TW201238968A - Metal complex dye composition, photoelectric transducing element and photoelectrochemical cell, and method for preparing metal complex dye - Google Patents

Abstract

This invention provides a metal complex dye composition with a high solubility to a solvent, and a photoelectric transducing element and a photoelectrochemical cell with a high photoelectric transducing efficiency. The metal complex dye composition contains, in a proportion of 0.5-5% by area in a 254 nm detection of HPLC, a metal complex dye of formula (1) and another metal complex dye with a specific structure. The formula (1) is expressed by: M1 (LL1)m1 (LL2)m2 (Z1)2 * (CI1)m3 (1), wherein M1 is a metal atom, LL1 is a bidentate ligand, LL2 is a bidentate ligand, Z1 is at least one ligand selected from isothiocyanato group, isocyanato group and isoselenocyanato group, CI1 represents a counter ion if a conter ion is required to neutralize charges, m1 and m2 are both equal to one, and m3 is an ineger equal to or larger than zero.

Description

[Technical Field] [Technical Field] The present invention relates to a metal complex pigment level product having high solubility in a solvent, and a photoelectric conversion element and a photoelectrochemical oil having high photoelectric conversion efficiency. ^ [Prior Art] The photoelectric conversion element can be used for various photo sensors, photocopiers, photoelectric cells (such as solar cells), and the like. In the photoelectric conversion element, various methods such as a photoelectric conversion element using gold, a photoelectric conversion element using a semiconductor, a photoelectric conversion element using an organic pigment or a dye, or a combination of these optical conversion elements have been realized. The towel, the solar battery of J Yangneng, which is exhausted by the forest, uses endless clean energy without fuel, and its practical use is expected. Among them, the solar cells of the lanthanum series have been researched and developed since the beginning, and they have also been popularized by the policies of various countries. Day Shixi is an inorganic material, and the yield and molecular modification naturally have limits. ~ Therefore, research on dye-sensitized solar cells is being carried out with all efforts. In addition, Graetzel et al. of the University of Lausanne University of Technology developed a pigmented two-type solar cell in which a pigment of a ruthenium complex is fixed on the surface of a titanium oxide film, which realizes an amorphous ruthenium conversion efficiency. In this way, ^ = sensitized solar cells have attracted the attention of researchers all over the world. In Patent Document 1, a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with ruthenium complex is used. In addition, there is a photoelectric conversion element which uses an inexpensive organic dye as a sensitizer, but it can be said that it is a photoelectric conversion element having high conversion efficiency. A technique for adsorbing the photoelectric conversion efficiency of the semiconductor microplate 4 201238968 41468pif by the photo-sensitizing dye of a specific structure has been proposed (for example, the light increase/decrease 2 and 3 described in Patent Documents 2 and 3). The solubility is low, so in the - fixed strip = solvent to the foot, in terms of photoelectric conversion efficiency, the amount of adsorption of the particles is not large or the main mold is not filled with a knife, so the amount of pigment used to resolve the heart for a long time 'depending on productivity [Patent Document] [Patent Document 1] U.S. Patent No. 5,463,057 [Patent Document 2] 曰 Patent No. 45% 4 No. 曰 [Patent Document 3] SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention provides a metal complex dye composition having high solubility in a solvent, and a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency. The inventors of the present invention have intensively studied and found that a metal complex dye containing a specific ligand has high solubility in a solvent. Further, since the amount of adsorption of the dye on the semiconductor fine particles can be increased, a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency can be provided. The present invention has been completed based on this finding. According to the present invention, the following is provided. <1> A metal complex dye composition comprising a metal complex dye represented by the following formula (1) and a metal complex dye represented by the following formula (5) And/or a metal complex dye represented by the following formula (6); a metal complex according to the area of 254 nm detected by HPLC (High Performance Liquid Chromatography) 201238968 The content ratio of the dye and the metal complex dye represented by the formula (6) is 0.5 to 5% in total. M1(LL1)mi(LL2)m2(21)2 . (CI1)^ Formula (1) [Formula In (1), Μ12 represents a metal atom, and LL1 is a bidentate ligand represented by the following formula (2), and is considered to be a bidentate ligand represented by the following formula (3); mi represents 1, M2 represents 1 'Zl indicates that the ligand 'is at least one selected from the group consisting of isothiocyanato, isocyanate and isocyanato; CI1 indicates that the counter ion 'm3' is required to neutralize the charge to the ion. The above integer.] R'» R.iB*' B*1 'General formula (2) [In the formula (2), R1URl4 and R21 to R24 independently represent an acidic group or a salt or a hydrogen atom thereof, RU to R14 And R21~r24 may be the same or different, but one of R11~R14 and R21~R24 is one less Or a salt thereof of the group.]

[In the general formula (3), n1 and n2 independently represent an integer of 〇~3, and Y1 and Y2 independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), but Ar1 and Ar2 independently represent the following a heteroaryl group represented by the formula (4). 6 201238968 41468pif

[In the formula (4), the compound of the formula (4) is a compound of the formula (4), and the radicals R3 to R33 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkyne atom, an oxygen atom, or at least one of which is an alkyl group. , alkoxy or alkynyl. X is a sulfur or a heterocyclic group. ]Ma atom or NR4 ' R4 is a hydrogen atom, an alkyl group, an aryl group M (LL1'(~1)(CN) · (c~ contains ▲ and formula (divalent LL) 2, Z1, Cl1, ml, m2 And m3 of m1(ll1Wu^2(cn): (Cl1) m3 General formula (6) [The meaning and general formula of 'μ1, ll1, LL2, Z1, Cl1, mb, m2 and m3 in the general formula (6) [2] The metal complex dye composition according to <1>, wherein LL2 in the formula 〇) is represented by the following formula (7).

In the formula (7), R41 to R43 and R51 to R53 independently represent at least one of a hydrogen atom, an alkyl group, 201238968-Ti-rv/opif alkoxy group 51 or Ί: Κ41 to R43. Silk, alkoxy or block 2 . At least one of R51 to R53 is an alkyl group, an alkoxy group or an alkynyl group. X1 and X are each independently a sulfur atom, an oxygen atom, a selenium atom or NR7, and R7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. [3] The metal complex dye composition according to <2>, wherein X1 and X2 in the formula (7) are a sulfur atom. The metal complex dye composition according to any one of <1>, wherein the metal complex dye represented by the formula (1) is represented by the following formula (8) Said. Rm

In the formula (8), R61 and R62 each independently represent an alkyl group, an alkoxy group or an alkynyl group, and Αι and A2 independently represent a carboxyl group or a salt thereof. [5] The metal complex dye composition according to any one of the above-mentioned (5), wherein the metal complex dye represented by the formula (5) is represented by the following formula ( 9) It is shown that the metal complex dye represented by the formula (6) is represented by the following formula (10). 8 201238968 41468pif

[In the formula (9), R7! and R72 independently represent an alkyl group, an alkoxy group or an alkynyl group, and a5 and A independently represent a group or a salt thereof. In the formula (10), R73 and R74 each independently represent an alkyl group, an alkoxy group or an alkynyl group, and A7 and A8 each independently represent a carboxyl group or a salt thereof. The metal complex dye composition according to any one of the above-mentioned items (5), wherein the metal complex dye represented by the formula (5) is represented by the following formula ( u) indicates that the metal complex dye represented by the formula (6) is represented by the following formula (12).

In the general formulae (11) and (12), R81 to R84 each independently represent an alkynyl group. A13 to A16 independently represent a radical or a salt thereof. &lt;7&gt; A method for producing a metal complex dye of the following formula (1), comprising: a metal complex dye comprising the following formula (13) and a general formula by external heating The temperature of the mixed solution of the compound of (14) increases. 201238968 β-Ι^Οδρίί M1(LL1)ml(LL2)m2(Z2)m4 · (CI1)^ General formula (13) [In the formula (13), the meanings of Μ1, LL1, LL2, Cl1, ml and m2 Same as in the general formula (1), Z2 is a 1- or 2-dentate ligand, m4 represents an integer of 1 to 2, when Z2 is a dental ligand, m4 represents 2, and Z2 is a 2-dentate ligand, m4 Indicates that 1, m5 is an integer of 0 or more. ]

MnQCN Formula (14) [In the formula (14), M11 represents an inorganic or organic ammonium ion, a proton or an alkali metal ion, and Q represents a sulfur atom, an oxygen atom or a collision atom. M'CLL'^KLL^CZ1^ - (CI1)^ Formula (1) [In the formula (1), Μ1 represents a metal atom, and LL1 is a 2-dentate ligand represented by the following formula (2)] LL2 is a bidentate ligand represented by the following formula (3); ml represents 1, m2 represents 1, m3 is an integer of 0 or more; and Z1 represents a ligand selected from isothiocyanato and isocyanide. At least one of an acid group and an isoselenocyano group; CI1 represents a counter ion when a charge is required to neutralize a charge. ]

[In the formula (2), R11 to R14 and R21 to R24 independently represent an acidic group or a salt thereof or a hydrogen atom, and R11 to R14 and R21 to R24 may be the same or different, but R11 to R14 and 201238968 41468pif R21 to R24 At least one is an acidic group or a salt thereof. ]

In the general formula (3), n1 and n2 independently represent an integer of 〇~3, and γΐ and γ2 independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), but Ar1 and Ar2 The heteroaryl group represented by the following formula (4) is independently represented. R33 R32 Formula (4) [In the formula (4), R31 to R33 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R31 to R33 is an alkyl group, an alkoxy group or Alkynyl; hydrazine is a sulfur atom, an oxygen atom, a selenium atom or NR4, and R4 is a hydrogen atom, an alkyl group, an aryl group or a hetero-matrix group. [8] The method for producing a metal complex dye according to <7>, wherein LL2 in the formula (1) is represented by the following formula (7).

