation can have substituent ring.
A particularly 1Or A 1Each A when a plurality of 1And A 2Or A 2Each A when a plurality of 2Be preferably formed and can have substituent ring, formed ring can be enumerated as unsaturated hydrocarbons ring or heterocycle.The unsaturated hydrocarbons ring can be enumerated as phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, indenes ring, Azulene ring, fluorenes ring, cyclobutane ring, cyclohexene ring, cyclopentene ring, cyclohexadiene ring, cyclopentadiene ring etc., and heterocycle can be enumerated as pyridine ring, pyrazine ring, piperidine ring, indole ring, furan nucleus, pyranoid ring,  azoles ring, thiazole ring, indole ring, benzothiazole ring, benzoxazol ring, quinoline ring, carbazole ring, chromene ring etc.Wherein preferred phenyl ring, cyclobutane ring, cyclopentene ring, cyclohexene ring, pyranoid ring, furan nucleus etc.These can have a substituting group as above-mentioned.Substituting group can with above-mentioned can have substituent aromatic residue and can have in the substituent aliphatic hydrocarbon residue a described substituting group of the ground term of replacement identical.In addition, can form cyclic ketone or ring-type thioketones etc. when containing carbonyl, thiocarbonyl group etc., these rings also can have substituting group.Substituting group can with above-mentioned can have substituent aromatic residue and can have in the substituent aliphatic hydrocarbon residue a described substituting group of the ground term of replacement identical.
By above-mentioned X 1Or X 1With A 1And A 2During formed heterocycle nitrogen atom, this nitrogen-atoms can be by quaternized, and can contain equilibrium ion this moment.Equilibrium ion is not particularly limited, and specifically can enumerate as F, Cl, Br, I, ClO 4, EF 4, PF 6, OH, SO 4 2, CH 3SO 4, toluenesulfonic acid ion etc., wherein preferred Br, I, ClO 4, BF 4, PF 6, CH 3SO 4, toluenesulfonic acid ion etc.In addition, in can the molecule by non-equilibrium ion or acidic groups neutralization such as intermolecular carboxyl.
In addition, acidic groups such as above-mentioned hydroxyl, phosphate, sulfonic group and carboxyl can form salt separately, this salt can enumerate as with the salt of alkali metal such as lithium, sodium, potassium, magnesium, calcium or alkaline-earth metal etc.; Or organic base, for example can enumerate the such salt of quaternary ammonium salt such as tetramethyl-ammonium, TBuA, pyridine , imidazoles , piperazine , piperidines .Y in the formula (1) 1Expression sulphur atom, selenium atom, tellurium atom, CR 3R 4Or NR 5, preferred sulphur atom, selenium atom, more preferably sulphur atom.R 3And R 4Can enumerate amino, can have substituent aliphatic hydrocarbon residue and maybe can have substituent aromatic residue etc. as hydrogen atom, halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or non-replacement.The amino of halogen atom, amide groups, alkoxyl, acyl group, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic residue can be same as described above separately.In addition, R 5Can enumerate as hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group etc.Can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, acyl group can be same as described above separately.In addition, work as m 1Be more than 2, Y 1When a plurality of, each Y 1Can be identical or different each other.Phenyl ring a in the formula (1) 1Can have one or more substituting groups.Substituting group can enumerate as the amino of halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue.In addition, phenyl ring a 1When having a plurality of substituting group, can mutually combine between a plurality of substituting groups to form to have substituent ring.Formed ring can be enumerated as above-mentioned saturated and undersaturated cyclic alkyl, unsaturated hydrocarbons ring and heterocycle etc., and these can have a substituting group as above-mentioned.Substituting group can with above-mentioned can have substituent aromatic residue and can have in the substituent aliphatic hydrocarbon residue a described substituting group of the ground term of replacement identical.The amino of halogen atom, amide groups, alkoxyl, acyl group, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic residue separately can be same as described above.
The ring b of formula (1) 1Can have one or more substituting groups, substituting group can enumerate as halogen atom, alkoxyl, acyl group, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue etc.Halogen atom, alkoxyl, acyl group, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic residue separately can be same as described above.
Compound shown in the formula (1) can obtain isomers such as cis body, trans body, is not particularly limited, and all can be suitable as light sensitizing pigment.
Methine shown in the formula (1) is that pigment is with the compound shown in the following formula (2).
A in the formula (2) 3And A 4, m 2, n 2, X 2, Y 2, phenyl ring a 2, the ring b 2Expression and the middle corresponding A of formula (1) separately 1And A 2, m 1, n 1, X 1, Y 1, phenyl ring a 1, the ring b 1Identical connotation.R 6And R 7Expression replaces or the amino of non-replacement, can have substituent aromatic residue separately.Replace or the amino of non-replacement, can have substituent aromatic residue separately can be same as described above.
Phenyl ring c 1Can further have one or more substituting groups, substituting group can enumerate as the amino of halogen atom, amide groups, hydroxyl, alkoxyl, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue maybe can have substituent aromatic residue, in addition, phenyl ring c 1When having a plurality of substituting group, can mutually combine between a plurality of substituting groups to form to have substituent ring.Formed ring can be enumerated as above-mentioned saturated and undersaturated cyclic alkyl, unsaturated hydrocarbons ring and heterocycle etc., and these can have a substituting group as above-mentioned.Substituting group can with above-mentioned can have substituent aromatic residue and can have in the substituent aliphatic hydrocarbon residue a described substituting group of the ground term of replacement identical.The amino of halogen atom, amide groups, alkoxyl, replacement or non-replacement, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic residue separately can be same as described above.
In addition, the methine shown in the formula (2) is that pigment is preferably with the compound shown in the following formula (3).
A in the formula (3) 5And A 6, m 3, n 3, X 3, Y 3, phenyl ring a 3, the ring b 3, phenyl ring c 2, R 11, R 12Each self-corresponding A in expression and the above-mentioned formula (2) 3And A 4, m 2, n 2, X 2, Y 2, phenyl ring a 2, the ring b 2, phenyl ring c 1, R 6, R 7Identical connotation.
The invention still further relates to following defined methine based compound, using by these methines is that dye-sensitized oxide semiconductor particulate can obtain superior effect.
(a) R in the above-mentioned formula (1) 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, X 1Be carboxyl, A 1Be hydrogen atom, A 2For the methine of cyano group is a pigment.
(b) R in the above-mentioned formula (1) 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, by X 1With A 2The methine that forms the rhodanine ring is a pigment.
(c) R in the above-mentioned formula (3) 11And R 12For replacing or the amino of non-replacement maybe can have substituent aromatic residue, m 3Be 0 to 3 integer, n 3Be 1 to 2 integer, X 3Be carboxyl, A 5Be hydrogen atom, A 6For the methine of cyano group is a pigment.
Methine shown in the formula (1) is in the pigment, at m 1Be under the situation of 0 following pigment (7), for example can make according to following represented reaction equation.Aniline is obtained anil (4) by the coupling of Wu Erman (Ullmann) reaction etc., after re-using alkali such as butyl lithium and metallizing, method by amide derivatives such as effect dimethyl formamide etc. or act on the method etc. of Weir David Smail reagent (Vilsmeier ' s reagent) reaction of dimethyl formamide etc. with making phosphoryl chloride phosphorus oxychloride can obtain the precursor compound (5) of compound (7).Work as n 1Be 2 when above; by the method for formoxyl etc. being carried out Claisen condensation (Claisen Condensation), the method for using amide derivatives such as dimethylamino methacrylaldehyde, dimethylamino vinyl methacrylaldehyde, will identical formoxyl etc. by Wittig (Wittig) reaction pass sharp refined (Grignard) react etc. and to make vinyl etc., can obtain acryl, pentadiene aldehyde radical etc. through carrying out above-mentioned formyl reaction etc. again.In addition, by with compound (5) and the compound (6) that contains active methylene group in the presence of base catalysts such as required NaOH, sodium methoxide, sodium acetate, diethylamine, triethylamine, piperidines, piperazine, diazabicyclo hendecene, in non-protonic solvents such as alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols or dimethyl formamide, N-methyl pyrrolidone or toluene, acetic anhydride equal solvent, under about 20 ℃ to about 180 ℃, preferred about 50 ℃ to about 150 ℃, carry out condensation, can obtain pigment (7).In addition, when X1 is carboxyl, phosphate, with respectively contain alkoxy carbonyl group, phosphate-based activity methene compound and compound (5) reacts after can obtain pigment (7) by hydrolysis.
