PHOTOSENSITIZER AND PHOTOELECTRIC CONVERSION DEVICE

Abstract

A photosensitizer is a dye represented by the following formula (I) or its salt. In the following chemical formula, m represents an integer of 0 through 4, and n represents an integer of 0 or 1, and p represents an integer of 0 to 2. R.sub.1, R.sub.2 and R.sub.3 represent a hydrogen atom, an alkyl group, an aryl group or the like. R.sub.4, R.sub.4, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 represent a hydrogen atom, an alkyl group and the like. X represents a carbonyl group or the like. Z.sub.1 and Z.sub.2 represent a carboxyl group or the like:

##STR00001##

Claims

1. A photosensitizer that is a dye represented by the following general formula (I) or its salt: ##STR00032## (In formula (I), m represents an integer of 0 through 4, and n represents an integer of 0 or 1, and p represents an integer of 0 to 2. R.sub.1 and R.sub.2 represent a hydrogen atom, an alkyl group or an aryl group, and may bind to each other to form an aromatic ring or an aliphatic ring. R.sub.3 represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic residue. R.sub.4, R.sub.4 and R.sub.4 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, a substituted amino group or a halogen atom, and may bind at R.sub.4 and R.sub.4 to form a ring structure. R.sub.5 and R.sub.6 represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, and may bind at R.sub.5 and R.sub.6 to form a ring structure. R.sub.7, R.sub.8 and R.sub.9 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group or an aryl group, and may bind at R.sub.7 and R.sub.8, or at R.sub.8 and R.sub.9 to form an aliphatic ring. X represents an oxygen atom, an alkylene group, or a carbonyl group. Z.sub.1 and Z.sub.2 represent a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a sulfone group or a substituted amino group, but Z.sub.1 and Z.sub.2 are hydrogen atoms not at the same time. Here, an acidic group is included as at least one substituent in a molecule).

2. A photoelectric conversion device comprising: a light absorption layer including the photosensitizer as defined in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0016] FIG. 1 is a schematic block diagram illustrating an embodiment of a photoelectric conversion device according to the present disclosure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Next, a photosensitizer of the present disclosure will be described in details.

##STR00003##

[0018] In general formula (I), m represents an integer of 0 through 4, and n represents an integer of 0 or 1, and p represents an integer of 0 to 2.

[0019] A compound represented by the aforementioned general formula (I) of the photosensitizer of the present disclosure may be a free acid represented by the general formula (I) or its salt. Salts of the compound represented by the general formula (I) are, for example, an alkali metal salt or alkali earth metal salt, such as carboxylic acid lithium, sodium, potassium, magnesium and calcium, or an alkylammonium salt, such as tetramethylammonium, tetrabutylammonium, pyridinium, piperidinium and imidazolium.

[0020] In the general formula (I), R.sub.1 and R.sub.2 represent a hydrogen atom, an alkyl group or an aryl group. Examples of the alkyl group are normal alkyl groups, such as a methyl group, an ethyl group and a propyl group, branched alkyl groups, such as an isopropyl group and an isobutyl group, and cyclic alkyl groups, such as a cyclopentyl group and a cyclohexyl group, and these alkyl groups may be further substituted by substituents that will be described later. Examples of the aryl group are phenyl, naphthyl, anthranil, phenanthrenyl, pyrenyl, indenyl, azulenyl and fluorenyl groups, and they may further have substituents. R.sub.1 and R.sub.2 may bind to each other to form an aromatic ring or an aliphatic ring. A ring structure formed in that case is, for example, benzene, naphthalene, cyclopentane, cyclopentanone, pyridine, piperidine, piperazine, pyrazole, pyrrole, imidazole, thiazole, indole, quinoline, carbazole and the like, and they may further have substituents, or further have ring structures as substituents.

[0021] Examples of the substituent are a cyano group, an isocyano group, thiocyanato group, an isothiocyanato group, a nitro group, a nitrosyl group, a sulfo group, a halogen atom, a hydroxyl group, a phosphate group, an organophosphate group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, an alkoxy group, an alkoxyalkyl group, a carboxyl group, an alkoxycarbonyl group, an alkyl group, an aryl group, an acyl group, and the like, but not particularly limited.

[0022] Specifically, as the acyl group, for example, an alkylcarbonyl group and an arylcarbonyl group having a carbon number of 1 to 10 are desirable. Examples of the halogen atom are atoms of chlorine, bromine, iodine and the like. Examples of the organophosphate group are an alkyl phosphate (C1-C4) ester group and the like. Examples of the substituted mercapto group are alkylthio groups, such as methylthio and ethylthio, and the like.

[0023] Examples of the substituted amino group are a mono- or di-alkylamino group, a mono- or di-arylamino group and the like, and specifically, a mono- or di-methylamino group, a mono- or di-ethylamino group, a mono- or di-propylamino group, a mono-phenylamino group, a benzylamino group and the like. Examples of the substituted amide group are an alkylamide group, an aromatic amide group and the like. Examples of the alkoxy group are an alkoxy group having a carbon number of 1 to 10, and the like. Examples of an alkoxyalkyl group are a (C1-C10) alkoxy (C1-C4) alkyl group, such as an ethoxyethyl group, and the like.

[0024] Examples of the alkoxycarbonyl group are an alkoxycarbonyl group having a carbon number of 1 to 10, such as an ethoxycarbonyl group, and the like. Further, an acidic group, such as a carboxyl group, a sulfo group and a phosphate group, may form an organic salt like a salt of metal, such as lithium, sodium, potassium, magnesium and calcium, and an ammonium salt, such as tetramethylammonium, tetrabutylammonium, pyridinium, piperidinium and imidazolium.

[0025] R.sub.3 represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic residue, and examples of the alkyl group and the aryl group are similar to the aforementioned examples. The aralkyl group means an alkyl group substituted by an aryl group as will be described later. Examples of the aralkyl group are a benzyl group, a phenylethyl group, a methylnaphthyl group and the like, and they may further have substituents. The heterocyclic residue means a group given by removal a hydrogen atom from a heterocyclic compound, and examples of the heterocyclic residue are pyridyl, pyradyl, piperidyl, pyrazolyl, morpholyl, indolinyl, thiophenyl, furyl, oxazolyl, thiazolyl, indolyl, benzothiazolyl, benzoxazolyl, quinolyl, rhodanile and the like, and they may further have substituents.

[0026] In the general formula (I), R.sub.4, R.sub.4 and R.sub.4 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, a substituted amino group or a halogen atom, examples of which are similar to the aforementioned examples. R.sub.4 and R.sub.4 may bind to each other to form a ring structure, examples of which are similar to the aforementioned examples.

[0027] In the general formula (I), R.sub.5 and R.sub.6 represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, examples of which are similar to the aforementioned examples. R.sub.5 and R.sub.6 may bind to each other to form a ring structure, examples of which are similar to the aforementioned examples.

[0028] In the general formula (I), R.sub.7, R.sub.8 and R.sub.9 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group or an aryl group, and examples of the alkyl group, the aralkyl group and the aryl group are similar to the aforementioned examples. Examples of the alkenyl group are a vinyl group and an allyl group, and they may further have substituents, and examples of which are similar to the aforementioned examples. R.sub.7 and R.sub.8, or R.sub.8 and R.sub.9 may bind to each other to form an aliphatic ring, examples of which are similar to the aforementioned examples.