In the formula (7), R41 to R43 and r5i to R53 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R41 to R43 is an alkyl group, an alkoxy group or an alkyne group. At least one of the radicals 'R51 to R53 is an alkyl group, an alkoxy group or an alkynyl group, and χι and 201238968 TI-TUOplf X2 are each independently a sulfur atom, an oxygen atom, a selenium atom or NR7, and the R7 is an argon donor or an alkyl group. , aryl or heterocyclic group. [9] The method for producing a metal complex dye according to <8>, wherein X1 and X2 in the formula (7) are sulfur atoms. The method for producing a metal complex dye according to any one of <7>, wherein the general formula (1) is represented by the following general formula (8), and the general formula (13) ) is represented by the following formula (15), and the formula (14) is represented by the following formula (10).

In the general formulae (8) and (10), M, r62, r91, and r92 independently represent a hydrogen atom, a group of A1 to A4, or a salt thereof, and in the formula (16), an inorganic or organic lining. The method for producing a metal complex dye according to any one of <7>, wherein the formula (1) is represented by the following formula (17) It is shown that the general formula (13) is represented by the general formula (18), and the general formula (14) is represented by the following general formula (19). 12 201238968 41468pif

[^(1^ A~A independently represents a rebel or a salt thereof, and Ml3 in the general formula (10) represents an inorganic or organic money ion, a proton or a metal ion.] &lt;12&gt; - a photoelectric conversion element, which is used as &lt; The metal complex dye composition according to any one of the above-mentioned items, wherein the metal complex dye composition is used as a sensitizing dye. <13> A photoelectric conversion element using w&lt;7&gt;~&lt; A metal complex dye produced by the method for producing a metal complex dye according to any one of the above-mentioned items. <14> A photoelectrochemical cell comprising the photovoltaic according to any one of <Bu> [Effect of the Invention] According to the present invention, a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency and excellent durability can be provided. The above and other features and advantages of the present invention can be appropriately referred to the accompanying drawings by The present inventors have further studied and found that gold 13 201238968-r L· is a complex compound containing a specific ligand, and has high solubility in a solvent, so that this can be improved. The amount of adsorption of the pigment on the semiconductor particles can be mentioned The present invention is based on this finding. A preferred embodiment of the photoelectric conversion element of the present invention will be described below with reference to the schematic cross-sectional view of Fig. 1. The photoelectric conversion element 1A includes a conductive support 1 and a photoreceptor layer 2, a charge transport layer 3, and a counter electrode 4 arranged in this order. The conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5. The photoreceptor layer 2 has semiconductor fine particles 22 At least a part of the sensitizing dye 21 (hereinafter also referred to as a dye) 21 sensitizing dye 21 is adsorbed to the semiconductor fine particles 22 (the sensitizing dye 21 is in an adsorption equilibrium state, and a part may exist in the charge transport layer; 3). The charge transport layer 3 The function is, for example, a hole transport layer. The conductive support 1 on which the photoreceptor layer 2 is formed serves as a working electrode in the photoelectric conversion element 1A. By using the external circuit 6 to operate the photoelectric conversion element 1 to function as a photoelectrochemical cell The role of 100.

The light-receiving electrode 5 includes a conductive branch body 1 and a photoreceptor layer 2 (semiconductor film) coated on the conductive support 1 and in which the semiconductor fine particles 22 are adsorbed with the sensitizing dye 21. The light incident on the photoreceptor layer 2 (semiconductor film) &amp; hair dye. The excitation pigment has high energy electrons. The electron self-sensitizing dye is transferred to the conduction band of the semiconductor fine particles 22 and then diffused to the conductive support. At this time, the molecules of the sensitizing dye 21 become oxides. The electrons on the electrode work by an external circuit and return to oxide, which acts as a photoelectrochemical cell. At this time, the light-receiving electrode 5 functions as a negative electrode of the battery: The photoreceptor layer 2 is composed of a porous semiconductor layer containing a layer of semiconductor fine particles Q 201238968 41468pif which adsorbs a dye described later. This pigment may be a pigment or the like partially dissociated in the electrolyte. The photoreceptor layer 2 is designed according to the purpose and has a multilayer structure. As described above, the photoreceptor layer 2 contains the semiconductor fine particles 22 to which the specific dye is adsorbed, so that the light-receiving sensitivity is high' and high photoelectric conversion efficiency can be obtained when used as a photoelectrochemical cell 1〇〇, and high durability is obtained. (Metal complex dye composition) The metal complex dye composition of the present invention contains a metal complex dye represented by the following formula (1) and a metal complex represented by the following formula (5). A complex dye and/or a metal complex dye represented by the following formula (6). The content of the metal complex dye represented by the formula (5) and the content represented by the formula (6) are 〇 5 to 5% in terms of the area detected by 254 nm of HPLC. U\hVU(^2)m2(Zl)2 . (CI1)^ General formula (1) [The metal atom of Μ1 in the formula (1), LL1 is a 2-dentate ligand represented by the following formula (2), LL2 Is a 2-dentate ligand represented by the following formula (3); and m2 is an integer of 1 'm3 is 0 or more; the Z1 ligand is selected from the group consisting of isothiocyanato, isocyanate, and selenium. At least one 'Z1' of the cyano group may be the same or different from each other, preferably the same; CI1 represents a counter ion when the charge is neutralized to the ion. r,2 R22 R'i^iR3 Formula (2) [In the formula (2), R11~r1 and R21~R24 independently represent an acidic group or a salt or a hydrogen atom thereof, and R11~14 and R21~R24 may be used. The same or different, but at least one of 15 201238968 R21 to R24 is an acidic group or a salt thereof

In the general formula (3), 'nl and n2 independently represent an integer of 〇~3, and γΐ and γ2 independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), Ar丨 and Ar2. The heteroaryl group represented by the following formula (4) is independently represented. General formula (4) [In the general formula (4), "W to R33 independently represents a hydrogen atom, an alkyl group, an alkoxy group or a block group". At least one of r31 to r33 is an alkyl group, an alkoxy group or an alkynyl group. . X is a sulfur atom, an oxygen atom, a selenium atom or NR4, and R4 is a hydrogen atom, an alkyl group, a aryl group or a heterocyclic group. 1 &amp;

Ml(LLl)mi(LL2)m2(Z1)(CN) - (CI1)^ General formula (5) L , () in the meaning of VI1, LL1, LL2, z1, Cl1, ml, m2 and m3 The same in the formula (1). ] M^LL1) mi(LL2)m2(CN)2 - (CI1)^ General formula (6) [201238968 4I4t of M1, LL1, LL2, Z1, Cl1, ml, m2 and m3 in formula (6)) 8pif The meaning is the same as in the formula (1). (A) Metal complex dye represented by the formula (1) (A1) The metal atom M1 M1 represents a metal atom. Preferably, Μι is a metal having a 4 or 6 coordination position, more preferably ruthenium, iron, osmium, copper, tungsten, chromium, molybdenum, nickel, palladium, platinum, diamond, rhenium, iridium, ruthenium, lanthanum or zinc. It is especially good for nails, iron or copper, and the best is 钌. It is preferably a price of 2. (A2) Ligand LL1 The ligand LLi is a 2-dental represented by the following general formula (2). The mi indicating the number of ligands LL1 is 1.