Figure C20048000692600261
Below for working as m 1It is the example of 0 o'clock compound.
With the particular instantiation of the pigment shown in the following formula (8) in table 1 and table 2.Phenyl abbreviates Ph as.In addition, with X 4And X 4With A 8Ring when forming ring (ring B) is described as follows.
Figure C20048000692600262
Table 1
Compound n 4 R 16 R 17 R 18 R 19 R 20 R 21 A 7 A 8 X 4
1 1 H H H H H H H H COOH
2 1 H H H H H H H CN COOH
3 1 CH 3 CH 3 CH 3 CH 3 H H H CN COOH
4 1 CH 3 CH 3 CH 3 CH 3 H H H COOH COOH
5 1 CH 3 CH 3 CH 3 CH 3 H H H CF 3 COOH
6 1 CH 3 CH 3 CH 3 CH 3 H H H COCF 3 COOH
7 1 CH 3 CH 3 CH 3 CH 3 H H H COCH 3 COOH
8 1 CH 3 CH 3 CH 3 CH 3 H H H CN COOH
9 1 CH 3 CH 3 CH 3 CH 3 H H H CN COOCH 3
10 1 CH 3 CH 3 CH 3 CH 3 H H H CN COOLi
11 1 CH 3 CH 3 CH 3 CH 3 H H H CN COONa
12 1 CH 3 CH 3 CH 3 CH 3 H H H CN COOK
13 1 CH 3 CH 3 CH 3 CH 3 H H H CN PO(OH) 2
14 1 C 2H 5 C 2H 5 C 2H 5 C 2H 5 H H H CN COOH
15 1 C 4H 9 C 4H 9 C 4H 9 C 4H 9 H H H CN COOH
16 1 C 8H 17 C 8H 17 C 8H 17 C 8H 17 H H H CN COOH
17 1 Ph Ph Ph Ph H H H CN COOH
18 1 Ph CH 3 Ph CH 3 H H H CN COOH
19 1 Ph H Ph H H H H CN COOH
20 1 CH 3 CH 3 CH 3 CH 3 OCH 3 H H CN COOH
21 1 CH 3 CH 3 CH 3 CH 3 OH H H CN COOH
22 1 CH 3 CH 3 CH 3 CH 3 H CH 3 H CN COOH
23 1 CH 3 CH 3 CH 3 CH 3 H H CH 3 CN COOH
24 2 CH 3 CH 3 CH 3 CH 3 H H H H COOH
25 3 CH 3 CH 3 CH 3 CH 3 H H H H COOH
26 4 CH 3 CH 3 CH 3 CH 3 H H H H COOH
27 5 CH 3 CH 3 CH 3 CH 3 H H H H COOH
28 6 CH 3 CH 3 CH 3 CH 3 H H H H COOH
29 7 CH 3 CH 3 CH 3 CH 3 H H H H COOH
Table 2
Compound n 4 R 16 R 17 R 18 R 19 R 20 R 21 A 7 A 8 X 4
30 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 1
31 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 2
32 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 3
33 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 4
34 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 5
35 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 6
36 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 7
37 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 8
38 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 9
39 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 10
40 1 CH 3 CH 3 CH 3 CH 3 H H H H Ring B 11
41 1 C 2H 5 C 2H 5 C 2H 5 C 2H 5 H H H H Ring B 12
42 1 C 4H 9 C 4H 9 C 4H 9 C 4H 9 H H H H Ring B 13
43 1 C 8H 17 C 8H 17 C 8H 17 C 8H 17 H H H By A 8With X 4Form ring B 14
44 1 Ph Ph Ph Ph H H H By A 8With X 4Form ring B 15
45 1 Ph CH 3 Ph CH 3 H H H By A 8With X 4Form ring B 16
46 1 Ph H Ph H H H H By A 8With X 4Form ring B 17
47 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 18
48 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 19
49 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 20
50 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 21
51 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 22
52 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 23
53 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 24
54 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 25
55 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 26
56 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 27
57 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 28
58 1 CH 3 CH 3 CH 3 CH 3 H H H By A 8With X 4Form ring B 29
Other example of pigment shown in the formula (8) is listed below.
Figure C20048000692600291
Figure C20048000692600301
Figure C20048000692600311
Figure C20048000692600321
Figure C20048000692600331
With the particular instantiation of the pigment shown in the following formula (9) in table 3 and table 4.Phenyl abbreviates Ph as.In addition, with X 5And X 5With A 10Ring when forming ring (ring B) is described as follows.
Figure C20048000692600351
Table 3
Compound n 5 R 22 R 23 R 24 R 25 R 26 R 27 A 9 A 10 X 5
107 1 H H H H H H H H COOH
108 1 H H H H H H H CN COOH
109 1 H CH 3 H CH 3 H H H CN COOH
110 1 H H H H H H H COOH COOH
111 1 H H H H H H H CF 3 COOH
112 1 H H H H H H H COCF 3 COOH
113 1 H H H H H H H COCH 3 COOH
114 1 H Ph H Ph H H H CN COOH
115 1 H H H H H H H CN COOCH 3
116 1 H H H H H H H CN COOLi
117 1 H H H H H H H CN COONa
118 1 H H H H H H H CN COOK
119 1 H H H H H H H CN PO(OH) 2
120 1 CH 3 H CH 3 H H H H CN COOH
121 1 C 4H 9 H C 4H 9 H H H H CN COOH
122 1 C 8H 17 H C 8H 17 H H H H CN COOH
123 1 Cl H Cl H H H H CN COOH
124 1 Br H Br H H H H CN COOH
125 1 I H I H H H H CN COOH
126 1 H H H H OCH 3 H H CN COOH
127 1 H H H H OH H H CN COOH
128 1 H H H H H CH 3 H CN COOH
129 1 H H H H H H CH 3 CN COOH
130 2 H H H H H H H H COOH
131 3 H H H H H H H H COOH
132 4 H H H H H H H H COOH
133 5 H H H H H H H H COOH
134 6 H H H H H H H H COOH
135 7 H H H H H H H H COOH
Table 4
Compound n 5 R 22 R 23 R 24 R 25 R 26 R 27 A 9 A 10 X 5
136 1 H H H H H H H H Ring B 1
137 1 H H H H H H H H Ring B 2
138 1 H H H H H H H H Ring B 3
139 1 H H H H H H H H Ring B 4
140 1 H H H H H H H H Ring B 5
141 1 H H H H H H H H Ring B 6
142 1 H H H H H H H H Ring B 7
143 1 H H H H H H H H Ring B 8
144 1 H H H H H H H H Ring B 9
145 1 H H H H H H H H Ring B 10
146 1 H H H H H H H H Ring B 11
147 1 H H H H H H H H Ring B 12
148 1 H H H H H H H H Ring B 13
149 1 H H H H H H H By A 10With X 5Form ring B 14
150 1 H H H H H H H By A 10With X 5Form ring B 15
151 1 H H H H H H H By A 10With X 5Form ring B 16
152 1 H H H H H H H By A 10With X 5Form ring B 17
153 1 H H H H H H H By A 10With X 5Form ring B 18
154 1 H H H H H H H By A 10With X 5Form ring B 18
155 1 H H H H H H H By A 10With X 5Form ring B 20
156 1 H H H H H H H By A 10With X 5Form ring B 21
157 1 H H H H H H H By A 10With X 5Form ring B 22
158 1 H H H H H H H By A 10With X 5Form ring B 23
159 1 H H H H H H H By A 10With X 5Form ring B 24
160 1 H H H H H H H By A 10With X 5Form ring B 25
161 1 H H H H H H H By A 10With X 5Form ring B 26
162 1 H H H H H H H By A 10With X 5Form ring B 27
163 1 H H H H H H H By A 10With X 5Form ring B 28
164 1 H H H H H H H By A 10With X 5Form ring B 29
Other example of pigment shown in the formula (9) is listed below.