[0029] In the general formula (I), X represents an oxygen atom, a sulfur atom, an alkylene group, a substituted amino group, a carbonyl group, a sulfonyl group, or an aliphatic spiro ring. Examples of the alkylene group are a dimethylmethylene group, a dibutylmethylene group and the like. Examples of the aliphatic spiro ring are cyclopentane, cyclohexane, cyclohexene, cyclohexadiene and the like, and they may further have substituents.

[0030] In the general formula (I), Z.sub.1 and Z.sub.2 represent a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a sulfone group or a substituted amino group, examples of which are similar to the aforementioned examples.

[0031] The compound represented by the general formula (I) includes an acidic group as at least one substituent in a molecule. It is desirable that the acidic group is one of a carboxy group, a sulfonic acid group, a phosphonyl group and a phosphoryl group and salts thereof. The acidic group may bind through a linking group, desirable examples of which are a carboxyvinylene group, a dicarboxyvinylene group, a cyanocarboxyvinylene group, a carboxyphenyl group and the like.

[0032] The compound represented by the general formula (I) may form E- and Z-geometric isomers at conjugate chain sites, and an optical isomer at 3a site of an indoline skeleton or a tetrahydroquinoline skeleton. Any of them has an effect as a photosensitizer, and is usable as the dye of the present disclosure.

[0033] Next, specific examples of the compound represented by the general formula (I) will be shown, but naturally, the present disclosure is not limited to the examples.

##STR00004## ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023##

[0034] Next, the synthesis route of the dye represented by the general formula (I) will be described.

##STR00024##

[0035] As a method for synthesizing intermediate (I), a so-called Fischer indole synthesis method, in which arylhydrazone produced from ketone and arylhydrazine is heated under acid catalyst, such as sulfuric acid, or the like may be used. Further, a Skraup method or the like may be used to synthesize a quinoline ring. These hetero-rings may be reduced to intermediate (1) by using an appropriate method, such as catalytic reduction.

[0036] Intermediate (2) is easily synthesizable by a coupling reaction between intermediate (1) and intermediate (3) using palladium catalyst.

[0037] As a method for synthesizing intermediate (4) from intermediate (2) (m=0), formylation typified by a Vilsmeier reaction may be named.

[0038] When a conjugated chain is introduced (m0), first, intermediate (2) is converted to a bromo-substituted product (5) by a halogenating agent, such as NBS (N-Bromosuccinimide). Then, after a conjugated chain is extended by Suzuki coupling or the like, intermediate (4) is synthesizable through formylation by a Vilsmeier reaction. It is possible to extend the conjugated chain and to introduce a formyl group in one step by using borate ester already having the formyl group in Suzuki coupling. The Suzuki coupling is a method in which an organic halogen compound and an organic boron compound are cross-coupled under palladium catalyst. The Suzuki coupling is a useful method that is widely used because of its relatively soft conditions and excellent selection characteristics of functional groups.

[0039] As a method for obtaining dye (6) by condensation of intermediate (4) and an enone compound, a method, such as aldol condensation and Knoevenagel condensation, by reaction between a carbonyl compound and active methylene, and a method of synthesizing olefin by a Wittig reaction may be named.

[0040] Next, the photoelectric conversion device of the present disclosure will be described with reference to drawings. FIG. 1 is a schematic block diagram illustrating an embodiment of a photoelectric conversion device in the present disclosure. A photoelectric conversion device 1 includes a semiconductor layer 3 having a light absorption layer formed by causing an oxide semiconductor layer to adsorb dye (the photosensitizer of the present disclosure), an electrolyte layer 4 and a counter electrode 5 deposited, in this order, on a substrate 2 having conductivity on its surface.

[0041] As the conductive substrate, a substrate, such as metal, the base of which itself has conductivity may be used. Alternatively, when the substrate has conductivity on its surface, glass or plastic may be used as the base. In this case, as the material of the conductive layer, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), gold, platinum or the like, or a combination of two or more of them may be used. It is possible to form a substrate having conductivity on its surface by directly forming this on the substrate by using a vacuum deposition method, a sputter deposition method, an ion plating method, a chemical vapor deposition method (CVD) and the like, or by attaching, onto the substrate, a film in which these kinds of material have been formed.

[0042] Specific examples of the oxide semiconductor are oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium and the like. The oxides of titanium, tin, zinc, niobium, tungsten and the like of them are desirable, and the oxides of tin and zinc are desirable from the viewpoints of (1) low cost, (2) easy formation of porous material, (3) conductivity, durability, stability and safety as an electrode, and (4) energy level matching characteristics with the photosensitizer synthesized in the present disclosure. There oxide semiconductors may be used alone or at least two kinds of them may be used together.

[0043] The oxide semiconductor may form porous material on the substrate by application of micro-particles of these oxide semiconductors onto the substrate, and by heating by an electric furnace, microwaves or the like, or by electrodeposition.

[0044] As a method for causing the oxide semiconductor layer to adsorb dye, a method, such as impregnating a substrate on which this oxide semiconductor layer has been formed in dye solution or dye dispersion solution, may be used, and the semiconductor layer is formable by this method. The concentration of the solution may be appropriately determined based on the dye. Examples of desirable solvent usable to dissolve the dye are methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide, acetone, t-butanol and the like.

[0045] Here, in the case that a thin-film of oxide semiconductor micro-particles adsorbs dye, co-adsorbent may be added to the dye solution. As the co-adsorbent, a steroid-based compound, such as cholic acid, crown ether, cyclodextrin, calixarene and polyethylene oxide, may be named. Deoxycholic acid, dehydrocholic acid, cholic acid methyl ester, sodium cholate and the like are more desirable.

[0046] The electrolyte layer may be formed by using liquid electrolyte in which a mixed solution of acetonitrile and ethylene carbonate, or methoxypropionitrile or the like is used as solvent, and electrolyte composed of metal iodine or iodide, such as lithium iodide, is added, coagulated electrolyte, such as polymer gel electrolyte solution, or solid electrolyte, such as p-type semiconductor and hole transport agent.

[0047] When a counter electrode requires transparency, the counter electrode may be produced in a similar manner to the aforementioned substrate having conductivity. When the counter electrode does not require transparency, the counter electrode may be produced by using carbon, conductive polymer, general metal or the like.

[0048] The photosensitizer of the present disclosure may be used also as a light absorption layer of an organic thin-film solar cell.

[0049] Next, the present disclosure will be described more in detail by using examples.