In the formula (2), R11 to Ri4 and R2i to R24 independently represent an acidic group or a salt thereof or a hydrogen atom, and R11 to R14 and R21 to R24 may be the same or different. R11 to RH and R to R may, for example, be a hydrogen atom or an acidic group (e.g., a carboxyl group, a carboxylic acid group, a hydroxyl group, or an acid group (the carbon number is preferably 1 to 2 Å, for example, _c〇NHOH, -CONCi^). ΟΉ, etc.), a thiol group (for example, -〇p(〇)(〇H)2, etc.) or a phosphonium group (such as _p(〇)(〇h.&gt;2, etc.) or the like. The acidic group may be bonded via a linking group, and a group in which the above-mentioned slow group, acid group, and a group is bonded via an acid group such as an acid group via a linking group is also included in the acidic group. R11 to R14 and R21~ At least one of R24 is an acidic group or a salt thereof. When R11 to R!4 and Rn to R24 are acidic groups, the acidic group is preferably an acidic group such as a carboxyl group, a sulfonic acid group or a phosphonium group, from the viewpoint of electron injection. Or such a salt, a carboxyl group or a phosphonium group or a salt thereof is more preferable, and a carboxyl group 17 201238968 -r J.-TVU^lf group or a salt thereof is particularly preferable. R1 LR14 and R2^R24 are an acidic group or a salt thereof. Or a hydrogen atom, the metal complex dye can be efficiently adsorbed to the semiconductor fine particles. (A3) Ligand LL2 The ligand LL2 is a bidentate ligand represented by the following formula (3). The number m2 of the ligand LL2 of LL2 represents 1. Double bond Z may also be the formula for the formula e.

In the general formula (3), n1 and n2 independently represent an integer of 0 to 3. Preferably, nl and n2 are 0 to 3'0~1. Y1 and Y independently represent a nitrogen atom or a heteroaryl group represented by the following formula (4). Ar1 and Ar2 independently represent a heteroaryl group represented by the formula (4). In the formula (4), R31 to R33 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an 'alkynyl group, and at least one of R31 to R33 is an alkyl group, an alkoxy group or an alkynyl group, and an alkyl group or a fast group is more preferable. Fast base is especially good. The bases may be straight keys or branches, and the carbon number is preferably 2 to 15, 3 to 12 is better, and 4 to 8 is particularly preferred. When the metal complex dye composition having such a hydrophobic substituent is used to adsorb the dye therein to the semiconductor fine particles, the water present in the electrolyte in the charge transport layer can be prevented from approaching, and the desorption of the pigment from the semiconductor fine particles can be suppressed. When the number of carbon atoms of the hydrophobic substituent is too large, it not only hinders the approach of water, but also hinders the proximity of, for example, iodine in the electrolyte, and the reduction by the redox system cannot be smoothly performed. When Y1 or Y2 is represented by the formula (4), it is preferably γι or conjugated to a pyridine ring and Ar1 and Ar2 are conjugated to a pyridine ring. Accompanied by the electron donating property of γι 201238968 41468pif or Y2 shown in the general formula, the silk occurs, and the metal of the shirt (10) molecule is in the direction of the metal complex compound, and = long wavelength Light in the area (long wave). In the formula (4), hydrazine is (4): 2 atoms, a selenium atom or NR4, R, a hydrogen atom, an alkyl group, an aryl group or a heterologous base. The X in the general formula (4) is preferably a sulfur atom or an argon, more preferably an atom, from the viewpoint of the stability of the nucleophilic species, the difficulty of oxidation, and the ease of formation. When the ligand LL2 has such a structure, it is possible to exhibit an effect of suppressing deterioration in battery performance and long-wavelength due to desorption of the dye.

A R31 R « General formula (4) The R5i group LL is preferably represented by the following formula (7), wherein r41 to R43 and independently represent a hydrogen atom, a pyridyl group, an alkoxy group or an alkynyl group. At least one of W3 is a burnt group, a silk base or a block base. At least one of r51 to r53 is an alkyl group, an alkoxy group or a block group. Each of ruthenium and osmium 2 is independently a sulfur atom or an oxygen atom: 3 NR 'R7 is a hydrogen atom, a silk, an aryl group or a heterocyclic group. , double button can be E or Z type. W3 is preferably silk, ·. It is preferably a cardinal group or an alkynyl group. In the formula (7), X1 and X2 are preferably a sulfur atom to drink an atom, more preferably. When the ligand LL2 has such a structure, when the sum of the formula (3) and the sum of u are 2 or more, it is difficult to oxidize and stabilize. 19 201238968 -Ti-ruupif

R«

The metal complex dye represented by the above formula (1) is preferably represented by the formula (8), R61 and R62 are independently a pendant group, an alkoxy group or an alkynyl group, and Al or A2 is independently a carboxyl group or a salt thereof. R61 and R62 are preferably an alkyl group or an alkynyl group. The metal complex dye represented by the formula (1) has a structure in which light of a long wavelength region is absorbed by the high electron donating property of the thiophene. Further, the vinyl thiophene bonded to the bipyridyl ring is bonded to. The substituent of the phenotype can exclude the water from approaching and can inhibit the desorption of the pigment from the semiconductor particles. Further, electron injection can be efficiently performed by a carboxyl group or a salt thereof, and light of a long wavelength region can be absorbed by an electron-donating isothiocyanate group. The metal complex dye represented by the above formula (1) has one each of L1 and LL2, and the dye is adsorbed on the surface of the semiconductor fine particles by the acidic group of LL1, and a hydrophobic group such as an alkyl group, an alkoxy group or an alkynyl group is used. The LL2 is disposed on the opposite side of the spatially semiconducting particle layer, and is effective for suppressing water contact and pigment desorption. (A4) Ligand Z1 The ligand Z1 is at least one selected from the group consisting of isothiocyanato, isocyanate and isodecyl. These groups have high electron donating properties and contribute to the long-wavelength of the pigment. The ligand Z1 is difficult to be an isothiocyano group or an isoindolyl group. (A5) CI1 in the ion CI1 pass $0) indicates whether the counter ion is required to neutralize the charge when the ion is cation or anion or has a positive ion 20 2〇1238968 4l468pif 3 mesh 2 metal in the pigment The ligand group and the number m3 taken are integers above 〇. When the dissociation group or the like has a dissociative group and the like, and the dye of the formula (1) &lt; ion a? becomes two: when the charge of the entire dye of the formula (1) is positive for the ion I, the inorganic ion is, for example, inorganic or organic. Record ions (such as tetrazolium ion, sputum ion, etc.), metal ions or protons. When the ion CI is a negative ion, it may be, for example, an inorganic or organic anion, and may be exemplified by a li anion (for example, a fluoride ion, a gas ion, a ionic ion, an iodide ion, or the like) or a substituted aryl acid ion (for example, a p-toluene). Continuation of acid ions, p-chloro pyridine ions, etc.), bismuth acid ions (eg, phthalic acid ion, 1,5, naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, etc.), alkane Sulfate ion (such as sulfhydryl sulfate ion), sulfate ion, thiocyanate ion, peroxy acid ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetic acid ion, trifluoromethanesulfonate ion, etc. . Further, the charge equalization uses an ionic polymer or other pigment having an opposite charge to the pigment, and a metal counter ion (e.g., biphenyl-1,2-dithiol nickel (in) or the like) can also be used. (B) Metal complex dye of the formula (5) or (6) The metal complex dye composition of the present invention contains a specific amount of the pigment in addition to the metal complex dye of the above formula (丨). At least one of the metal complex dye represented by the above formula (5) and the one represented by the following formula (6) is prepared according to the area % of 254 nm detected by HPLC, and the formula (5) is shown. The content of the compound represented by the formula (6) is 0.5 to 5% of the composition. The metal complex dye of the formula (5) has one cyano group as a ligand, and has two cyano groups as a ligand in the group 1 201238968 Hi^oopif 1(6). In the formula (5), the meanings of M1, ll1, ll2, bis, Cl, cucurbit m2 and m3 are the same as those in the above formula (6), M1, LL1, LL2, Z1, CI1, 0 V, I