Figure C20048000692600381
Figure C20048000692600391
Figure C20048000692600401
Methine shown in the formula (1) is in the pigment, m 1Be under the situation of the pigment (1) more than 1, can make via the reaction equation of the following stated.Methine shown in the formula (1) is that the compound of the synthetic intermediate formula (14) of pigment can be via the method (opening the 2000-252071 communique as the spy) in general little storehouse etc., (with compound (10) as boration compound (11), react with compound (12)) make (Z represents halogen atoms such as Cl, Br, I in the following reaction equation, compound (12)).In addition, with alkali such as butyl lithium with formula (13) compound metalization after, by acting on the method etc. of the Weir David Smail agent reaction of dimethyl formamide etc., can obtain the precursor compound (14) of compound (1) with the method for amide derivatives such as dimethyl formamide reaction or with making phosphoryl chloride phosphorus oxychloride.Work as n 1Be 2 when above; by the method for formoxyl etc. being carried out Claisen condensation, the method for using amide derivatives such as dimethylamino methacrylaldehyde, dimethylamino vinyl methacrylaldehyde, identical formoxyl etc. is made vinyl etc. via Wittig reaction or Grignard reaction etc.; via carrying out above-mentioned formyl reaction etc., can obtain acryl, pentadiene aldehyde radical etc. again.In addition, with compound (14) and the compound (6) that contains active methylene group in the presence of base catalysts such as required NaOH, sodium methoxide, sodium acetate, diethylamine, triethylamine, piperidines, piperazine, diazabicyclo hendecene, in non-protonic solvents such as alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols or dimethyl formamide, N-methyl pyrrolidone or toluene, acetic anhydride equal solvent, under about 20 ℃ to about 180 ℃, preferred about 50 ℃ to about 150 ℃, carry out condensation, can obtain pigment (1).In addition, X 1During for carboxyl, phosphate, by will respectively contain alkoxy carbonyl group, phosphate-based activity methene compound and compound (14) reacts after can obtain compound (1) by hydrolysis.
Figure C20048000692600411
Below enumerate the compound example.
With the particular instantiation of the pigment shown in the following formula (15) in table 5 to table 7.Phenyl abbreviates Ph as.In addition, with X 6And X 6With A 12Ring when forming ring (ring B) is described as follows.
Figure C20048000692600421
Table 5
Compound m 4 n 6 R 28 R 29 R 30 R 31 Y 4 A 11 A 12 X 6
193 1 1 H H H H S H H COOH
194 1 1 H H H H Se H OH COOH
195 1 1 H H H H NH H H COOH
196 1 1 H H H H NCH 3 H H COOH
197 1 1 CH 3 CH 3 H H S H CN COOH
198 1 1 CH 3 CH 3 H H Se H CONH 2 COOH
199 1 1 C 2H 5 C 2H 5 H H S H CN COOH
200 1 1 C 2H 5 C 2H 5 H H Te H CN COOH
201 1 1 C 3H 7 C 3H 7 H NO 2 S H CN COOH
202 1 1 C 4H 9 C 4H 9 H H S H CN COOH
203 1 1 C 8H 17 C 8H 17 H H S H CN COOH
204 1 1 C 18H 37 C 18H 37 H H S H CN COOH
205 1 1 Ph Ph H H S H CN COOH
206 1 1 Ph H H H S H CN COOH
207 1 1 Ph CH 3 H H S H CN COOH
208 1 1 Ph C 2H 5 H H S H CN COOH
209 1 1 Ph C 18H 37 H H S H CN COOH
210 1 1 CH 3 C 2H 5 H Cl S H CN COOE
211 1 1 COCH 3 C 2H 5 H H S H CN COOH
212 1 1 CH 3 CH 3 H H S CH 3 CN COOH
213 1 1 CH 3 CH 3 H CN S C 4H 9 CN COOH
214 1 1 CH 3 CH 3 H H S C 8H 17 CN COOH
215 1 1 CH 3 CH 3 H OCH 3 S H CN COOH
216 1 1 CH 3 CH 3 H OC 2H 5 S H CN COOH
217 1 1 Ph Ph H OC 8H 17 S H CN COOH
218 1 1 Ph Ph H OH S H CN COOH
219 1 1 Ph Ph CH 3 CH 3 S H CN COOH
220 1 1 Ph Ph NHCOCH 3 OCH 3 S H CN COOH
221 1 1 Ph Ph CH 3 Ph S H CN COOH
222 1 1 Ph Ph H H S H COOH COOH
223 1 1 Ph Ph H H S H CN COOLi
224 1 1 Ph Ph H COCH 3 S H CN COONa
225 1 1 Ph Ph H H S H CN COOK
Table 6
Compound m 4 n 6 R 28 R 29 R 30 R 31 Y 4 A 11 A 12 X 6
226 1 1 Ph Ph H C 8H 17 S H CN COOH
227 1 1 Ph Ph H H S H CN PO(OH) 2
228 1 1 Ph Ph H H S H CF 3 COOH
229 1 1 Ph Ph H H S H COCH 3 COOH
230 1 1 Ph Ph H H S H COCF 3 COOH
231 1 1 Ph Ph Ph Ph S H CN SO 3H
232 1 1 Ph Ph H H S H NO 2 COOH
233 1 1 Ph Ph H H S H CN COOCH 3
234 1 1 Ph Ph H H S H COOCH 3 COOCH 3
235 1 1 Ph Ph H H S H Cl COOH
236 1 1 Ph Ph H H S CH 3 CH 3 COOH
237 1 1 Ph Ph H H S Ph H CONH 2
238 1 2 Ph Ph H N(CH 3) 2 S H H COOH
239 1 2 Ph Ph H H S CH 3 H COOH
240 1 2 Ph Ph H H S H CH 3 COOH
241 1 3 Ph Ph H H S H H COOH
242 1 4 Ph Ph H H S H H COOH
243 1 5 Ph Ph H H S H H COOH
244 1 7 Ph Ph H H S H H COOH
245 2 1 CH 3 CH 3 H H S H CN COOH
246 2 1 Ph Ph H H S H CN COOH
247 2 1 Ph Ph H H S CH 3 CN COOH
248 3 1 Ph Ph H H S H CN COOH
249 4 1 Ph Ph H H S H CN COOH
250 5 1 Ph Ph H H S H CN COOH
251 7 1 Ph Ph H H S H CN COOH
252 2 2 Ph Ph H H S H H COOH
253 3 2 Ph Ph H H S H H COOH
254 4 2 Ph Ph H H S H H COOH
255 5 2 Ph Ph H H S H H COOH
Table 7
Compound m 4 n 6 R 28 R 29 R 30 R 31 Y 4 A 11 A 12 X 6
256 1 1 Ph Ph H H S H H Ring B 1
257 1 1 Ph Ph H H S H H Ring B 2
258 1 1 Ph Ph H H S H H Ring B 3
259 1 1 Ph Ph H H S H H Ring B 4
260 1 1 Ph Ph H H S H H Ring B 5
261 1 1 Ph Ph H H S H H Ring B 6
262 1 1 Ph Ph H H S H H Ring B 7
263 1 1 Ph Ph H H S H H Ring B 8
264 1 1 Ph Ph H H S H H Ring B 9
265 1 1 Ph Ph H H S H H Ring B 10
266 1 1 Ph Ph H H S H H Ring B 11
267 1 1 Ph Ph H H S H H Ring B 12
268 1 1 Ph Ph H H S H H Ring B 13
269 1 1 Ph Ph H H S H By A 12With X 6Form ring B 14
270 1 1 Ph Ph H H S H By A 12With X 6Form ring B 15
271 1 1 Ph Ph H H S H By A 12With X 6Form ring B 16
272 1 1 Ph Ph H H S H By A 12With X 6Form ring B 17
273 1 1 Ph Ph H H S H By A 12With X 6Form ring B 18
274 1 1 Ph Ph H H S H By A 12With X 6Form ring B 19
275 1 1 Ph Ph H H S H By A 12With X 6Form ring B 20
276 1 1 Ph Ph H H S H By A 12With X 6Form ring B 21
277 1 1 Ph Ph H H S H By A 12With X 6Form ring B 22
278 1 1 Ph Ph H H S H By A 12With X 6Form ring B 23
279 1 1 Ph Ph H H S H By A 12With X 6Form ring B 24
280 1 1 Ph Ph H H S H By A 12With X 6Form ring B 25
281 1 1 Ph Ph H H S H By A 12With X 6Form ring B 26
282 1 1 Ph Ph H H S H By A 12With X 6Form ring B 27
283 1 1 Ph Ph H H S H By A 12With X 6Form ring B 28
284 1 1 Ph Ph H H S H By A 12With X 6Form ring B 29
The particular instantiation of the pigment shown in the following formula (16) is in table 8 to table 9.Phenyl abbreviates Ph as.In addition, X 7And X 7With A 14Ring when forming ring (ring B) is described as follows.