EXAMPLES

[0050] The structure of intermediates (A-01) through (A-03), intermediate aldehyde (B-01) through (B-13) and an intermediate (C-01) in the present examples is representable by the following chemical formulae:

##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##

[Synthesis of Intermediates]

(Synthesis of Aldehyde (B-01))

[0051] Intermediate (A-01) (5.2 g), intermediate (A-03) (11.7 g), potassium t-butoxide (5.5 g), palladium acetate (74 mg) and tri t-butylphosphine (0.3 g) were dissolved in m-xylene (40 mL), and the inside of the system was substituted with nitrogen. After then, the inside of the system was stirred for 8 hours while heated at 120 C. After the reacted mixture was cooled down to room temperature, undissolved substance was filtered out, and filtrate was washed with water, and dried with anhydrous sodium sulfate. After then, brown oil was obtained by concentration under reduced pressure (15.0 g). Next, this brown oil (15.0 g) was dropped into Vilsmeier reagent prepared by dropping phosphoryl chloride (10.0 g) into DMF (25 mL) under ice cooling, and stirred for 3 hours at room temperature. Water (100 ml) was added to the reacted solution, and then, 25% sodium hydroxide aqueous solution was added so as to become pH11. Extraction on this reacted solution was performed with chloroform, and an organic layer was dried with anhydrous sodium sulfate. After then, a residue obtained by concentration under reduced pressure was separated and purified by column chromatography (silica gel, developing solvent: CHCl.sub.3). Accordingly, 11.6 g of ocher solid of aldehyde (B-01) was obtained (yield was 80%).

[0052] With respect to the obtained aldehyde (B-01), structure was identified by an NMR analysis.

[0053] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0054] (ppm)=9.70 (1H, s), 7.61 (1H, dd, J=1.6, 1.2 Hz), 7.50 (1H, dd, J=8.4, 1.6 Hz), 7.24-7.41 (10H, m), 7.07 (2H, d, J=9.2 Hz), 7.03 (2H, d, J=8.8 Hz), 6.95 (1H, s), 6.85 (1H, d, J=8.4 Hz), 4.83-4.87 (1H, m), 3.78-3.83 (1H, m), 2.00-2.10 (1H, m), 1.82-1.91 (2H, m), 1.73-1.80 (1H, m), 1.62-1.71 (1H, m), 1.40-1.52 (1H, m)

(Synthesis of Aldehyde (B-02))

[0055] Aldehyde (B-02) was synthesized through a similar route to (Synthesis of aldehyde (B-01)) also by using corresponding intermediates.

[0056] With respect to the obtained aldehyde (B-02), structure was identified by an NMR analysis.

[0057] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0058] (ppm)=9.71 (1H, s), 7.72 (1H, d, J=8.0 Hz), 7.68 (1H, d, J=6.8 Hz), 7.66 (1H, s), 7.54 (1H, dd, J=8.0, 1.2 Hz), 7.43 (1H, d, J=6.8 Hz), 7.36 (1H, d, J=2.0 Hz), 7.33 (1H, dd, J=7.2, 1.2 Hz), 7.31 (1H, dd, J=7.6, 2.0 Hz), 7.26 (1H, dd, J=8.4, 2.0 Hz), 6.85 (1H, d, J=8.4 Hz), 5.00 (1H, br.t, J=7.2 Hz), 3.87 (1H, dt, J=8.4, 2.4 Hz), 2.04-2.14 (1H, m), 1.88-1.99 (2H, m), 1.76-1.85 (1H, m), 1.67-1.75 (1H, m), 1.52-1.61 (1H, m), 1.51 (3H, s), 1.50 (3H, s)

(Synthesis of Aldehyde (B-03))

[0059] Aldehyde (B-03) was synthesized through a similar route to (Synthesis of aldehyde (B-01)) also by using corresponding intermediates.

[0060] With respect to the obtained aldehyde (B-03), structure was identified by an NMR analysis.

[0061] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0062] (ppm) 9.71 (1H, s), 7.70 (1H, d, J=8.1 Hz), 7.67 (1H, d, J=6.3 Hz), 7.66 (1H, s), 7.54 (1H, dd, J=8.3, 1.4 Hz), 7.25-7.35 (5H, m), 6.83 (1H, d, J=8.3 Hz), 5.02 (1H, br.t, J=6.8 Hz), 3.87 (1H, br.t, J=7.3 Hz), 2.05-2.14 (1H, m), 1.90-1.98 (6H, m), 1.69-1.81 (2H, m), 1.50-1.59 (1H, m), 1.09 (4H, m), 0.72 (3H, t, J=7.3 Hz), 0.68 (3H, t, J=7.3 Hz), 0.59-0.73 (4H, m)

(Synthesis of Aldehyde (B-04))

[0063] After coupling of intermediate (A-01) and intermediate (A-03) in a similar method to (Synthesis of Aldehyde (B-01)), the coupled product was brominated by NBS, and reacted with boronic acids, and the reacted product was reacted with Vilsmeier reagent. Accordingly, synthesis was performed.

[0064] With respect to the obtained aldehyde (B-04), structure was identified by an NMR analysis.

[0065] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0066] (ppm)=9.82 (1H, s), 7.67 (1H, d, J=4.0 Hz), 7.24-7.39 (13H, m), 7.05 (2H, d, J=8.8 Hz), 7.00 (2H, d, J=9.2 Hz), 6.95 (1H, d, J=8.0 Hz), 6.94 (1H, s), 4.75-4.80 (1H, m), 3.81-3.86 (1H, m), 2.02-2.11 (1H, m), 1.77-1.93 (3H, m), 1.61-1.71 (1H, m), 1.43-1.54 (1H, m)

(Synthesis of Aldehyde (B-05))

[0067] Aldehyde (B-05) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0068] With respect to the obtained aldehyde (B-05), structure was identified by an NMR analysis.

[0069] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0070] (ppm)=9.83 (1H, s), 7.66-7.70 (3H, m), 7.41-7.44 (3H, m), 7.23-7.36 (5H, m), 6.97 (1H, d, J=8.0 Hz), 4.92-4.95 (1H, m), 3.87-3.91 (1H, m), 2.07-2.13 (1H, m), 1.86-1.98 (3H, m), 1.58-1.62 (1H, m), 1.51 (3H, s), 1.50 (3H, s)

(Synthesis of Aldehyde (B-06))

[0071] Aldehyde (B-06) was synthesized through a similar route to (Synthesis of aldehyde (B-4)) also by using corresponding intermediates.

[0072] With respect to the obtained aldehyde (B-06), structure was identified by an NMR analysis.

[0073] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0074] (ppm)=9.83 (1H, s), 7.68 (1H, d, J=4.0 Hz), 7.67 (1H, d, J=10.0 Hz), 7.63 (1H, dd, J=8.8, 8.8 Hz), 7.44 (1H, br.s), 7.41 (1H, dd, J=8.8, 8.0 Hz), 7.33 (1H, d, J=6.8 Hz), 7.31 (1H, d, J=6.4 Hz), 7.26-7.28 (3H, m), 7.25 (1H, s), 6.94 (1H, d, J=8.4 Hz), 4.94-4.98 (1H, m), 3.86-3.91 (1H, m), 2.06-2.16 (1H, m), 1.90-2.01 (6H, m), 1.79-1.88 (1H, m), 1.67-1.75 (1H, m), 1.52-1.63 (1H, m), 1.04-1.16 (4H, m), 0.72 (3H, t, J=7.2 Hz), 0.69 (3H, t, J=7.2 Hz), 0.61-0.71 (4H, m)

(Synthesis of Aldehyde (B-07))

[0075] Aldehyde (B-07) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0076] With respect to the obtained aldehyde (B-07), structure was identified by an NMR analysis.