The meanings of Li, ml, m2 and m3 are the same as those of the general formula (1), and are omitted for repetition. From the viewpoints of performance such as conversion efficiency, it is preferred that the meanings of ruthenium 1, IX1, LL2, Z1, α1, ml, m2 and m3 in the general formulae (5) and (6) are the same as those in the general formula (1). , mUl^ll^^xcn) · (CI1)m3 General formula (5) - (CI&gt;)m3 General formula (6) The cyano group has a lower electron donating property than the isothiocyanate group. Therefore, a metal complex dye represented by the general formula (5) of one cyano group and two cyano formulas (6) have a lower HOMO level, and the thief is longer, and is adsorbed to the semiconductor. When the color is sensitive, the light on the side cannot be effectively increased, resulting in a decrease in conversion efficiency. / However, when the area detected by 254 nm of HPLC is calculated by the formula (5 shows the metal complex dye and the content of the formula (6) is 金属·5~5 of the metal erb composition. When %, the conversion efficiency is not lowered, the doping of the pigment in the solution towel is drastically improved, and the amount of dye adsorption on the semiconductor particles is increased, and the photoelectric conversion efficiency is high, and the pigment solution is short. Preparation in time to improve the productivity of photoelectric conversion element fabrication. The reason for the improvement of solubility in solution is still uncertain, but it is considered that although the basic skeleton is common to the metal complex dye represented by the general formula (1), $22 201238968 41468pif 0.5 to 5% of a metal complex dye having a cyano group different in chemical nature, so the crystal arrangement of the metal complex dye is different from that of 0.5% or less. The content of the metal complex dye and the formula (6) is 〇5 to 5% based on the area detected by 254 nm of HPLC, and is obtained by analysis under the following conditions: the column is YMC YMC-Pack ODS-AM312 150 mm x 6.0 mm ID·, flow rate 0.75 ml/min, oven 40 ° C, the composition of the solution is tetrahydrofuran / water = 63 / 37 (containing 〇.ι〇 / 0 trifluoroacetic acid buffer), the measurement time is 50 minutes. When the metal complex dye represented by the general formula (5) When the metal complex dye represented by the following formula (6) is represented by the following formula (10), the metal complex dye represented by the formula (9) and the formula (10) The total content of the content shown is preferably 0.5 to 5% based on the area of 254 nm of HPLC. In the formula (9), R71 and R72 are independently alkyl, alkoxy or alkynyl groups, and A5, A6. Independently, it represents a carboxyl group or a salt thereof. In the formula (1), R73 and R74 each independently represent an alkyl group, an alkoxy group or an alkynyl group, and A7 and A8 each independently represent a carboxyl group or a salt thereof. R71 and R72 are preferably an alkyl group or an alkynyl group. R73 and R74 are preferably an alkyl group or an alkynyl group. The metal complex dye represented by the formula (5) is represented by the formula (6), and the metal complex dye is contained. The total of the ratio is 0.5 to 5% of the area detected by 254 nm of HPLC, and the absorption of the dye is long-waved due to the electron donating property of the thiophene ring, and the cyano group does not cause a significant conversion caused by short-waveization. Rate reduction 'available The effect of the cleavage is improved. The total content of the metal complex dye represented by the formula (5) and the formula (6) is preferably 〇.5 to 4.5 按 according to the area of the 254 nm detected by HPLC. /0'〇.5~4% is better, 0.5~3.5% is especially good. ΙΪ 23 201238968

&gt; Λ I R72

A® formula (9)

I ^CN f^N^j CN A7

A8 Formula (10) A preferred compound of the metal complex represented by the formula (5) is represented by the following formula (11) and the metal complex dye represented by the formula (6) is represented by the following formula ( 12) Representation. R8i~rm in the ^(11) and (12) independently represent an alkynyl group, and the eight to three to eighty 16 independently represent a rebel or a salt thereof. Since the metal complex dye of this structure is fast-radical based on r81 to r84, the effect of the long-wavelength and ε-increased by the π π* transition of the mountain due to the extension of the common (four) system can be exhibited. In addition, it is estimated that the target r81~r84 is fast two's. Therefore, the metal complex dye of the structure is increased with respect to the quinone ring r81~r84 or by the π electron, and it is possible that the pigment is adsorbed on the surface of the half grain. It is easy to occur in the middle of the molecule to facilitate long-wave enthalpy, preferably a carbon number of 3 to 13 or a branched alkynyl group, more preferably a carbon number of 3 to 8, and a particularly preferred one having a carbon number of 4 to 7.

The metal complex dye composition of the formula (12) is preferably a metal complex of the formula (1) 24 201238968 41468pif compound dye and a metal complex dye of the formula (5) and/or a formula (6) The one shown is soluble in an organic solvent. Such an organic solvent may, for example, be an alcohol solvent (methyl yeast, ethanol, isopropanol, etc.), a nitrile solvent (acetonitrile, propionitrile, decyloxypropionitrile, valeronitrile, etc.), an ester solvent (ethyl acetate, butane). Ester, etc., amidoxime solvent (dimercaptoamine, dimercaptoacetamide, N-methyl II, etc.), halogen solvent (dioxane, di-ethane, There are no particular restrictions on benzene, gas, etc., benzene, benzene, benzene, and the like. Further, it may be a mixed solvent containing a plurality of solvents. (C) Method for producing metal complex dye The metal complex dye of the formula (1) of the present invention can be produced by a method comprising the steps of externally heating to cause a metal containing the following formula (13). The temperature of the mixed solution of the compound dye and the compound of the following formula (14) increases.

Ml(LL1)ml(LL2)m2(Z2)m4*(CI1)^ General formula (13) The meanings of Μ1, LL1, LL2, Cl1, ml and m2 in the formula (13) are the same as those of the formula (1) . Z2 is a 1 or 2 tooth ligand. Z2 is preferably a halogen atom (fluorine, chlorine, bromine, iodine), water, dimethylammoniumamine, -〇_C (=〇xCH2Bu C(=0)-〇- (P an integer of 0 or more) Preferably, it is 0~6' 〇~4 is better 0~2 especially good) 'More preferably chlorine atom, water, dimercaptoamine group, especially good for gas atom. m4 Table 1~2 integer' When Z2 is a one-dentate ligand, m4 represents 2, and when Z is a 2-dentate ligand, m4 represents that when l°m4 is 2, Z2 may be the same gas, preferably the same. m5 is an integer of 〇 or more. The compound of 14) is represented by the following chemical formula: 25 201238968 —

MnQCN General formula (14) ^In the formula (4), Μ I indicates an inorganic or organic ammonium ion, a proton or a metal ion i; Q represents a sulfur atom, an oxygen atom, and a fine liver. The sub-grain M+ is preferably inorganic or organic. Ammonium ions (such as NH4+, NBu4+, Ν^Η), + metal ions (such as Na+, K+, Li+), more preferably Nh4+, 2-4, κ', especially NH4+, K+. With respect to the metal complex color of the formula (1), the absorption wavelength, that is, the electron donating property of the QCN as a ligand, Q is preferably a sulfur atom or a sulfonate, more preferably a sulfur atom. The metal complex dye represented by the formula (1) is represented by the following formula as described above. M (LLl)mi(LL2)m2(Zi)2 . (CIi)m3 In the formula (1), 'Μ1 represents a metal atom, and LLi is a 2-dentate coordination of the following, τ τ 2 4 ) It is not uniform with m2; i. /矣 is a 2-dentate ligand represented by the following formula (3); at least one of ml ί=code cyano, Z1 may be the same or different from each other ί 3 A 0 CI indicates the counter ion when the ion is required to neutralize the charge; m3 is an integer of 0 or more. R_ Formula (2) [In the formula (2), R11 to R14 and R21 to R24 are independently a hydroxyl group or a salt thereof or 26 201238968 41468pif a hydrogen atom, and Rn to R14 and R21 to R24 may be the same or different. At least one of t, R and R21 to R24 is an acidic group or a salt thereof. ]

[In the general formula (3), ηb n2 independently represents an integer of 〇~3, and γΐ, Y2 independently represents a hydrogen atom or a general formula (4) riding-aryl group, and Afl and W: show the following formula ( 4) The heteroaryl group shown. You have the general formula (4) [wherein si SR33 is independently represented by a gas atom, a pyridyl group, an alkoxy group or a block group, at least one hydroxy group, a residue group or an alkynyl group in R to R; X is a sulfur atom, Oxygen liver, _ sub or postal, hydrogen atom, recorded, aryl or heterocyclic group. The descriptions of the above general formulae (1) to (4) are the same as those described above, and are omitted for repetition. The metal complex dye of the present invention can be produced by the following synthesis scheme, and is produced by the method comprising the following step (4), (4) external heating to heat a mixture of the metal complex dye containing the above formula (10) and the compound of the above formula (10) 'Let it rise in temperature. The mixture of the metal complex dye containing the above formula (13) and the compound of the above formula (14) is preferably an organic solvent, and may be exemplified by an alcohol solvent (methanol, ethanol, propanol, isopropanol, butyl). Alcohol, etc., nitrile 4'K acetonitrile, propionitrile, methoxypropionitrile, valeronitrile, etc.), g solvent (acetic acid B 27 201238968 酉曰, Γ · butyl internal fermentation, etc.), guanamine solvent (Jude , than slightly burned ketone), South · methyl ethyl bromide, gas benzene, gas imitation, etc.), benzene, toluene gas: burning, two gas agents. Further, it may be a mixed solvent containing a plurality of solvents: a: an amine green is an alcohol solvent, a nitrile solvent, a ruthenium pigment, and a compound of the formula (14)