Figure C20048000692600471
Table 8
Compound m 5 n 7 R 32 R 33 R 34 R 35 R 36 R 37 Y 5 A 13 A 14 X 7
285 1 1 H H H H H H S H H COOH
286 1 1 H H H H H H NH H H COOH
287 1 1 H H H H H H NCH 3 H H COOH
288 1 1 H H H H H H NPh H H COOH
289 1 1 H H H H H H S H CN COOH
290 1 1 H H CH 3 CH 3 CH 3 CH 3 S H CN COOH
291 1 1 H H CH 3 CH 3 CH 3 CH 3 NH H CN COOH
292 1 1 H H CH 3 CH 3 CH 3 CH 3 NCH 3 H CN COOH
293 1 1 H H CH 3 CH 3 CH 3 CH 3 NPh H CN COOH
294 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOH
295 1 1 H H C 3H 7 C 3H 7 C 3H 7 C 3H 7 S H CF 3 COOH
296 1 1 H H C 4H 9 C 4H 9 C 4H 9 C 4H 9 S H CN COOH
297 1 1 H H C 8H 17 C 8H 17 C 8H 17 C 8H 17 S H CN COOH
298 1 1 H H C 18H 37 C 18H 37 C 18H 37 C 18H 37 S H CN COOH
299 1 1 H H Ph Ph Ph Ph S H CN COOH
300 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S CH 3 CN COOH
301 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S F CN COOH
302 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S Cl CN COOH
303 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S Br CN COOH
304 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S I CN COOH
305 1 1 H OH C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOH
306 1 1 CH 3 H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOH
307 1 1 CH 3 OCH 3 C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOH
308 1 1 CH 3 C 8H 17 C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOH
309 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COOH COOH
310 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COONa COONa
311 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOLi
312 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COONa
313 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN COOK
314 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN PO(OH) 2
315 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COCH 3 COOH
316 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COCF 3 COOH
317 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COCH 2F COOH
318 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H COCHF 2 COOH
319 2 1 H H Ph Ph Ph Ph S H H COOH
320 3 1 H H Ph Ph Ph Ph S H H COOH
Table 9
Compound m 5 n 7 R 32 R 33 R 34 R 35 R 36 R 37 Y 5 A 13 A 14 X 7
321 4 1 H H Ph Ph Ph Ph S H H COOH
322 5 1 H H Ph Ph Ph Ph S H H COOH
323 6 1 H H Ph Ph Ph Ph S H H COOH
324 1 2 H H Ph Ph Ph Ph S H H COOH
325 1 3 H H Ph Ph Ph Ph S H H COOH
326 1 4 H H Ph Ph Ph Ph S H H COOH
327 1 5 H H Ph Ph Ph Ph S H H COOH
328 1 6 H H Ph Ph Ph Ph S H H COOH
329 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 1
330 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 2
331 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 3
332 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 4
333 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 5
334 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 6
335 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 7
336 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 8
337 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 9
338 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 10
339 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 11
340 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 12
341 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H CN Ring B 13
342 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14X 7Form ring B 14
343 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 15
344 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 16
345 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 17
346 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 18
347 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 19
348 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14 and X 7Form ring B 20
349 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 21
350 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 22
351 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 23
352 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 24
353 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 25
354 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 26
355 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 27
356 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 28
357 1 1 H H C 2H 5 C 2H 5 C 2H 5 C 2H 5 S H By A 14With X 7Form ring B 29
With the particular instantiation of the pigment shown in the following formula (17) in table 10 to table 11.Phenyl abbreviates Ph as.In addition, with X 3And X 3With A 8Ring when forming ring (ring B) is described as follows.