[0077] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0078] (ppm)=9.96 (1H, s), 7.69 (1H, d, J=8.0 Hz), 7.67 (1H, d, J=7.2 Hz), 7.43 (1H, s), 7.40-7.42 (2H, m), 7.36 (1H, d, J=2.0 Hz), 7.33 (1H, dt, J=7.2, 1.2 Hz), 7.27 (1H, dt, J=7.2, 1.2 Hz), 7.24 (1H, dd, J=8.0, 1.6 Hz), 7.09 (1H, s), 6.96 (1H, d, J=8.0 Hz), 4.91-4.95 (1H, m), 3.86-3.91 (1H, m), 2.93 (2H, dd, J=8.0, 7.6 Hz), 2.06-2.16 (1H, m), 1.82-2.02 (3H, m), 1.67-1.75 (3H, m), 1.53-1.63 (1H, m), 1.51 (3H, s), 1.50 (3H, s), 1.30-1.43 (6H, m), 0.90 (3H, t, J=6.8 Hz)

(Synthesis of Aldehyde (B-08))

[0079] Aldehyde (B-08) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0080] With respect to the obtained aldehyde (B-08), structure was identified by an NMR analysis.

[0081] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0082] (ppm)=9.96 (1H, s), 7.67 (1H, d, J=8.0 Hz), 7.65 (1H, d, J=8.8 Hz), 7.43 (1H, s), 7.40 (1H, dd, J=8.4, 1.6 Hz), 7.32 (2H, dd, J=7.2, 6.0 Hz), 7.26 (2H, dd, J=7.6, 7.6 Hz), 7.24 (1H, s), 7.09 (1H, s), 6.94 (1H, d, J=8.4 Hz), 4.94-4.98 (1H, m), 3.86-3.90 (1H, m), 2.93 (2H, dd, J=8.0, 7.6 Hz), 2.06-2.15 (1H, m), 1.91-2.01 (6H, m), 1.79-1.88 (1H, m), 1.67-1.75 (3H, m), 1.52-1.62 (1H, m), 1.30-1.43 (6H, m), 1.04-1.16 (4H, m), 0.90 (3H, t, J=6.8 Hz), 0.71 (3H, t, J=7.2 Hz), 0.69 (3H, t, J=7.2 Hz), 0.60-0.70 (4H, m)

(Synthesis of Aldehyde (B-09))

[0083] Aldehyde (B-09) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0084] With respect to the obtained aldehyde (B-09), structure was identified by an NMR analysis.

[0085] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0086] (ppm)=9.60 (1H, d, J=7.6 Hz), 7.68 (2H, dd, J=8.8, 8.0 Hz), 7.53 (1H, d, J=15.6 Hz), 7.42 (1H, d, J=7.6 Hz), 7.39 (1H, s), 7.37 (2H, dd, J=8.4, 7.6 Hz), 7.33 (1H, dt, J=7.6, 7.2 Hz), 7.27-7.29 (2H, m), 7.24 (1H, dd, J=8.8, 8.4 Hz), 7.17 (1H, d, J=3.6 Hz), 6.98 (1H, d, J=8.4 Hz), 6.44 (1H, dd, J=7.6, 7.6 Hz), 4.90-4.94 (1H, m), 3.86-3.91 (1H, m), 2.07-2.16 (1H, m), 1.83-2.01 (3H, m), 1.66-1.75 (1H, m), 1.55-1.64 (1H, m), 1.51 (3H, s), 1.50 (3H, s)

(Synthesis of Aldehyde (B-10))

[0087] Aldehyde (B-10) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0088] With respect to the obtained aldehyde (B-10), structure was identified by an NMR analysis.

[0089] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0090] (ppm)=9.60 (1H, d, J=8.0 Hz), 7.66 (2H, ddd, J=9.6, 9.2, 7.2 Hz), 7.53 (1H, d, J=15.6 Hz), 7.40 (1H, br.s), 7.37 (1H, dd, J=8.4, 2.0 Hz), 7.33 (1H, d, J=7.2 Hz), 7.32 (1H, s), 7.28-7.30 (2H, m), 7.24-7.27 (2H, m), 7.18 (1H, d, J=4.0 Hz), 6.96 (1H, d, J=8.4 Hz), 6.44 (1H, dd, J=15.6, 7.6 Hz), 4.93-4.97 (1H, m), 3.87-3.90 (1H, m), 2.06-2.16 (1H, m), 1.91-2.01 (6H, m), 1.80-1.89 (1H, m), 1.67-1.75 (1H, m), 1.53-1.63 (1H, m), 1.05-1.14 (4H, m), 0.72 (3H, t, J=7.2 Hz), 0.69 (3H, t, J=7.6 Hz), 0.61-0.69 (4H, m)

(Synthesis of Aldehyde (B-11))

[0091] Aldehyde (B-11) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0092] With respect to the obtained aldehyde (B-11), structure was identified by an NMR analysis.

[0093] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0094] (ppm)=9.60 (1H, d, J=8.0 Hz), 7.68 (1H, d, J=8.0 Hz), 7.66 (1H, d, J=8.8 Hz), 7.61 (1H, d, J=15.6 Hz), 7.41 (1H, d, J=7.2 Hz), 7.39 (1H, s), 7.35-7.38 (2H, m), 7.33 (1H, dt, J=7.2, 1.2 Hz), 7.27 (1H, dt, J=7.2, 1.2 Hz), 7.24 (1H, dd, J=8.4, 2.0 Hz), 7.05 (1H, s), 6.97 (1H, d, J=8.0 Hz), 6.40 (1H, dd, J=15.2, 7.6 Hz), 4.90-4.94 (1H, m), 3.86-3.90 (1H, m), 2.72 (2H, dd J=8.0, 7.6 Hz), 2.06-2.17 (1H, m), 1.83-2.03 (3H, m), 1.62-1.75 (3H, m), 1.51 (3H, s), 1.50 (3H, s), 1.47-1.55 (1H, m), 1.31-1.42 (6H, m), 0.90 (3H, t, J=6.8 Hz)

(Synthesis of Aldehyde (B-12))

[0095] Aldehyde (B-12) was synthesized through a similar route to (Synthesis of aldehyde (B-04)) also by using corresponding intermediates.

[0096] With respect to the obtained aldehyde (B-12), structure was identified by an NMR analysis.

[0097] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0098] (ppm)=9.61 (1H, d, J=7.6 Hz), 7.67 (1H, d, J=8.8 Hz), 7.63-7.66 (1H, m), 7.62 (1H, d, J=15.2 Hz), 7.39 (1H, s), 7.36 (1H, dd, J=8.0, 1.6 Hz), 7.33 (1H, d, J=7.2 Hz), 7.31 (1H, d, J=6.4 Hz), 7.25-7.28 (2H, m), 7.24 (1H, s), 7.06 (1H, s), 6.95 (1H, d, J=8.4 Hz), 6.40 (1H, dd, J=15.6, 8.0 Hz), 4.93-4.96 (1H, m), 3.86-3.90 (1H, m), 2.72 (2H, dd, J=8.0, 7.6 Hz), 2.06-2.15 (1H, m), 1.90-2.01 (6H, m), 1.80-1.89 (1H, m), 1.62-1.74 (3H, m), 1.51-1.61 (1H, m), 1.28-1.42 (6H, m), 1.05-1.14 (4H, m), 0.90 (3H, t, J=7.2 Hz), 0.72 (3H, t, J=7.2 Hz), 0.69 (3H, t, J=7.2 Hz), 0.61-0.70 (4H, m)

(Synthesis of Aldehyde (B-13))

[0099] Aldehyde (B-13) was synthesized through a similar route to (Synthesis of aldehyde (B-01)) by using intermediate (A-02) and intermediate (A-03).