The method of heating the liquid to raise its temperature must be from J / . The method of heating from the outside means that the above mixture is heated by the quality of the mixture. The medium can be exemplified by oil, and =wu. The method of irradiating microwaves or the like is to absorb the microwave by the substance and convert the micron into heat by heating. It can be said that the twist from the inside does not include three heating. Internal heating by irradiation of microwaves or the like is based on heating principle and external: differently, the metal complex is directly heated, and the metal complex compound of the formula (13) contained in the test mixture is excessively heated due to excessive heating energy or the formula (Μ) The compound or the metal complex dye of the formula (1) is decomposed or the like (so that it is not preferable for the metal complex dye of the present invention). The method of external heating is preferably a method of heating the mixture by means of an oil bath or steam. The heating temperature and reaction time can be appropriately selected depending on the metal complex dye to be reacted or the solvent to be used. The heating temperature is preferably from 90 to 170 ° C, more preferably from 90 to 160 ° C, and from 100 to 15 Torr. (: Excellent, 1〇〇~14 (TC best. The reaction time is preferably 30 minutes~12 hours' 1~8 hours better, 2~6 hours especially good. 28 201238968 41408pif Metal of general formula (13) The complex dye may be obtained by introducing LL1 and LL2 into a compound having Ru as shown in the following scheme. The Ru source is not particularly limited, and examples thereof include ruthenium chloride or a hydrate thereof, and the like, and are preferably valences. The order of introduction of di-KiLi and ll2 which are divalent is not particularly limited, but is preferably introduced from LL2. z2 is often dependent on the Ru source, and may be borrowed with additives (iodinated clock, potassium carbonate, K0-C (=0) )-(CH2)pC(=0)-0K (p is an integer above 〇), etc.)). Further, the solvent can be coordinated to form Z2. Continued in the resulting metal containing formula (13) The compound (14) is added to the solution of the pigment, and the metal complex dye of the formula (1) is obtained by external heating as described above. LL2 Ru source --- solvent LL1

;Ru&lt; (Z2)m3

General formula (13)

MnQCN General formula (14) Heating* (LL1)

General formula (1) The ligand LL2 in the above formula (13) is preferably represented by the following formula (7). In the formula (7), R41 to R43 and -π each represent a hydrogen atom, a burnt group, an alkoxy group or a block group. At least Hgj is a burnt group, an alkoxy group or an alkynyl group among R41 to R43. At least one of r51 to r53 is an alkyl group, an alkoxy group or an alkynyl group. Χ1, X2 is a sulfur atom, oxygen Y, 4f atom: $NR7, R7 money atom, silk, aryl or heterocyclic group. R to R are preferably an alkyl group or an alkynyl group. R53 is preferably an alkyl group or an alkynyl group. 29 201238968 X!, X2 in the formula (7) is preferably a sulfur atom

Shixi atom, sulfur atom is better. The general formula (7) is preferably a metal complex dye of the formula (I3) which is represented by the following formula (15)

Independently represents a carboxyl group or a salt thereof. In the formula (16), M!2 represents an inorganic or organic recording ion, a proton or an alkali metal ion. R61, R62, R9!, and R92 are preferably an alkyl group or an alkynyl group. When the metal complex dye (13) and the compound of the formula (14) are in such a structure, the metal complex dye (13) has a thiophene ring which is stable to the compound (14) of the nucleophilic species, so that it can be suppressed. In an undesired nucleophilic reaction, a gas having a high desorption energy and a low nucleophilic energy is used as a leaving group, whereby a metal complex dye of the formula (8) in which the NCS group is selectively coordinated to a ruthenium atom can be efficiently produced.

General formula (8) Formula (15) Formula 6) 201238968 41468pif Preferably, the metal complex dye of the formula (13) is represented by the following formula (i8) and the compound of the formula (14) is A method of producing a metal complex dye represented by the following formula (17) by the following formula (19). In the general formulae (17) and (18), R10, R1Q2, r111 and RH2 independently represent an alkynyl group, and a9 to a12 independently represent a carboxyl group or a salt thereof. In the formula (19), M13 represents an inorganic or organic recording ion, a proton or a metal ion. R101, R102, R111 and R112 are preferably a direct bond or a branched fast radical having a carbon number of 3 to 13, wherein a carbon number of 3 to 8 is more preferable, and a carbon number of 4 to 7 is particularly preferable.

The maximum absorption wavelength of the dye represented by the formula (1) in the solution is in the range of 5 Å to 700 nm, more preferably in the range of 5 Å to 650 nm. The following is a specific example of the dye having the structure represented by the formula (1) used in the present invention, but the present invention is not limited thereto. Further, when the dye in the following specific examples contains a ligand having a proton-dissociable group, the ligand may be dissociated as needed to form a salt with the counter ion. Further, an isomer based on a double bond site or an isomer of a position based on a complex of a complex compound may be present, but the isomer may be of any type or a mixture. 31 201238968 C5H1in

D-2

D&lt;6

32 201238968. HIHOOpif

(D) Charge Transporter In the electrolyte composition used in the photoelectric conversion element 10 of the present invention, the redox pair may be exemplified by iodine and iodide (e.g., lithium iodide, tetrabutylammonium iodide, 33 201238968. -Tl- a combination of TUUpif tetrapropylammonium, etc., 桉 粗 粗 1 γ tt , chlorinated methyl viologen, 淳 己 a kylvlologen) (eg, basal essence, benzyl violet tetrafluoroborate) and Combination of enemy if, (4) benzene (such as p-benzoquinone, naphthalene dip, etc.) invites group t, bivalent iron complex and trivalent iron complex (such as k blood salt and blood a combination of ^, etc., wherein a combination of lysines is preferred. The second cation, preferably a 5- or 6-membered ring containing a nitrogen-containing aromatic cation is not an iodide salt, preferably used together = 2. Japanese Patent Re-publication No. W095/18456, Japanese Journal No., Electrochemistry No. 65, No. 923 (199), such as rust salt, rust salt, and three-pin salt. The electrolyte composition used in the photoelectric conversion element 10 of the present invention has a ratio of the ratio of the rhodium content to the heterocyclic fourth-order gas compound, preferably from 2 to 2 Gwt%, more preferably from G5 to 5 wt%. . The electrolyte composition used in the photoelectric conversion element 10 of the present invention may contain a solvent. The solvent content of the electrolyte composition towel is preferably 5 〇 Wt% or less of the total composition, more preferably 3 〇 wt% or less, and particularly preferably i 〇 wt% or less. In order to obtain high ion mobility at a low viscosity or to increase an effective carrier concentration at a high dielectric constant, or both, the solvent is preferably an ion conductivity, and a carbon compound (carbonic acid) is exemplified. , propylene carbonate, etc.), heterocyclic compounds (3-methyl 2 ♦ stimulating compounds (two Yao, two ethylene), chain _ (ethylene glycol bis, propylene glycol, two thieves, polyethylene glycol, Pro, polypropylene glycol thieves, etc.), alcohols (methanol, ethanol, ethylene glycol single ship, propylene glycol mono-, polyethylene glycol mono-, polypropylene glycol mono-thief, etc.), more (ethylene glycol, propylene glycol, Polyethylene glycol, poly 34 201238968 41468pif propylene glycol, glycol), nitrile compound (acetonitrile, glutaronitrile, methoxy b., nitrile, dicyandiethyl sulphate (Lysyl ester, vinegar vinegar, phosphine 酉 U曰Special), aprotic polar solvent (dimethyl sulfite, sulfolane, etc.), water, and the aqueous electrolyte described in Japanese Patent Laid-Open Publication No. 2000-36332, Japanese Patent Laid-Open No. 2000-36332 The electrolyte solvent described in the Japanese Patent Publication No. 243,134, and the Japanese Patent Publication No. WO/. These solvents may be used in combination of two or more. Further, as the electrolyte solvent, an electrochemically active salt which is liquid at room temperature and has a melting point lower than room temperature may be used, and exemplified by 丨_ethyl_3_methylimidazole rust Trifluoromethane acid salt, K butyl-3_methyl_pin trifluoroantimonate, etc., such as sputum, 疋, 疋 疋 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 荨 。 。 。 。 。 A polymer or an oil gelling agent may be added to the electrolyte composition used in the photoelectric conversion element of the present invention, or may be gelled by a polymerization of a polyfunctional monomer or a crosslinking reaction of a polymer (solidification). When the electrolyte composition is gelled by adding a polymer, Polymer Electrolyte Reviews-1 &amp; 2 ( JR MacCallum A CA can be added)