Figure C20048000692600491
Table 10
Compound m 6 n 8 R 38 R 39 R 40 R 41 R 42 R 43 Y 6 A 15 A 16 X 8
358 1 1 H H H H H H S H H COOH
359 1 1 H H H H H H NH H H COOH
360 1 1 H H H H H H NCH 3 H H COOH
361 1 1 H H H H H H NPh H H COOH
362 1 1 H H H H H H S H CN COOH
363 1 1 H H H H H H S H CN COOH
364 1 1 H H CH 3 CH 3 CH 3 CH 3 NH H CN COOH
365 1 1 H H CH 3 CH 3 CH 3 CH 3 NCH 3 H CN COOH
366 1 1 H H H CH 3 H CH 3 S H CN COOH
367 1 1 H H H C 2H 5 H 5 C 2H 5 S H CN COOH
368 1 1 H H H C 3H 7 H C 3H 7 S H CN COOH
369 1 1 H H H C 4H 9 H C 4H 9 S H CN COOH
370 1 1 H H H C 8H 17 H C 8H 17 S H CN COOH
371 1 1 H H H C 18H 37 H C 18H 37 S H CN COOH
372 1 1 H H H Ph H Ph S H CN COOH
373 1 1 H H H C 2H 5 H C 2H 5 S CH 3 CN COOH
374 1 1 H H H C 2H 5 H C 2H 5 S F CN COOH
375 1 1 H H H C 2H 5 H C 2H 5 S Cl CN COOH
376 1 1 H H H C 2H 5 H C 2H 5 S Br CN COOH
377 1 1 H H H C 2H 5 H C 2H 5 S I CN COOH
378 1 1 H OH H C 2H 5 H C 2H 5 S H CN COOH
379 1 1 CH 3 H H C 2H 5 H C 2H 5 S H CN COOH
380 1 1 CH 3 OCH 3 H C 2H 5 H C 2H 5 S H CN COOH
381 1 1 CH 3 C 8H 17 H C 2H 5 H C 2H 5 S H CN COOH
382 1 1 H H H C 2H 5 H C 2H 5 S H COOH COOH
383 1 1 H H H C 2H 5 H C 2H 5 S H COONa COONa
384 1 1 H H H C 2H 5 H C 2H 5 S H CN COOLi
385 1 1 H H H C 2H 5 H C 2H 5 S H CN COONa
386 1 1 H H H C 2H 5 H C 2H 5 S H CN COOK
387 1 1 H H H C 2H 5 H C 2H 5 S H CN PO(OH) 2
388 1 1 H H H C 2H 5 H C 2H 5 S H COCH 3 COOH
389 1 1 H H H C 2H 5 H C 2H 5 S H COCF 3 COOH
390 1 1 H H H C 2H 5 H C 2H 5 S H COCH 2F COOH
391 1 1 H H H C 2H 5 H C 2H 5 S H COCHF 2 COOH
392 2 1 H H H Ph H Ph S H H COOH
393 3 1 H H H Ph H Ph S H H COOH
394 4 1 H H H Ph H Ph S H H COOH
Table 11
Compound M 6 n 8 R 38 R 39 R 40 R 41 R 42 R 43 Y 6 A 15 A 16 X 8
395 5 1 H H H Ph H Ph S H H COOH
396 6 1 H H H Ph H Ph S H H COOH
397 1 2 H H H Ph H Ph S H H COOH
398 1 3 H H H Ph H Ph S H H COOH
399 1 4 H H H Ph H Ph S H H COOH
400 1 5 H H H Ph H Ph S H H COOH
401 1 6 H H H Ph H Ph S H H COOH
402 1 1 H H H H H H S H CN Ring B 1
403 1 1 H H H H H H S H CN Ring B 2
404 1 1 H H H H H H S H CN Ring B 3
405 1 1 H H H H H H S H CN Ring B 4
406 1 1 H H H H H H S H CN Ring B 5
407 1 1 H H H H H H S H CN Ring B 6
408 1 1 H H H H H H S H CN Ring B 7
409 1 1 H H H H H H S H CN Ring B 8
410 1 1 H H H H H H S H CN Ring B 9
411 1 1 H H H H H H S H CN Ring B 10
412 1 1 H H H H H H S H CN Ring B 11
413 1 1 H H H H H H S H CN Ring B 12
414 1 1 H H H H H H S H CN Ring B 13
415 1 1 H H H H H H S H By A 16With X 8Form ring B 14
416 1 1 H H H H H H S H By A 16With X 8Form ring B 15
417 1 1 H H H H H H S H By A 16With X 8Form ring B 16
418 1 1 H H H H H H S H By A 16With X 8Form ring B 17
419 1 1 H H H H H H S H By A 16With X 8Form ring B 18
420 1 1 H H H H H H S H By A 16With X 8Form ring B 19
421 1 1 H H H H H H S H By A 16With X 8Form ring B 20
422 1 1 H H H H H H S H By A 16With X 8Form ring B 21
423 1 1 H H H H H H S H By A 16With X 8Form ring B 22
424 1 1 H H H H H H S H By A 16With X 8Form ring B 23
425 1 1 H H H H H H S H By A 16With X 8Form ring B 24
426 1 1 H H H H H H S H By A 16With X 8Form ring B 25
427 1 1 H H H H H H S H By A 16With X 8Form ring B 26
428 1 1 H H H H H H S H By A 16With X 8Form ring B 27
429 1 1 H H H H H H S H By A 16With X 8Form ring B 28
430 1 1 H H H H H H S H By A 16With X 8Form ring B 29
Formula (15) other example to the pigment shown in the formula (17) is recited in down.
Figure C20048000692600521
Figure C20048000692600531
Figure C20048000692600541
Figure C20048000692600551
Figure C20048000692600561
Figure C20048000692600581
Figure C20048000692600601
The structure of ring B is as follows.
Figure C20048000692600611
Dye-sensitized electrooptical device of the present invention is the device of the pigment of load type on the oxide semiconductor particulate (1).In optimal way, dye-sensitized electrooptical device of the present invention is to use the oxide semiconductor particulate to make the film of oxide semiconductor on substrate, then the pigment of load type (1) on this film.
As the substrate that is provided with oxide semiconductor thin-film among the present invention, its surface preferably has conductivity, and this substrate is obtained being easy on the market.Particularly, for example, can use the film of metals such as the conductive metal oxide of tin oxide that the indium that mixed, fluorine, antimony are set etc. or copper, silver, gold and the material that obtains on glass surface or Polyethylene Terephthalates or polyether sulfone etc. have the surface of macromolecular material of the transparency.This conductivity is usually below preferred 1000 Ω, below preferred especially 100 Ω.
In addition, as the particulate preferable alloy oxide of oxide semiconductor, specifically can enumerate oxide as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium etc.The oxide of wherein preferred titanium, tin, zinc, niobium, indium etc., most preferably titanium oxide, zinc oxide, tin oxide.These oxide semiconductors can use separately, but can mix or coating use on semiconductor surface.In addition, the average grain diameter of the particulate of oxide semiconductor is generally 1 to 500nm, and preferred 1 to 100nm.In addition, the particulate of this oxide semiconductor can with particle diameter big with particle diameter little mix after, use after perhaps can making multilayer.
Oxide semiconductor thin-film can by with the oxide semiconductor particulate by modes such as sprayings directly in film forming method on the substrate, substrate separated out with electric means as electrode the semiconductive particles film method, the precursor of semiconductive particles such as the slurry of semiconductive particles or semiconductor alkoxide is hydrolyzed after the pastel that contains particulate that obtains is coated on the substrate, dry, sclerosis or sintering wait to be made.On the performance of oxide semiconductor electrode, preferably use the method for slurry.In this method, slurry is that the oxide semiconductor particulate of 2 aggegations is disperseed in decentralized medium to make that by well-established law average 1 particle diameter is 1 to 200nm to get.
So long as can make just can using arbitrarily that semiconductive particles disperses, can use alcohol as the decentralized medium that disperses slurry as water, ethanol etc.; The hydrocarbon of the ketone of acetone, acetylacetone,2,4-pentanedione etc. or hexane etc., these can mix use, and in addition, the viscosity that can reduce slurry when making water changes therefore preferred.And, can use with the stable dispersion stabilizer that turns to purpose of dispersity the oxide semiconductor particulate.The concrete row of employed dispersion stabilizer can be lifted as acid such as acetate, hydrochloric acid, nitric acid or acetylacetone,2,4-pentanedione, acrylic acid, polyethylene glycol, polyvinyl alcohol etc.
The substrate of coating slurry can carry out roasting, and this sintering temperature is generally more than 100 ℃, and is preferred more than 200 ℃, and the upper limit is roughly below the fusing point (softening point) of base material, is limited to 900 ℃ on usually, and is preferred below 600 ℃.That is, the present invention is not particularly limited roasting time, in preferably approximately 4 hours.The thickness of film on substrate is generally 1 to 200 μ m, preferred 1 to 50 μ m.When carrying out roasting, the coating portion welding of oxide semiconductor particulate, but this welding there is no special influence to the present invention.
Oxide semiconductor also can carry out 2 times to be handled.Promptly for example, by with solution such as the alkoxide of the same metal of semiconductor, chloride, itrated compound, sulfide in directly, substrate together with carrying out drying or roasting again after thin film dipped, can be improved the performance of semiconductive thin film.Metal alkoxide can be enumerated as titanium ethanolate, isopropyl titanate, tert-butyl alcohol titanium, positive dibutyl-diacetyl tin etc., uses these alcoholic solution.Chloride can be enumerated as titanium tetrachloride, butter of tin, zinc chloride etc., uses its aqueous solution.The oxide semiconductor thin-film that so obtains is that the particulate by oxide semiconductor is become.