[0100] With respect to the obtained aldehyde (B-13), structure was identified by an NMR analysis.

[0101] .sup.1H NMR (400 MHz, CDCl.sub.3)

[0102] (ppm)=9.28 (1H, d, J=8.0 Hz), 7.76 (1H, s), 7.49-7.54 (1H, s), 7.28-7.38 (10H, m), 7.23-7.25 (2H, m), 7.16-7.21 (1H, m), 6.97-6.99 (3H, m), 6.89 (1H, d, J=7.3 Hz), 4.58 (1H, ddd, J=8.9, 6.7, 2.5 Hz), 4.12 (1H, dt, J=6.1, 2.5 Hz), 2.03-2.14 (2H, m), 1.89-1.98 (2H, m), 1.63-1.72 (1H, m), 1.41-1.53 (1H, m)

(Synthesis of Intermediate (C-01))

[0103] Methyl acetoacetate (12.00 g) and triethylamine (33.78 g) were dropped into acetic anhydride solution (75 mL) of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.18 g), and stirred for 1.5 hours while heated at 100 C. After the reacted mixture was cooled down to room temperature, solvent was distilled away, and the remaining product was separated and purified by column chromatography (silica gel, developing solvent: CHCl.sub.3/MeOH=10/1). Accordingly, black liquid was obtained (12.65 g). Next, ammonium acetate (6.49 g) was added to methanol solution (150 mL) of the obtained black liquid (12.65 g), and stirred for 3 hours while heated at 75 C., and the product was solidified. Coarse crystals were separated by filtration, and washed with methanol. Accordingly, 5.76 g of intermediate (C-01) was obtained as yellow solid (yield was 44%). With respect to the obtained intermediate (C-01), structure was identified by an NMR analysis. Here, hydrogen of carboxylic acid was not observed.

[0104] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0105] (ppm)=7.92 (H, d, J=7.6 Hz), 7.80 (1H, s), 7.25 (1H, d, J=7.6 Hz), 7.14 (1H, br.s), 3.49 (3H, s)

Synthesis of Example 1 (I-03)

[0106] Aldehyde (B-01) (0.88 g) and intermediate (C-01) (0.50 g) were dissolved in acetic acid (10 mL), and stirred for 4 hours while heated at 100 C. When the reacted mixture was cooled down to room temperature, the reacted mixture was solidified. Coarse crystals were separated by filtration, and separated and purified by column chromatography (silica gel, developing solvent:

CHCl.sub.3/MeOH=100/1). Accordingly, 0.85 g of dye (I-03) was obtained as brown solid (yield was 69%). max=545 nm (CHCl.sub.3).

[0107] With respect to the dye (I-03), structure was identified by an NMR analysis.

[0108] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0109] (ppm)=13.65 (1H, br.s), 8.67 (1H, br.s), 8.33 (1H, dd, J=8.0, 7.6 Hz), 8.24 (1H, d, J=11.6 Hz), 8.20 (1H, br.s), 7.94 (1H, dd, J=7.6, 7.6 Hz), 7.65 (1H, s), 7.41-7.49 (3H, m), 7.30-7.38 (5H, m), 7.19-7.23 (4H, m), 7.11 (1H, s), 7.07 (2H, d, J=8.4 Hz), 6.87 (1H, d, J=8.8 Hz), 5.07-5.11 (1H, m), 3.82-3.87 (1H, m), 2.03-2.12 (1H, m), 1.69-1.83 (2H, m), 1.59-1.67 (2H, m), 1.27-1.38 (1H, m)

Synthesis of Example 2 (I-05)

[0110] Dye (I-05) was obtained as black solid using aldehyde intermediate (B-02) by using a similar method to Example 1. max=541 nm (CHCl.sub.3).

[0111] With respect to the obtained dye (I-05), structure was identified by an NMR analysis.

[0112] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0113] (ppm)=13.63 (1H, br.s), 8.72 (1H, br.s), 8.35 (1H, d, J=8.0 Hz), 8.28 (1H, br.s), 8.25 (1H, d, J=11.6 Hz), 7.95 (1H, dd, J=8.0, 7.6 Hz), 7.90 (1H, d, J=8.4 Hz), 7.83 (1H, d, J=7.2 Hz), 7.69 (1H, s), 7.67 (1H, d, J=1.6 Hz), 7.56 (1H, d, J=7.2 Hz), 7.41 (1H, dd, J=8.0, 1.2 Hz), 7.36 (1H, dd, J=8.0, 7.2 Hz), 7.32 (1H, dd, J=8.4, 7.2 Hz), 6.87 (1H, d, J=8.4 Hz), 5.24-5.27 (1H, m), 3.90-3.94 (1H, m), 2.08-2.18 (1H, m), 1.74-1.88 (3H, m), 1.64-1.73 (1H, m), 1.50 (3H, s), 1.47 (3H, s), 1.37-1.53 (1H, m)

Synthesis of Example 3 (I-06)

[0114] Dye (I-06) was obtained as black solid using aldehyde intermediate (B-03) by using a similar method to Example 1. max=546 nm (CHCl.sub.3).

[0115] With respect to the obtained dye (I-06), structure was identified by an NMR analysis.

[0116] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0117] (ppm)=13.07 (1H, br.s), 8.17 (1H, br.s), 7.81 (1H, dd, J=7.6, 7.2 Hz), 7.73 (2H, d, J=9.6 Hz), 7.41 (1H, d, J=8.0 Hz), 7.34 (1H, d, J=8.4 Hz), 7.27 (1H, d, J=7.2 Hz), 7.14 (1H, s), 6.99 (1H, s), 6.92 (1H, d, J=6.8 Hz), 6.88 (1H, d, J=8.0 Hz), 6.83 (1H, dd, J=7.2, 6.0 Hz), 6.80 (1H, dd, J=7.2, 6.4 Hz), 6.30 (1H, d, J=8.4 Hz), 4.72-4.75 (1H, m), 3.36-3.40 (1H, m), 1.57-1.65 (1H, m), 1.43-1.56 (4H, m), 1.28-1.35 (1H, m), 1.11-1.26 (3H, m), 0.84-0.95 (1H, m), 0.45-0.59 (4H, m), 0.16 (3H, t, J=7.2 Hz), 0.10 (3H, t, J=7.2 Hz), 0.02-0.04 (4H, m)

Synthesis of Example 4 (I-26)

[0118] Dye (I-26) was obtained as black solid using aldehyde intermediate (B-04) by using a similar method to Example 1. max=607 nm (CHCl.sub.3).