A compound or the like described by Vincent Co., Ltd., ELSEVIER APPLIED SCIENCE), in which case polyacrylonitrile or polyvinylidene fluoride is preferably used. When the electrolyte composition is gelated by the addition of an oil gelling agent, the oil gelling agent can be used by J. Chem. Soc. Japan, Ind. Chem. Soc., 46779 (1943), J. Am. Chem. Soc., Ill, 5542 (1989), J. Chem. Soc., Chem. Commun., 390 (1993), Angew. Chem. Int. Ed Engl., 35, 1949 (1996) 'Chem. Lett., 885 (1996) 'J. Chem. Soc., Chem. Commun., 545 (1997), etc., preferably a compound having a guanamine structure for use in 35 201238968. When the electrolyte composition is gelated by polymerization of a polyfunctional monomer, the following method is preferred: a solution is prepared from a polyfunctional monomer, a polymerization initiator, an electrolysis, and a solvent, by a casting method or a coating method. The immersion method and the impregnation sleeve are used to form a sol-like electrolyte layer on the electrode carrying the pigment, and then gelled by radical polymerization of a polyfunctional monomer. More preferably, it is a compound having two or more ethylenically unsaturated groups: vinyl stupid, ethylene glycol diacrylate vinegar, ethylene glycol dimethacrylic acid brewing, dihydric alcohol diacrylate, diethylene glycol Dimercapto acrylate, triethylene succinate &quot; I propyl benzoic acid 8, diethylene glycol dimercapto acrylate vinegar, pentaerythritol tripropylene decyl ester, trihydroxy decyl propane triacrylate, and the like. - It can be formed by polymerization of a mixture containing a single precursor, in addition to the above-mentioned polyfunctional monomer. Monofunctional monomer f or ~silicic acid (acid, methacrylic acid, itaconic acid, etc.) or decylamine or vinyl ester (vinyl acetate, etc.), maleic i cisene or t Some derived _ (sodium dimethyl sulphate, sodium salt, 'pre-dibasic acid), benzoic acid, acid-based riding acrylonitrile, diene (butadiene, cyclopentane) Ethyl, three-side B compound (benzene (10), p-chlorobenzene N-ethyl suspected beauty, ^ methyl styrene, styrene sodium, etc.), guanamine, Ν, B, Hall, Ν乙妇基_Νmethylmethamine, 1 ethyl ethoxylate, propyl propyl ethanoamine, ethylene benzoic acid, vinyl acid ● sodium, methacrylic sodium, partial Erdun ethylene, partial ethylene, ethylene (methyl ethylene), ethylene, 36 201238968 ^I408pif butene, isobutylene, N-phenyl maleimide, etc. Relative to Lai, multi-functional single Preferably, the amount of the monomer is 〇^7〇wt/., more preferably L0~50wt%. The above monomer can be jointly studied by Otsu Takayuki and Katsuyuki Yasushi, "Experimental Method for Polymer Synthesis" (Chemical Fellow) or Dalongxing "Lecture Aggregation The i-radical polymerization (1)" (Chemicals) describes a general polymer synthesis method, that is, polymerization by radical polymerization. The monomer for gel electrolyte used in the present invention can be heated, light or electron beam. Radical polymerization or electrochemical radical polymerization, particularly preferably by free radical polymerization: The polymerization initiator which can be preferably used at this time is: 2, 2, azobisisobutyrazo double (2, 4) Azo-based initiators such as _ dimethyl valeronitrile, 2, 2, azobis(2-methylpropionic acid) bis-formaldehyde 2,2 azobisisobutyric acid dimethyl vinegar, Oxidation, base, benzophenone, peroxyoctanoic acid, tertiary peroxide, etc., peroxide initiators, etc. The total amount of polymerization is preferably 0.01 to 20 wt%, more preferably Preferably, it is 0.1 to 10 wt〇/0. The weight composition of the monomer in the gel electrolyte is preferably 〇·5~% wt%, more preferably L0 〜50 wt%. The electrolyte is crosslinked by the polymer. When the composition gel 彳b, it is preferred to add a polymer having a crosslinkable reaction group f and a crosslinking agent to the composition. The preferred reactive group is a ring, a miso, a ring, and a shot. Ring, three, (4) a nitrogen-containing heterocyclic ring such as a ring K ring or a ring-nosed ring, and preferably a cross (IV) is a compound (electrophilic agent) having a functional group capable of nucleophilic attack by a nitrogen atom of 2 g, for example, a bifunctional or higher chiral burning _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ NaBr, KBr, CsBr, 37 201238968t I Λ ( Lyil.

CaBr 2 special), four-stage bromine salt (brominated tetraalkyl sulfonate, desertified pyridine rust, etc.), metal complex (ferrocyanate _ ferric cyanide, ferrocene _ ferrocene ion, etc. ), a sulfur compound (polysulfide, alkylthiol-alkyl disulfide, etc.), ruthenium pigment, hydroquinone-oxime, and the like. These compounds can also be used in combination. Further, in the present invention, a tertiary butyl group 0 or a 2-methyl group described in j. Am. Ceram. Soc., 80 (12), 3157-3171 (1997) can be added. A preferred concentration range for the basic compound such as hydrazine or 2,6-dimethylpyridine is 〇〇5 to 2Μ. Further, the electrolyte of the present invention may use a charge transport layer containing a hole conductor material. As the conductor material of the hole, a 9,9, _ snail vaccine or the like can be used. Further, the electrode layer, the photoreceptor layer (photoelectric conversion layer), the charge transport layer (hole transport layer), the conductive layer, and the counter electrode layer may be sequentially laminated. The hole transport layer can be made using a hole transport material that functions as a germanium type semiconductor. In contrast to the hole transport layer, for example, an inorganic or organic hole transport material can be used. ^, the machine hole transmission material can be exemplified by CuI, (10), then #. The other electric materials and the materials to be transferred can be exemplified by a polymer-transfer material of a polymer system and a low-molecular system. In addition, the low score + system sense, the door flat machine has, hydrazine derivatives, stupid methylamine derivatives. j, organic poly-wet is different from previous carbon-based polymers, = non-localized σ electrons contribute to light transmission, and mobility, so it is better (10) y, Rev. B, 35, period (] 987) y Electric (four) - machine ί = only good can be 'no special restrictions, can be exemplified: inter-electrical transfer and complex. Among them, it is preferred that the donor material i receives = 38 201238968 41468pif intermolecular charge transport complex. Among them, an intermolecular f-load migration complex formed by an organic donor and an organic acceptor can be preferably used. The thickness of the conductive layer is not particularly limited, and it is preferably such that the porous material can be completely buried. -

The above donor material is preferably a material in which electrons are concentrated in the molecular structure. For example, the organic organic material may, for example, be a material having an amine group, a hydroxy group, an ether group, a selenium or a sulfur atom in a molecular electronic system, and specific examples thereof include a phenylamine system, a diphenylmethane system, and an oxazole system. A phenolic or tetrathiafulvalene-based material. The acceptor material is preferably a material lacking electrons within the molecular structure. For example, the organic acceptor material may, for example, be a fullerene or a molecule having 7 or a substituent having a substituent such as a nitro group, a cyano group, a fluorenyl group or a halogen group in the electronic system, and specifically, a pcBM ([6,6]- phenyl-C61-butyric acid methyl ester), benzoquinone, naphthoquinone, etc., anthraquinone, anthrone, four gas abbreviated, tetrabromo adenine, tetracyanoquinone dioxane, tetracyano Vinyl and the like. (E) Conductive support body As shown in FIG. 1, the photoelectric conversion element of the present invention forms a photoreceptor layer 2' on the conductive support 1 which adsorbs the sensitizing dye 21 on the porous semiconductor fine particles 22. to make. As will be described later, for example, a dispersion of the semiconductor fine particles can be applied onto the conductive support and dried, and then immersed in the dye solution of the present invention to produce the photoreceptor layer 2. As the conductive support 1, a support which is electrically conductive like a metal or a glass or a polymer material having a conductive film layer on its surface can be used. The conductive support 1 is preferably substantially transparent, that is, the light transmittance is 10% or more, preferably 50% or more, and more preferably 80% or more. As the conductive support 1, a support in which a conductive metal oxide is coated on a glass or a polymer material can be used. At this time, the coating 1' of the conductive metal oxide is preferably 0.1 to 1 〇〇 g per 1 m 2 of the glass or polymer material support. When a transparent conductive support is used, it is preferred that light is incident from the side of the support. The polymer material to be preferably used may, for example, be tetraethylidene cellulose (TAC), polyethylene terephthalate (pet), polyethylene naphthalate (PEN), or syndiotactic polystyrene ( SPS), polyphenylene sulfide (PPS), polycarbonate (pc), polyarylate (PAR), polysulfone (pSF), polyacetate (PES), polyetherimide (PEI), cyclic poly Olefins, brominated phenoxy groups, and the like. In the conductive support body, a light management function can be provided on the surface, and an antireflection film in which a high refractive film and a low refractive index oxide film are alternately laminated in Japanese Patent Laid-Open Publication No. 2003-123859 can be used. The light guiding function described in JP-A-2002-260746. • In addition, it is also preferable to use a metal branch body, and examples thereof include titanium, aluminum, copper nickel, iron, stainless steel, and copper. These metals can also form alloys. More preferably titanium, aluminum, copper, and particularly preferably titanium or aluminum. The conductive branch body 1 preferably has an ultraviolet light blocking function, for example, H · , a method of changing the ultraviolet light into a visible light (four) light material, a surface of the transparent floor 2, or a method of making the outer line absorbent. The function described in Japanese Laid-Open Patent Publication No. Hei 11-250944, and the like. Niu Tongjia ^ conductive film can be exemplified by: metal (such as turn, gold, silver, Hao Cai, etc.), carbon or conductive metal oxide (indium-tin composite oxide 4 doped fluorine * conductive metal oxide Wait). The thickness of the conductive film is preferably 0.01 to 30 hui' 0.03 to 25 _ more seven 201238968 41468pif 0.05 to 20 ywm. The lower the surface resistance of the conductive support 1 is, the better the range is preferably Ω/cm 2 or less, more preferably 1 〇 Ω/cm 2 or less. The lower limit is not particularly limited to about Ι.ΙΩ/cm2. When the cell area is increased, the resistance value of the conductive film becomes large, so that the collector electrode can also be disposed. Any one or two of a gas barrier film and an ion diffusion preventing film may be disposed between the conductive support 丨 and the transparent conductive film. A resin film or an inorganic film can be used for the gas barrier layer. Further, a layer containing a transparent electrode and a porous semiconductor electrode photocatalyst may be provided. The transparent conductive film may also be a laminated structure, and a preferred method is, for example, laminating fluorine-doped tin oxide (ft 〇) on indium tin oxide (ITO). (F) Semiconductor Fine Particles As shown in Fig. 1, the photoelectric conversion element 1 of the present invention forms a photoreceptor layer 2 on the conductive support 1, and the photoreceptor layer 2 is a sensitizing dye 21 adsorbed on the porous semiconductor fine particles 22 to make. As described later, for example, the dispersion of the semiconductor fine particles 22 can be applied onto the conductive support 1 and dried, and then immersed in the above-mentioned dye solution to produce the photoreceptor layer 2. The semiconductor fine particles 22 are preferably metal chalcogenides (e.g., oxides, sulfides, selenides, etc.) or fine particles of perovskite. The metal may preferably be an oxide of titanium, tin, zinc, antimony, bismuth, vanadium, niobium or a button, cadmium sulfide or cadmium selenide. The perovskite is preferably exemplified by barium titanate or calcium titanate. Among them, titanium oxide, zinc oxide, tin oxide, and oxidized crane are particularly preferred. In the element of the present invention in which the semiconductor-conducting carrier is an electron-based n-type and the carrier is a 201238968 袅·v hole, the n-type is preferably used from the viewpoint of conversion efficiency. The n-type semiconductor has an n-type semiconductor having a high electron carrier concentration in addition to an intrinsic semiconductor having an equal concentration of carriers of an electron-charged hole (e.g., an intrinsic semiconductor) except for an impurity level. The n-type inorganic semiconductor which can be preferably used in the present invention is:

Ti02, TiSr03, ZnO, Nb203, Sn02, W03, Si, CdS, CdSe, V205, ZnS, ZnSe, SnSe, KTa03, FeS2 'PbS, InP, GaAs,

CuInSz, CuInSez, and the like. The most preferred n-type semiconductors are Ti〇2, ZnO, Sn〇2, WO3, and Nb2〇3. Further, a semiconductor material obtained by compounding a plurality of such semiconductors can also be preferably used. The method for producing the semiconductor fine particles 22 is preferably a gel-sol method described in "The Science of Sol-Gel Method" by Agfa-Shofu Co., Ltd. (1998). In addition, a method developed by Degussa to produce an oxide by hydrolysis of a chloride in an acid hydrogen salt is also preferred. When the semiconductor fine particles are titanium oxide, the sol-gel method, the gel-sol method, and the high-temperature hydrolysis method of the vaporized acid in the acid hydrogen salt are all good, and the "titanium oxide property and application technology" of Kiyono can also be used. Published, 1997) The sulfuric acid method and gas method are described. Another sol-gel method - preferably: Barbe is equal to J〇urnal 〇f the

The method described in American Ceramic Society, Vol. 80, No. 12, 3157~3171 (1997), or Burnside is equal to the method described by chemistry 她f her, toe 10, No. 9, 2419~2425. Further, as for the method for producing the semiconductor fine particles, for example, the method for producing the two-parts is preferably a four-gasification method of burning a titanium chloride, a hydrolysis of a stable chalcogenide complex, and an orthotitanic acid 42 201238968 41468pif. A method for producing a oxidized granule of a core/shell structure by hydrolyzing, partially or partially decomposing a semiconductor fine particle, and then removing a soluble P-knife. ^ The crystal structure of the arsenic can be exemplified by anatase type, brookite type or Meng, 'worker', preferably anatase type, brookite type. The second tube, the nanowire, and the nano-hybrid are dioxins, and the non-metal 70 is used. Additives in Titanium Dioxide 哎 In order to prevent the binder from being used for neeking, =2 =! Use additives on the surface. Additives are fibrous substances such as cellulose, gold II, 12, charge transfer bonding molecules such as Ben Yao and Wei compounds, and tilted dendrimers. The surface defects or the like on the shot may also be subjected to a titanium oxide test or a redox treatment before the dye adsorption. It can also be treated, hydrogen peroxide treatment, dehydrogenation treatment, TTVftii rolling, such as (9) semiconductor recording her Γ u milk, oxygen class treatment. The porous f-semiconductor fine particle coating layer can be obtained by the method of dispersing liquid on the above-mentioned conductive branch body 1, and the solid of the semi-conductive || fine particles in the semiconductor fine particle dispersion can be added into the semiconductor. The particulate dispersion is generally less than 1 Gwt%. The method for producing the conductive particle dispersion can be exemplified by the above-mentioned melt-gel method. In the case of synthesizing a semiconductor, it is precipitated as a fine particle in a solvent and is smashed into ultrafine particles by the irradiation of ultrasonic waves, etc. Method, or mechanical pulverization and grinding using a grinder or a latex =. As the dispersing solvent, one or more of water and various organic solvents can be used. There are = agents can be exemplified: methanol, ethanol, isopropanol, fragrant (four), pine (four), etc. _, Azaki _, acetic acid and other acids, three gas A, B guess. When dispersing, a small amount of a polymer such as polyethylene glycol, a base-based cellulose, or a methyl cellulose, a surfactant, an i' or a solution may be used as a dispersing aid. However, most of the dispersing aids are removed in advance by performing a film forming step w' on a conductive support or a method using a separation membrane or a centrifugal separation method. The semiconductor fine particle dispersion / semi-conductive It fine particles may be contained in an amount of 10% by weight or less, preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, particularly preferably 5% '5°/°. Below, the best 0.2 ° / ί &gt;. In other words, the semiconductor component of the semiconductor sakisaki dispersant may be less than 10% by weight of the entire dispersion liquid, and preferably contains only semiconductor fine particles and a dispersion solvent. If the viscosity of the semiconductor particle dispersion of the helmet 1 is too high, the dispersion will be agglomerated and the film cannot be formed. Conversely, if the viscosity of the dispersion is too low, the liquid will flow and the film cannot be formed. Therefore, the viscosity of the dispersion is preferably at 25. (The following is 10 to 300 N s/m2'. More preferably, it is 50 to 200 N.s/m2 at 25 ° C. Regarding the method of applying the semiconductor fine particle dispersion, the method of applying the method can be carried out by using a roll method, The immersion method, etc. The method of metering can use the air knife method, the blade method, etc. Further, the common method of the application method and the metering method is preferably: the line disclosed by Japanese Patent Publication No. Sho 58-4589 The sliding method 201238968 41468pif coating method, the curtain method, etc. described in the bar method, the specification of the U.S. Patent No. 2,681,294, etc. Further, it is preferable to use a general-purpose machine by a spin method or a spray coating method. The wet printing method is preferably a plate type, The three printing methods of lithographic and gravure are representative of gravure, rubber plate, = plate printing, etc. The new semiconductor film of the present invention has a strong cohesive force. Lincai support body & combined = raw 'In this case, you can use UV Wei treatment to make a table _ clear axis hydrophilic brother to make the coated half (four) residual dispersion lai lead f to find the body of the wire to increase, resulting in semiconductor particles The coating of the dispersion is easy to carry out. The preferred thickness of the granule layer is 〇]~1 〇〇1~30/mi' is preferably 2~25&quot;m. The carrying capacity of the conductor particles per i m2 branch body is preferably 0.5~400g, More preferably, it is 5 to 1 〇〇 g. The chemistry is to strengthen the electronic contact between the semiconductor fine particles and improve the adhesion to the branch ′ and to heat the coated layer to dry the coated semiconductor fine particle dispersion to form a porous f semiconductor fine particle layer. · In addition, in addition to heat treatment, light energy can also be used. For example, titanium can be used as a semi-conductive photo-deposited surface that absorbs semiconductor light particles 22 such as ultraviolet light. The surface of the semiconductor fine particles 22 is activated only by the light of the light, etc. The semiconductor fine particles 22 are irradiated with light that can be absorbed, and the impurities adsorbed on the surface of the semiconductor fine particles 22 are decomposed by activation of the surface thereof, which is a state in which the above object can be achieved. In the case of heat treatment and ultraviolet light, it is preferred that the rotating particles 22 are attracted to (four) light, and at the same time (10) C or more and 250 t or less or preferably 1 〇 (rc is heated to ± 15 〇ΐ or less. The briquette 22 is photoexcited and can be photo-decomposed and cleaned. Micro-45 201438968 Impurities in the grain layer 'and enhance the physical bonding between the particles. / In addition, the semiconductor fine particle dispersion is applied to the above-mentioned conductive support 俨 1 ^ can be added to the light to 'can be other treatment. For example, Japanese Patent Laid-Open Publication No. 2003-500857, etc., for example, Japanese Patent Publication No. JP-A No. Hei. Examples of the plasma, the microwave, and the electric current can be obtained by the Japanese Patent Laid-Open No. (4), and the like. For the chemical treatment, for example, JP-A-2001-357896 can be cited. In the method of applying the semiconductor fine particles 22 to the conductive support 丨, in addition to the above method of applying the semiconductor fine particle dispersion to the conductive support 1, the method described in Japanese Patent No. 2664194 (using the semiconductor fine particles 22) can be used. A method in which a precursor is coated on a conductive support crucible and hydrolyzed by moisture in the air to obtain a semiconductor fine particle film). The hydrazine can be exemplified by (Ni^hTiF6, titanium peroxide, metal alkoxide-metal complex-metal organic acid salt, etc. Further, a metal organic oxide (alkoxide, etc.) coexisted by coating may be mentioned. A method of forming a semiconductor film by heat treatment or light treatment, and a method of setting a pH of a slurry, a slurry, and a