Then the method to load pigment on the oxide semiconductor particulate that forms film like is illustrated.As being the method for pigment load with the methine shown in the formula (1), can be set forth in the solution that obtains through dissolving in the solvent that can dissolve this pigment or when the dissolubility of pigment was low, dipping was provided with the method for the substrate of above-mentioned oxide semiconductor thin-film in the dispersion liquid that obtains disperseing pigment.Concentration in solution or the dispersion liquid can suitably be determined according to pigment.The semiconductive thin film of making on the substrate is immersed in this solution.Dip time is approximately the boiling point from the room temperature to the solvent, and dip time is about 1 minute to about 48 hours in addition.Can be used to dissolve the solvent of pigment, specifically can enumerate as, methyl alcohol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide, acetone, the tert-butyl alcohol etc.The pigment concentration of solution is generally 1 * 10 -6M to 1M, preferred 1 * 10 -5M to 1 * 10 -1M.So can obtain containing electrooptical device of the present invention by dye-sensitized film like oxide semiconductor particulate.
By the methine of the formula of load (1) is that pigment can be a kind, also can several mixing.In addition, when mixing, pigment of the present invention can be mixed mutually, also can mix other pigment or metal complex dye.Particularly, can utilize the absorbing wavelength of wide region, obtain the high solar cell of conversion efficiency by the different pigment of blended absorbent wavelength.Though the example of the metal complex dye that can mix is not particularly limited, but preferably at M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Graetzel, J.Am.Chem.Soc., the 115th volume, the ruthenium complex and the quaternary salt thereof that are disclosed in 6382 pages (1993), phthalocyanine, porphyrin etc., the organic pigment that mixing utilizes can be enumerated the phthalocyanine as no metal, porphyrin or cyanine, merocyanine, oxonol, triphenyl methane system, methines such as the acrylic acid series pigment that is disclosed in the WO2002011213 communique are pigment, or xanthene system, azo system, anthraquinone system, pigments such as perylene system.Preferred ruthenium complex or methines such as merocyanine, acrylic acid series are pigment.Pigment can be adsorbed on the semiconductive thin film successively when using more than 2 kinds pigment, also can adsorb behind the mixed dissolution.
The ratio of hybrid pigment is not particularly limited, and can select optimum ratio according to pigment separately, general preferred from etc. mole be mixed to preferred 1 pigment and use about more than 10% mole.Use is the solution of hybrid pigment mixed dissolution or dispersion, and on the oxide semiconductor particulate during adsorpting pigment, the concentration that the pigment in the solution adds up to is identical in the time of can be with a kind of a load.Solvent when using hybrid pigment can use above-mentioned solvent, and the solvent that employed each pigment is used can be identical or different.
On the film of oxide semiconductor particulate during the load pigment, in order to prevent to assemble between the pigment, under the coexistence of inclusion compound, load pigment effectively.This inclusion compound can be enumerated as steroids based compounds such as cholic acid, crown ether, cyclodextrin, calixarenes (calixarene), polyethylene glycol oxide etc., cholic acid class, polyethylene glycol oxides etc. such as preferred deoxycholic aicd, dehyrodesoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium taurocholate.In addition, behind the load pigment, the compound etc. that can use amines such as 4-tert .-butylpyridine and have acidic groups such as acetate, propionic acid is handled the semi-conducting electrode surface.Processing method for example can adopt the substrate of the semiconductive particles film that will be provided with the load pigment to be immersed in method in the ethanolic solution of amine etc.
Solar cell of the present invention is by electrooptical device electrode (negative electrode), counterelectrode (anode), redox electrolytes matter or the formations such as hole transporting material or p N-type semiconductor N of load pigment on above-mentioned oxide semiconductor particulate.The form of redox electrolytes matter, hole transporting material, p N-type semiconductor N etc. can be enumerated as liquid, solidifying body (gel and gel), solid etc.Aqueous enumerating as redox electrolytes matter, fuse salt, hole transporting material, p N-type semiconductor N etc. being dissolved in solution in each solvent and normal temperature fuse salt etc.; Solidifying body (gel and gel) can be enumerated as these being contained in the form in polymer substrate and the low molecular gel agent etc.Solid then can use redox electrolytes matter, fuse salt, hole transporting material, p N-type semiconductor N etc.Hole transporting material can be enumerated as using discotic mesogenic phases such as electroconductive polymer, benzophenanthrene (triphenylene) based compound such as amine derivative or polyacetylene, polyaniline, polythiophene.In addition, the p N-type semiconductor N can be enumerated as CuI, CuSCN etc.Counterelectrode has conductivity, preferably the reduction reaction of redox electrolytes matter is played those of catalyst action.For example can use evaporation platinum, carbon, rhodium, ruthenium etc. on glass or macromolecule book film, or be coated with electrically conductive microparticle those.
The redox electrolytes matter that is used in solar cell of the present invention can be enumerated as being the halogen compound of equilibrium ion with the halogen ion and being that the burning reduction of metal complexs such as electrolyte, hydroferrocyanate-ferricyanide and ferrocene-ferricinum ion, cobalt complex etc. is electrolyte, alkyl sulfide-alkyl disulfide, 4 by the zirconyl oxyhalides reduction that the halogen molecule constitutes, the reduction of organic oxidations such as 4 '-bipyridilium pigment, quinhydrones-quinone is an electrolyte etc., and preferred zirconyl oxyhalides reduction is an electrolyte.The zirconyl oxyhalides reduction that is made of halogen compound-halogen atom is that the halogen molecule in the electrolyte can be enumerated as iodine molecule and molecular bromine etc. preferred iodine molecule.In addition, be that the halogen compound of equilibrium ion can be enumerated as LiI, NaI, KI, CsI, CaI with the halogen ion 2, MgI 2, halogen such as metal halide salt such as CuI or tetraalkyl ammonium iodide, imidazoles  iodide, pyridine  iodide organic quaternary ammonium salt etc., preferably be the salt of equilibrium ion with the iodide ion.Iodide ion is the salt of equilibrium ion, can enumerate as lithium iodide, sodium iodide, iodate leptodactyline etc.
In addition, when redox electrolytes matter constituted with the solution form that contains it, its solvent used those of inertia on electrochemistry.Can enumerate as acetonitrile, propylene carbonate, ethylene carbonate, the 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, gamma-butyrolacton, dimethoxy-ethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl carbonate, 1, the 2-dimethoxy-ethane, dimethyl formamide, dimethyl sulfoxide (DMSO), 1, the 3-dioxolanes, methyl formate, the 2-methyltetrahydrofuran, 3-methoxyl group- azoles alkane-2-ketone, sulfolane, oxolane, water etc., wherein preferred acetonitrile, propylene carbonate, ethylene carbonate, the 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, 3-methoxyl group- azoles alkane-2-ketone, gamma-butyrolacton etc.These can be used singly or two or more kinds in combination.Under the situation of gel-like electrolyte, can enumerate as the electrolyte that in matrix such as low polymer and polymer, contains electrolyte or electrolyte solution, at W.Kubo, K.Murakoshi, T.Kitamura, K.Hanabusa, H.Shirai, and S.Yanagida, Chem.Lett., the electrolyte that contains electrolyte or electrolyte solution in the low molecular gel agent of putting down in writing in 1241 pages (1998) etc. equally.The concentration of redox electrolytes matter is generally 0.01 to 99 weight %, preferred 0.1 to 90 weight %.
Solar cell of the present invention is on the electrooptical device (negative electrode) of load pigment on the oxide semiconductor particulate on the substrate, disposes the counterelectrode (anode) relative with this negative electrode.Can get by the solution that filling between these the two poles of the earth contains redox electrolytes matter.