[0119] With respect to the obtained dye (I-26), structure was identified by an NMR analysis.

[0120] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0121] (ppm)=13.62 (1H, br.s), 8.32 (1H, dd, J=8.0, 7.6 Hz), 8.23 (1H, d, J=10.4 Hz), 8.17 (1H, d, J=4.0 Hz), 7.95 (1H, s), 7.92 (1H, d, J=8.0 Hz), 7.59 (1H, d, J=4.4 Hz), 7.57 (1H, s), 7.45 (1H, d, J=6.8 Hz), 7.42 (1H, d, J=7.6 Hz), 7.39-7.52 (2H, m), 7.33 (1H, d, J=6.8 Hz), 7.30 (1H, s), 7.29 (1H, d, J=7.2 Hz), 7.26-7.36 (3H, m), 7.20 (1H, d, J=7.2 Hz), 7.09 (2H, d, J=8.4 Hz), 7.05 (1H, s), 7.00 (2H, d, J=8.4 Hz), 6.94 (1H, dd, J=8.4, 3.2 Hz), 4.85-4.88 (1H, m), 3.80-3.84 (1H, m), 2.00-2.10 (1H, m), 1.76-1.86 (2H, m), 1.55-1.70 (2H, m), 1.27-1.39 (1H, m)

Synthesis of Example 5 (I-27)

[0122] Dye (I-27) was obtained as blackish purple solid using aldehyde intermediate (B-05) by using a similar method to Example 1. max=616 nm (CHCl.sub.3).

[0123] With respect to the obtained dye (I-27), structure was identified by an NMR analysis.

[0124] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0125] (ppm)=13.66 (1H, br.s), 8.35 (1H, d, J=8.0 Hz), 8.25 (1H, br.s), 8.24 (1H, d, J=8.4 Hz), 8.20 (1H, d, J=4.4 Hz), 7.98 (1H, s), 7.94 (1H, d, J=8.0 Hz), 7.81 (1H, d, J=8.4 Hz), 7.76 (1H, d, J=7.2 Hz), 7.62-7.63 (1H, m), 7.62 (1H, s), 7.58-7.61 (1H, m), 7.54 (1H, s), 7.53 (1H, d, J=6.8 Hz), 7.33 (1H, dd, J=8.0, 6.8 Hz), 7.28 (1H, dd, J=7.6, 6.4 Hz), 6.98 (1H, dd, J=8.4, 8.4 Hz), 5.04-5.07 (1H, m), 3.86-3.91 (1H, m), 2.05-2.16 (1H, m), 1.73-1.92 (3H, m), 1.60-1.70 (1H, m), 1.48 (3H, s), 1.47 (3H, s), 1.37-1.52 (1H, m)

Synthesis of Example 6 (I-28)

[0126] Dye (I-28) was obtained as black solid using aldehyde intermediate (B-06) by using a similar method to Example 1. max=619 nm (CHCl.sub.3).

[0127] With respect to the obtained dye (I-28), structure was identified by an NMR analysis.

[0128] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0129] (ppm)=13.67 (1H, br.s), 8.34 (1H, dd, J=9.2, 8.4 Hz), 8.25 (1H, d, J=10.4 Hz), 8.21 (1H, d, J=4.0 Hz), 8.00 (1H, s), 7.94 (1H, d, J=8.0 Hz), 7.80 (1H, d, J=8.4 Hz), 7.74 (1H, d, J=7.2 Hz), 7.67 (1H, d, J=4.4 Hz), 7.65 (1H, s), 7.58 (1H, d, J=8.4 Hz), 7.42 (1H, d, J=7.2 Hz), 7.40 (1H, s), 7.30-7.33 (2H, m), 7.27 (1H, dd, J=7.6, 7.2 Hz), 6.94 (1H, dd, J=8.4, 2.8 Hz), 5.08-5.12 (1H, m), 3.86-3.90 (1H, m), 1.94-2.15 (5H, m), 1.72-1.88 (3H, m), 1.61-1.69 (1H, m), 1.35-1.46 (1H, m), 0.99-1.11 (4H, m), 0.67 (3H, t, J=7.6 Hz), 0.63 (3H, t, J=7.2 Hz), 0.50-0.57 (4H, m)

Synthesis of Example 7 (I-31)

[0130] Dye (I-31) was obtained as black solid using aldehyde intermediate (B-07) by using a similar method to Example 1. max=617 nm (CHCl.sub.3).

[0131] With respect to the obtained dye (I-31), structure was identified by an NMR analysis.

[0132] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0133] (ppm)=13.60 (1H, br.s), 8.28 (1H, dd, J=8.0, 6.4 Hz), 8.18 (1H, d, J=3.2 Hz), 7.87 (1H, dd, J=7.2, 6.8 Hz), 7.80 (1H, d, J=1.2 Hz), 7.80 (1H, d, J=8.0 Hz), 7.75 (1H, d, J=7.6 Hz), 7.59 (1H, s), 7.52-7.55 (4H, m), 6.95 (1H, dd, J=8.4, 3.6 Hz), 5.01-5.05 (1H, m), 3.83-3.87 (1H, m), 2.82 (2H, t, J=7.2 Hz), 2.06-2.15 (1H, m), 1.73-1.90 (3H, m), 1.61-1.68 (3H, m), 1.48 (3H, s), 1.47 (3H, s), 1.40-1.46 (1H, m), 1.25-1.83 (6H, m), 0.86 (3H, dd, J=6.8, 6.4 Hz)

Synthesis of Example 8 (I-32)

[0134] Dye (I-32) was obtained as black solid using aldehyde intermediate (B-08) by using a similar method to Example 1. max=621 nm (CHCl.sub.3).

[0135] With respect to the obtained dye (I-32), structure was identified by an NMR analysis.

[0136] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0137] (ppm)=13.61 (1H, br.s), 8.28 (1H, dd, J=7.2, 6.4 Hz), 8.18 (1H, d, J=6.0 Hz), 7.86 (1H, dd, J=7.2, 6.8 Hz), 7.79 (1H, s), 7.78 (1H, d, J=9.2 Hz), 7.73 (1H, d, J=7.2 Hz), 7.59 (1H, br.s), 7.52 (1H, s), 7.50-7.55 (1H, m), 7.41 (1H, d, J=6.8 Hz), 7.38 (1H, s), 7.31 (1H, dd, J=7.6, 7.2 Hz), 7.29 (1H, s), 7.27 (1H, dd, J=8.4, 8.4 Hz), 6.90 (1H, dd, J=8.4, 8.4 Hz), 5.04-5.07 (1H, m), 3.81-3.85 (1H, m), 2.81 (2H, dd, J=7.6, 7.2 Hz), 1.94-2.13 (5H, m), 1.58-1.86 (6H, m), 1.19-1.46 (7H, m), 0.98-1.10 (4H, m), 0.85 (3H, t, J=6.4 Hz), 0.66 (3H, t, J=7.2 Hz), 0.62 (3H, t, J=7.2 Hz), 0.46-0.48 (4H, m)

Synthesis of Example 9 (I-44)

[0138] Dye (I-44) was obtained as purple solid using aldehyde intermediate (B-09) by using a similar method to Example 1. max=642 nm (CHCl.sub.3).

[0139] With respect to the obtained dye (I-44), structure was identified by an NMR analysis.

[0140] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0141] (ppm)=13.61 (1H, br.s), 8.31-8.34 (1H, m), 8.23 (1H, br.s), 7.89-7.97 (2H, m), 7.85 (1H, d, J=14.8 Hz), 7.79 (1H, d, J=8.0 Hz), 7.74 (1H, d, J=7.2 Hz), 7.61 (1H, d, J=11.6 Hz), 7.48 (1H, d, J=14.4 Hz), 7.45-7.55 (5H, m), 7.32 (1H, t, J=7.2 Hz), 7.25-7.29 (2H, m), 6.94 (1H, d, J=8.4 Hz), 4.99-5.02 (1H, m), 3.82-3.87 (1H, m), 2.04-2.14 (1H, m), 1.74-1.94 (3H, m), 1.60-1.70 (1H, m), 1.47 (6H, m), 1.37-1.52 (1H, m)

Synthesis of Example 10 (I-45)

[0142] Dye (I-45) was obtained as black solid using aldehyde intermediate (B-10) by using a similar method to Example 1. max=647 nm (CHCl.sub.3).

[0143] With respect to the obtained dye (I-45), structure was identified by an NMR analysis.

[0144] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0145] (ppm)=13.69 (1H, br.s), 8.34 (1H, ddd, J=7.6, 3.6, 1.2 Hz), 8.23 (1H, d, J=2.4 Hz), 7.90-7.94 (2H, m), 7.87 (1H, d, J=14.8 Hz), 7.77 (1H, d, J=8.0 Hz), 7.72 (1H, d, J=7.2 Hz), 7.63 (1H, dd, J=11.2, 2.0 Hz), 7.57 (1H, s), 7.52 (1H, d, J=4.0 Hz), 7.49 (1H, d, J=4.0 Hz), 7.46-7.48 (1H, m), 7.41 (1H, d, J=6.8 Hz), 7.36 (1H, s), 7.25-7.33 (3H, m), 6.91 (1H, d, J=8.0 Hz), 5.03-5.06 (1H, m), 3.82-3.86 (1H, m), 1.94-2.11 (5H, m), 1.70-1.88 (3H, m), 1.60-1.68 (1H, m), 1.34-1.44 (1H, m), 1.01-1.09 (4H, m), 0.66 (3H, t, J=7.6 Hz), 0.63 (3H, t, J=8.0 Hz), 0.50-0.57 (4H, m)

Synthesis of Example 11 (I-47)

[0146] Dye (I-47) was obtained as black solid using aldehyde intermediate (B-11) by using a similar method to Example 1. max=655 nm (CHCl.sub.3).

[0147] With respect to the obtained dye (I-47), structure was identified by an NMR analysis.

[0148] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0149] (ppm)=13.61 (1H, br.s), 8.30 (1H, ddd, J=7.6, 1.6, 1.6 Hz), 8.20 (1H, s), 8.02 (1H, d, J=14.4 Hz), 7.83-7.90 (2H, m), 7.78 (1H, d, J=8.0 Hz), 7.74 (1H, s), 7.72 (1H, dd, J=6.8, 1.6 Hz), 7.55 (1H, s), 7.52 (1H, d, J=7.6 Hz), 7.49 (1H, d, J=1.2 Hz), 7.45 (1H, ddd, J=8.4, 4.0, 2.0 Hz), 7.38 (1H, s), 7.32 (1H, ddd, J=7.2, 7.2, 1.2 Hz), 7.25-7.29 (2H, m), 6.93 (1H, dd, J=8.4, 1.2 Hz), 4.98-5.01 (1H, m), 3.81-3.86 (1H, m), 2.74 (2H, dd, J=8.0, 6.8 Hz), 2.03-2.13 (1H, m), 1.73-1.91 (3H, m), 1.57-1.67 (3H, m), 1.47 (3H, s), 1.46 (3H, s), 1.28-1.48 (7H, m), 0.87 (3H, t, J=6.8 Hz)

Synthesis of Example 12 (I-48)

[0150] Dye (I-48) was obtained as black solid using aldehyde intermediate (B-12) by using a similar method to Example 1. max=661 nm (CHCl.sub.3).

[0151] With respect to the obtained dye (I-48), structure was identified by an NMR analysis.

[0152] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0153] (ppm)=13.62 (1H, br.s), 8.28 (1H, d, J=8.0 Hz), 8.19 (1H, s), 7.99 (1H, d, J=14.4 Hz), 7.81-7.89 (2H, m), 7.75 (1H, d, J=8.0 Hz), 7.71 (1H, d, J=8.4 Hz), 7.70 (1H, dd, J=9.2, 3.2 Hz), 7.52 (1H, br.s), 7.41-7.44 (1H, m), 7.40 (1H, d, J=7.2 Hz), 7.36 (1H, s), 7.34 (1H, s), 7.30 (1H, dd, J=7.2, 6.4 Hz), 7.24-7.28 (2H, m), 6.87 (1H, dd, J=8.8, 2.4 Hz), 4.98-5.01 (1H, m), 3.78-3.82 (1H, m), 2.72 (2H, dd, J=7.6, 7.2 Hz), 1.93-2.11 (5H, m), 1.70-1.86 (3H, m), 1.56-1.65 (3H, m), 1.25-1.41 (7H, m), 0.98-1.10 (4H, m), 0.86 (3H, t, J=6.8 Hz), 0.65 (3H, t, J=7.2 Hz), 0.62 (3H, t, J=7.2 Hz), 0.48-0.57 (4H, m)

Synthesis of Example 13 (I-75)

[0154] Dye (I-75) was obtained as blackish purple solid using aldehyde intermediate (B-13) by using a similar method to Example 1. max=595 nm (CHCl.sub.3).

[0155] With respect to the obtained dye (I-75), structure was identified by an NMR analysis.

[0156] .sup.1H NMR (400 MHz, DMSO-d.sub.6)

[0157] (ppm)=13.60 (1H, br.s), 9.59 (1H, s), 8.54 (1H, s), 8.35 (1H, d, J=7.2 Hz), 8.32-8.34 (1H, m), 8.24 (1H, d, J=10.0 Hz), 7.93 (1H, dd, J=8.4, 7.6 Hz), 7.63 (1H, dd, J=8.0, 7.2 Hz), 7.43-7.47 (2H, m), 7.32-7.40 (6H, m), 7.19-7.25 (4H, m), 7.10-7.16 (5H, m), 4.87-4.90 (1H, m), 4.08-4.12 (1H, m), 2.10-2.20 (1H, m), 1.93-2.00 (1H, m), 1.83-1.90 (1H, m), 1.73-1.82 (1H, m), 1.63-1.72 (1H, m), 1.38-1.48 (1H, m)

<Dye for Comparison>

[0158] Dyes for comparison will be listed next.