(embodiment)
Followingly be described in more detail the present invention, but the present invention is not limited to these embodiment according to embodiment.In an embodiment so long as there is not specially appointed part all to be expressed as mass parts.Following absorption spectrum, NMR spectrum, each free UV visual spectrophotometer of luminescent spectrum (JASCOV-570 Japan beam split company makes), nuclear magnetic resonance measuring device (manufacturing of Gemini 300 Varian companies), spectrofluorimeter (JASCO FP-600 Japan beam split company makes) are measured.
Embodiment 1
1 part of following compound (532) and 0.45 part of malonic methyl ester nitrile are dissolved in 10 parts of ethanol, in this solution, add 0.05 part of Piperazine anhydrous.After carrying out 2 hours back flow reaction, the solid that cooling is obtained filters, cleans, dry.This solid carried out 2 hours back flow reaction in 20 parts of ethanol in the presence of 1 part of potassium hydroxide.Add 50 parts of water in reaction solution, then with the hydrochloric acid neutralization, after the orange crystallization filtration of separating out, washing is carried out recrystallization with ethanol again, obtains 0.71 part of compound as tenne crystallization (197).
λmax(EtOH：435nm)
1H-NMR(PPM：d6-DMSO)：2.97(s.CH 3.6H)，6.77(d.arom.2H)，7.42(d.thio.1H)，7.56(d.arom.2H)，7.66(d.thio.1H)，8.08(s.-CH＝.1H)
Figure C20048000692600671
Embodiment 2
Except replace 1 part of compound (532) with 1.6 parts of following compounds (533), carry out the same treatment with embodiment 1, obtain 0.98 part of compound (205) as tenne crystallization.
λmax(EtOH：431)
1H-NMR(PPM：d6-DMSO)：6.98(d.arom.2H)，7.12(m.arom.6H)，7.37(m.arom.4H)，7.64(d.thio.1H)，7.69(d.arom.2H)，8.00(d.thio.1H)，8.47(s.-CH＝.1H)
Figure C20048000692600672
Embodiment 3
Except replace 1 part of compound (532) with 1.7 parts of following compounds (534), carry out the same treatment with embodiment 1, obtain 1.23 parts of compounds (523) as the brown crystallization.
λmax(EtOH：457nm)
1H-NMR(PPM：d6-DMSO)：6.98(d.arom.2H)，7.01-7.20(m.(arom.6H+-CH＝.1H))，7.27-7.44(m.(arom.4H+-CH＝.1H))，7.64(d.thio.1H)，7.68(d.arom.2H)，7.99(d.thio.1H)，8.47(s.-CH＝.1H)
Figure C20048000692600681
Embodiment 4
Except replace 1 part of compound (532) with 1.9 parts of following compounds (535), carry out the same treatment with embodiment 1, obtain 1.40 parts of compounds (246) as the brown crystallization.
λ max (EtOH:460nm), luminous greatly (EtOH:621nm))
1H-NMR(PPM：d6-DMSO)：6.97(d.arom.2H)，7.08(m.arom.6H)，7.35(m.arom.4H)，7.49(d.thio.1H)，7.58(d.thio.1H)，7.62(d.thio.1H)，7.62(d.arom.2H)，7.94(d.thio.1H)，8.43(s.-CH＝.1H)
Figure C20048000692600682
Embodiment 5
1 part of compound (533) and 0.83 part of rhodanine-3-acetate are dissolved in 10 parts of ethanol, after carrying out 2 hours back flow reaction, the solid that cooling is obtained filters, cleans, dry, carry out recrystallization with ethanol again, obtain 1.54 parts of compounds (272) as the brown crystallization.
λmax(EtOH：476nm)
1H-NMR(PPM：d6-DMSO)：4.71(s.CH 2.2H)，6.97(d.arom.2H)，7.12(m.arom.6H)，7.36(m.arom.4H)，7.66(d.thio.1H)，7.72(d.arom.2H)，7.82(d.thio.1H)，8.16(s.-CH＝.1H)
Embodiment 6
Except replace 1 part of compound (532) with 1.7 parts of following compounds (536), carry out the same treatment with embodiment 1, obtain 1.23 parts of compounds (14) as the brown crystallization.
λmax(EtOH：422nm)
Figure C20048000692600691
Embodiment 7
Except replace 1 part of compound (532) with 1.9 parts of following compounds (537), carry out the same treatment with embodiment 1, obtain 1.23 parts of compounds (91) as the brown crystallization.
λmax(EtOH：451nm)
Figure C20048000692600692
Embodiment 8
Except replace 1 part of compound (532) with 1.7 parts of following compounds (538), carry out the same treatment with embodiment 1, obtain 1.23 parts of compounds (108) as the brown crystallization.
λmax(EtOH：417nm)
1H-NMR(PPM：d6-DMSO)：7.04(d.arom.2H)，7.17-7.41(m.arom.7H)，7.48(m.arom.4H)，7.66-7.78(m.arom.7H)，7.98(d.arom.2H)，8.17(s.-CH＝.1H)
Figure C20048000692600701
Embodiment 9
Pigment is dissolved to 3.2 * 10 in EtOH -4M.At room temperature in this solution dipping porous substrate (under 450 ℃ on the transparent conductivity glass electrode with 30 minutes semiconductor electrode film of porous acidifying titanium sintering) 3 hours make the load pigment to an evening, with solvent clean, dry, obtain the electrooptical device of dye-sensitized semiconductive thin film.To be adjusted to 1.6 * 10 in each comfortable EtOH solution of 2 kinds of pigments in embodiment 19 and 20 -4M similarly obtains electrooptical device by 2 kinds of pigments of load.In addition, in embodiment 16,19 and 20, the 0.2M titanium tetrachloride aqueous solution drips on the thin film of titanium oxide part of semiconductor electrode film, after at room temperature leaving standstill 24 hours, wash, carry out roasting in 30 minutes under 450 ℃ again, the semiconductor electrode film that the use titanium tetrachloride is handled is the load pigment similarly.In embodiment 15, add cholic acid to 3 * 10 during the load pigment in addition as inclusion compound -2M modulates previous pigment solution, and load on semiconductive thin film obtains the dye-sensitized semiconductive thin film that cholic acid is handled.The surface is fixing to clamp this film by the conductive glass of platinum sputter, and injection contains electrolytical solution in its space.Respectively with iodine/lithium iodide/1,2-dimethyl-3-n-pro-pyl imidazoles  iodide/tert .-butylpyridine is dissolved to the electrolyte of 0.1M/0.1M/0.6M/1M in the 3-methoxypropionitrile in the electrolyte use.
The actual effect of the size of battery to be determined partly is 0.25cm 2Light source uses the 500W xenon lamp, obtains 100mW/cm by AM (air quality) 1.5 filters 2Short circuit current, release voltage, conversion efficiency are measured with constant pressure and constant flowmeter (potentio-galvanostat).
Table 12
Embodiment Organic pigment Short circuit current (mA/cm 2) Release voltage (V) Conversion efficiency (%) The TiCl of film 4Handle Have or not cholic acid
9 14 9.2 0.67 4.3 Be untreated Do not have
10 91 10.0 0.65 4.6 Be untreated Do not have
11 108 8.7 0.69 4.3 Be untreated Do not have
12 197 8.6 0.66 4.0 Be untreated Do not have
13 205 9.4 0.68 4.5 Be untreated Do not have
14 246 9.8 0.67 4.6 Be untreated Do not have
15 246 11.8 0.67 5.6 Be untreated Have
16 246 13.5 0.67 6.5 Handle Do not have
17 272 8.6 0.64 3.8 Be untreated Do not have
18 523 8.9 0.67 4.2 Be untreated Do not have
19 14+108 10.1 0.67 4.9 Handle Do not have
20 246+523 13.9 0.66 6.6 Handle Do not have
According to table 12, using by the methine shown in the formula (1) as can be seen is dye-sensitized electrooptical device, visible light can be carried out effectively the electricity conversion.