##STR00030## ##STR00031##

[Production of Photoelectric Conversion Device]

(Production of Photoelectrode Layer)

[0159] An FTO glass with an FTO electrode coating formed on one of its surfaces was used as an electrode substrate, and titanium oxide paste (manufactured by JGC Catalysts and Chemicals Ltd., PST-18NR) was applied to the electrode surface of this FTO glass by using a squeegee method. After the paste was dried at 125 C. for 6 minutes, the paste was fired at 325 C. for 5 minutes, and at 375 C. for 5 minutes, and at 450 C. for 15 minutes, and at 500 C. for 15 minutes. Accordingly, a titanium oxide coating with the coating thickness of 10 m was formed. Each of dyes obtained in Examples 1 through 13 and Comparative Examples 1 through 6 was dissolved in acetonitrile/t-butyl alcohol=1/1 to get the concentration of 200 M, and the FTO glass with this titanium oxide coating formed was immersed in this solution for 90 minutes. Accordingly, photoelectric conversion layer was produced. Here, cholic acid was added, as an additive, to get the concentration of cholic acid of 0.4 mM.

(Formation of Electrolyte Layer)

[0160] 1,2-dimethyl-3-propylimidazolium iodide, iodine, lithium iodide and 4-t-butylpyridine were mixed into 3-methoxypropionitrile solution so as to be 1,2-dimethyl 3-propylimidazolium iodide (0.60 M), iodine (0.05M), lithium iodide (0.10 M) and 4-t-butylpyridine (0.05 M), and this was used as electrolyte solution. An electrolyte layer was formed by arranging this electrolyte solution between a counter substrate using the same FTO glass as the electrode substrate and the aforementioned photoelectrode layer.

<Evaluation>

[0161] Each of the photoelectric conversion devices (light receiving area is 0.20 cm.sup.2) produced as described above was illuminated at the illumination intensity of 100 mW/cm.sup.2 by using CEP-2000 manufactured by Bunkoukeiki Co., Ltd., and short circuit current (mA) and open circuit voltage (V) of the photoelectric conversion devices were measured, and short circuit current density (mA/cm.sup.2) was obtained from the short circuit current and the light receiving area. Next, maximum power Wmax(mW) was observed by changing a resistance value connected between the electrodes of the photoelectric conversion device, and fill factor FF and photoelectric conversion efficiency (%) were obtained by the following expressions. Table 1 shows an evaluation result in the case of using titanium oxide. Further, Table 2 shows an evaluation result in the case that zinc oxide was used instead of titanium oxide in production of the photoelectrode layer.

[00001]$\begin{array}{cc}\mathrm{FF}=\frac{W.Math..Math.\max \left(\mathrm{mW}\right)}{\begin{array}{c}\mathrm{Short}.Math..Math.\mathrm{Circuit}.Math..Math.\mathrm{Current}\left(\mathrm{mA}\right)\\ \mathrm{Open}.Math..Math.\mathrm{Circuit}.Math..Math.\mathrm{Voltage}\left(V\right)\end{array}}& \left[\mathrm{Mathematicla}.Math..Math.1\right]\\ \mathrm{Photoelectric}.Math..Math.\mathrm{Conversion}.Math..Math.\mathrm{Efficiency}\left(\%\right)=\frac{\begin{array}{c}\mathrm{Short}.Math..Math.\mathrm{Circuit}.Math..Math.\mathrm{Current}.Math..Math.\mathrm{Display}\left(\mathrm{mA}.Math.\text{/}.Math.{\mathrm{cm}}^2\right)\\ \mathrm{Open}.Math..Math.\mathrm{Circuit}.Math..Math.\mathrm{Voltage}\left(V\right)\mathrm{FF}\end{array}}{100.Math.\left(\mathrm{mW}.Math.\text{/}.Math.{\mathrm{cm}}^2\right)}100& \left[\mathrm{Mathematical}.Math..Math.2\right]\end{array}$

TABLE-US-00001 TABLE 1 Absorption Short Circuit Open Circuit Fill Photoelectric Conversion Maximum in Current Density Voltage Factor Efficiency Dye Name Hue CHCl.sub.3 (nm) (mA/cm.sup.2) (V) FF (%) Comparative D-01 Reddish 546 9.73 0.70 0.65 3.61 Example 1 Purple Example 1 I-03 545 12.60 0.63 0.61 4.81 Example 2 I-05 541 11.29 0.61 0.62 4.33 Example 3 I-06 546 12.01 0.61 0.60 4.40 Comparative D-02 Purple 598 10.44 0.54 0.61 3.47 Example 2 Example 13 I-75 595 15.38 0.59 0.58 5.22 Comparative D-03 Bluish 604 9.16 0.51 0.68 3.15 Example 3 Purple Example 4 I-26 607 15.75 0.57 0.61 5.43 Comparative D-04 Blue 616 8.94 0.48 0.60 2.57 Example 4 Example 5 I-27 616 15.75 0.56 0.58 5.10 Example 6 I-28 619 13.47 0.56 0.66 4.97 Example 7 I-31 617 17.72 0.58 0.57 5.85 Example 8 I-32 621 16.58 0.59 0.58 5.69 Comparative D-05 Indigo- 647 0.41 0.37 0.73 0.11 Example 5 Blue Example 9 I-44 642 9.25 0.46 0.67 2.88 Example 10 I-45 647 6.90 0.49 0.71 2.41 Comparative D-06 Bluish 658 0.44 0.34 0.71 0.11 Example 6 Green Example 11 I-47 655 11.02 0.49 0.65 3.50 Example 12 I-48 661 9.50 0.51 0.67 3.25

TABLE-US-00002 TABLE 2 Absorption Short Circuit Open Photoelectric Maximum Current Circuit Conversion in CHCl.sub.3 Density Voltage Fill Factor Efficiency Dye Name Hue (nm) (mA/cm.sup.2) (V) FF (%) Comparative D-01 Reddish 546 7.60 0.58 0.64 2.81 Example 1 Purple Example 3 I-06 546 9.82 0.60 0.60 3.53 Comparative D-04 Blue 616 1.59 0.52 0.79 0.66 Example 4 Example 7 I-31 617 11.54 0.62 0.59 4.22 Example 8 I-32 621 10.23 0.64 0.59 3.86 Comparative D-06 Bluish 658 0.35 0.31 0.60 0.07 Example 6 Green Example 12 I-48 661 7.11 0.51 0.65 2.35

[0162] As Table 1 shows, in all of the examples in which the dye of the present disclosure was used as a photosensitizer, an improvement in photoelectric conversion efficiency was observed, compared with comparative examples, in which dye of corresponding hue was used. It was possible to improve the photoelectric conversion efficiency for all of the hues from reddish purple to bluish green. The improvement in the conversion efficiency was great especially in the region of bluish purple to bluish green, which is 600 to 700 nm. It was able to obtain dye of practical use level that can cover a wide range of hue.

[0163] Further, as Table 2 shows, a great improvement in photoelectric conversion efficiency was recognized also for zinc oxide.

[0164] As the examples clearly show, the photosensitizer of the present disclosure can improve the adsorption stability of dye as well as improving the photoelectric conversion efficiency. Further, since a wide range of hue is coverable, the dye of the present disclosure is usable in a dye-sensitized solar cell, the design characteristics of which are also emphasized. Further, it is possible to obtain photoelectric conversion efficiency that is not inferior to titanium oxide even for zinc oxide, which is excellent electrode material.