(utilizing on industry possibility)
In dye-sensitized electrooptical device of the present invention, the pigment that has the specific part structure by use, can provide the solar cell that conversion efficiency is high and stability is high. In addition, use, with oxide semiconductor particulate dye-sensitized more than 2 kinds, can be found out the raising of conversion efficiency by also.

Claims (22)

1. electrooptical device is characterized in that, using by the methine shown in the formula (1) is dye-sensitized oxide semiconductor particulate,
Figure C2004800069260002C1
Wherein, m 1Be 0 o'clock, R 1And R 2Respectively as shown in the formula shown in (3 ') and the formula (3 "),
Figure C2004800069260006C1
In formula (3 ') and formula (3 "), phenyl ring c 2Can further have one or more substituting groups; can enumerate halogen atom as this substituting group; amide groups; hydroxyl; carbon number is 1～20 alkoxyl; be selected from amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the replacement in the phenyl-acetamides base or the amino of non-replacement; can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent carbon number in 1～20 the aliphatic hydrocarbon residue and be 1～20 aliphatic hydrocarbon residue; maybe can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings; in addition by mutually combining phenyl ring c between a plurality of substituting groups 2Can form and to have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be the substituent ring in 1～20 the aliphatic hydrocarbon residue, R 11And R 12Expression can have the sulfonic group of being selected from separately; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings.
2. electrooptical device as claimed in claim 1, wherein, the methine shown in the formula (1) is that pigment is, the R in the formula (1) 1And R 2For having the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the compound that carbon number is the aromatic residue of 5～16 aromatic rings.
3. electrooptical device as claimed in claim 2, wherein, the methine shown in the formula (1) is that pigment is the compound shown in the following formula (2),
Figure C2004800069260008C1
In the formula (2), m 2, n 2, X 2, A 3, A 4, Y 2, a 2And b 2Expression and the corresponding m of formula (1) separately 1, n 1, X 1, A 1, A 2, Y 1, a 1And b 1The same connotation, phenyl ring c 1Have with formula (3 ') and formula (3 ") in corresponding c 2Identical implication, R 6And R 7Expression is selected from amino separately; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the replacement in the phenyl-acetamides base or the amino of non-replacement perhaps can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings.
4. electrooptical device as claimed in claim 3, wherein, the methine shown in the formula (2) is that pigment is the compound shown in the following formula (3),
Figure C2004800069260009C1
In the formula (3), m 3, n 3, X 3, A 5, A 6, Y 3, a 3And b 3Separately the expression with formula (1) in corresponding m 1, n 1, X 1, A 1, A 2, Y 1, a 1And b 1The same connotation, phenyl ring c 2Have with formula (3 ') and formula (3 ") in corresponding c 2Identical implication, R 11And R 12Expression is selected from amino separately; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the replacement in the phenyl-acetamides base or the amino of non-replacement perhaps can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings.
5. electrooptical device as claimed in claim 4, wherein, the methine shown in the formula (3) is that pigment is, the R in the formula (3) 11And R 12Compound for the amino that is selected from replacement in amino, list or dimethylamino, list or diethylamino, list or dipropyl amino, list or diphenyl amino, list or dinaphthyl amino, monoalkyl list phenyl amino, acetamido, the phenyl-acetamides base or non-replacement.
6. electrooptical device as claimed in claim 4, wherein, the methine shown in the formula (3) is that pigment is, the R in the formula (3) 11And R 12For having the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent carbon number in 1～20 the aliphatic hydrocarbon residue and be the compound of 5～16 aromatic residue.
7. electrooptical device as claimed in claim 6, wherein, the methine shown in the formula (3) is that pigment is, the X in the formula (3) 3Compound for carboxyl.
8. electrooptical device as claimed in claim 7, wherein, the methine shown in the formula (3) is that pigment is, the X in the formula (3) 3Be carboxyl and and X 3Nearest A 6For cyano group, carboxyl or carbon number are 1～10 the alkyl-carbonyl or the compound of aryl carbonyl.
9. electrooptical device as claimed in claim 6, wherein, the methine shown in the formula (3) is that pigment is, the X in the formula (3) 3With with X 3Nearest A 6Formation can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be the compound of the substituent ring in 1～20 the aliphatic hydrocarbon residue.
10. electrooptical device as claimed in claim 4, wherein, the methine shown in the formula (3) is that pigment is, the m in the formula (3) 3It is 1 to 3 compound.
11. as the electrooptical device of claim 10, wherein, the methine shown in the formula (3) is that pigment is, the n in the formula (3) 3It is 1 to 4 compound.
12. electrooptical device as claimed in claim 4, wherein, the methine shown in the formula (3) is that pigment is, the Y in the formula (3) 3Compound for sulphur atom.
13. electrooptical device as claimed in claim 1 is characterized in that, using by the methine shown in the formula (1) is more than one of pigment, and the oxide semiconductor that uses metal complex and/or have the organic pigment sensitizing of formula (1) structure in addition.
14. electrooptical device as claimed in claim 1, wherein, the oxide semiconductor particulate contains titanium dioxide as necessary composition.
15. electrooptical device as claimed in claim 1, wherein, the oxide semiconductor particulate contains must composition as the zinc of metal ingredient or tin conduct.
16. electrooptical device as claimed in claim 1, wherein, in the presence of inclusion compound, load pigment on the oxide semiconductor particulate.
17. the manufacture method of electrooptical device is characterized in that, the pigment shown in the load type (1) on the oxide semiconductor particulate that forms film like.
18. solar cell is characterized in that, uses the electrooptical device of claim 1.
19. the oxide semiconductor particulate is dye-sensitized by the methine shown in the above-mentioned formula (1) to (3).
20. methine is a pigment, wherein in above-mentioned formula (1), and R 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, X 1Be carboxyl, A 1Be hydrogen atom, A 2Be cyano group.
21. methine is a pigment, wherein above-mentioned formula (1), R 1And R 2Be phenyl ring, Y 1Be sulphur atom, m 1Be 1 to 2 integer, n 1Be 1 integer, by X 1, A 1With A 2Form the rhodanine ring.
22. methine is a pigment, wherein in above-mentioned formula (3), and R 11And R 12For being selected from amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the replacement in the phenyl-acetamides base or the amino of non-replacement maybe can have the sulfonic group of being selected from; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings; m 3Be 0 to 3 integer, n 3Be 1 to 2 integer, X 3Be carboxyl, A 5Be hydrogen atom, A 6Be cyano group, work as m 3Be 0 o'clock, R 11And R 12Expression can have the sulfonic group of being selected from separately; sulfamoyl; cyano group; isocyano group; thiocyano; the isocyanide sulfenyl; nitro; nitroso; halogen atom; hydroxyl; phosphate; phosphate-based; amino; list or dimethylamino; list or diethylamino; list or dipropyl amino; list or diphenyl amino; list or dinaphthyl amino; monoalkyl list phenyl amino; acetamido; the phenyl-acetamides base; sulfydryl; alkylthio group; thiophenyl; amide groups; alkylamidoalkyl; aryl amido group; the alkoxyl of carbon number 1～20; phenoxy group; naphthoxy; carbon number is 1～10 alkyl-carbonyl or aryl carbonyl; aldehyde radical; carbon number is 1～10 alkoxy carbonyl group; contain carbon number and be the aromatic residue of 5～16 aromatic rings and carbon number and be substituent in 1～20 the aliphatic hydrocarbon residue and have the aromatic residue that carbon number is 5～16 aromatic rings.
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