property of dispersed titanium oxide particles in which an inorganic precursor is present. In the slurry, if it is a small amount, a binder may be added, and the binder may, for example, be cellulose, fluoropolymer, parent rubber, polybutyl titanate, dimethyl cellulose, etc. with the semiconductor particles 22 or The technique related to the formation of the precursor layer can be exemplified by a physical method such as corona discharge, plasma, ultraviolet light, etc., which is a method of 〇8pif under-reduction, by means of chemistry or polyethylene dioxygen chemistry. The intermediate film for bonding such as polyaniline is used as the conductive film for coating the semiconductor fine particles 22. It is preferable to exemplify the Japanese Patent Laid-Open No. 4-No. 43 (2). Your bulletin (also the 法法法可娜m listen In addition, it is also possible to use electrophoresis-electrolytic method. It is a method of temporarily producing a coating film on a heat-resistant substrate and transferring it to a plastic. It is preferably a Japanese material. Method for transferring vinyl acetate vinegar (EVA); ^ Patent Publication No. 2003-98977, for forming a semiconductor layer on a sacrificial substrate containing an inorganic salt removable by an ultraviolet solvent, and then transferring the organic layer to the organic substrate A method of removing a sacrificial substrate, etc. The semiconductor fine particles 22 are preferably capable of adsorbing a large amount of sensitizing dyes. For example, in the case where the semiconductor fine particles U are coated on the conductive branch body i, the surface area thereof is relatively The projected area is preferably 1 〇 or more, more preferably 倍倍 or more. The upper limit is not particularly limited, and is usually about 5000 times. A preferred structure of the semiconductor fine particles 22 is, for example, Japanese Patent Laid-Open Publication No. 2001-93591, etc. The larger the thickness of the semiconductor fine particle layer, the more the amount of the sensitizing dye 21 that can be carried per unit area, so the higher the light absorption efficiency, but the generated electric (four) diffusion distance increases, and thus the loss due to charge recombination. Also getting bigger. Half The preferred thickness of the conductor particle layer varies depending on the use of the component, and is typically (^^(^/^. When used in a photoelectrochemical cell, it is preferably a dip, a melon 47 201238968 muopif = better. Semi-conducting rhyme (4) After the cloth is placed on the support, in order to make the particles mate with each other, it can also be heated at a temperature of just ~~. (:: 1 minute~1〇 hour. Using glass as a support material, the gamma temperature is preferably .6〇使用 When the polymer material is used as the branch body, it is preferably heated after film formation below 250t. The film forming method at this time may be (1) wet method, (2) dry method, (3) method (including electrolysis method). Any one of them is preferably (1) wet method or (7) dry type, more preferably (1) wet method. Further, the coating amount of the semiconductor fine particles 22 per 1 m of support is 0.5 to 500 g '5 to 1 〇〇g is better. In order to make the semiconductor fine particles 22 sensitize the dye 21, it is preferable to soak the semiconductor film 22 which is sufficiently dried in the coating liquid and the dye-dye solution of the dye of the present invention for a long time. The solvent used for the dye solution for dye adsorption can be used as long as it can dissolve the sensitizing dye 2 of the present invention. Thus, the solvent for dissolving the metal complex dye composition in the present invention is an organic solvent, and examples thereof include a nonpolar solvent, a polar aprotic solvent, a polar protic solvent, a material, and the like. Solvents, polar 14 aprotic solvents, polar protic solvents are preferred, for example, alcohol, decyl alcohol, isopropanol, toluene, tertiary butanol, acetonitrile, acetone, n-butanol, N, N-dimercaptoamine, N,N•dimercaptoacetamide, and the like. Among them, ethanol and toluene can be preferably used. The solubility of the metal complex pigment composition in the above solvent in the above invention is 25. (: Preferably, it is 100 mg/L or more, more preferably 1〇5 mg/L or more, and particularly preferably 110 mg/L or more. The pigment solution for dye adsorption containing the solvent and the pigment of the present invention can be seen as 48 201238968 HlHOOpif The adsorption of the sensitizing dye 21 may be performed before the application of the semiconductor fine particles 22, or may be performed after the application. Further, the semiconductor fine particles 22 may be simultaneously coated and adsorbed with the sensitizing dye 21. The sensitizing dye 21 is removed by washing. When the coating film is to be calcined, the adsorption of the sensitizing dye 21 is preferably carried out after the calcination, and it is particularly preferable to rapidly adsorb the sensitizing dye 21 before the water is adsorbed on the surface of the coating film. The sensitizing dye 21 may be one type of the above-mentioned dye A1, and may be further mixed with other dyes. In order to increase the wavelength range of photoelectric conversion as much as possible, a mixed dye may be selected. When the dye is mixed, it is preferred to dissolve all the pigments. The pigment solution for pigmentation adsorption. The amount of the sensitizing dye 21 is generally 0.01 to 100 millimoles per 1 m2 of the building body, preferably 0 to 1 to 5 millimoles, and 1 to 1 inch. It is especially good at this time. The amount of the sensitizing dye 21 is preferably set to 5 mol% or more. Further, the amount of the sensitizing dye 21 adsorbed on the semiconductor fine particles 22 is preferably (^(8) 丨 丨 莫 莫 〇 〇 The sensitizing effect of the semiconductor can be sufficiently obtained by setting the amount of the dye in this way. On the other hand, if the amount of the pigment is small, the sensitizing effect is insufficient, and if the amount of the pigment is too long, the pigment is not attached to the semiconductor. In addition, in order to reduce the interaction between the dyes such as association, the colorless compound may be co-adsorbed. The co-adsorbed hydrophobic compound may, for example, be a steroid compound having a carboxyl group (e.g., bile acid, pivalate) Pivaloyl acid, etc. After the sensitizing dye 21 is adsorbed, the surface of the semiconductor fine particles 22 may be treated with an amine. Preferred amines may, for example, be 4-tributylpyridine or polyvinylpyridin. When these are liquids, they can be used directly as 'soluble in organic solvents. Counter electrode 4 is used as the positive electrode of photoelectrochemical cell. Counter electrode 4 is generally synonymous with the conductive checker 1 of the previous 49 201238968, and the strength is fully maintained. In the composition, The support body of the counter electrode is not necessarily required, but it is advantageous in terms of airtightness when it has a branch body. The material of the counter electrode 4 may be, for example, a surface, carbon, a conductive polymer, etc. Carbon and a conductive polymer. The structure of the counter electrode 4 is preferably a structure having a high current collecting effect, and a preferred example thereof is exemplified by Japanese Patent Laid-Open No. Hei 10-505192, etc. The light-receiving electrode 5 can be made of titanium oxide and tin oxide ( In the case of the mixed electrode of the electrode of the titanium oxide, such as Ti〇2/Sn〇2), etc., the mixed electrode of the titanium oxide can be exemplified by Japanese Patent Laid-Open No. 3913, etc. The mixed electrode other than titanium oxide can be exemplified by: Japanese Patent Laid-Open Bulletin No. -18., issue number bulletin, etc. It is also possible to have a structure in which the first light-emitting layer of the first light-emitting layer, the conductive layer, the second photoelectric conversion layer, and the second layer are formed in this order: at this time, the first! When the dye used differs from the J Μ α ^ 5/ used in the second electroconversion layer, the absorption spectrum is preferably different. The creator 2 electrode 5 can also be formed in series in order to increase the utilization of incident light, etc., as described in Japanese Patent Laid-Open Publication No. 9 and the like. In the layer of the light illuminating ^5, it is also possible to provide effective light scattering and anti-shipping, and it is preferable to exemplify the functions described in the Japanese Patent Publication. The reverse current caused by the direct contact of the force 4/6 electrolysis solution with the electrode, and the conductive layer between the conductive layer and the thin layer of the semiconductor layer are preferably formed to prevent short-circuiting, such as the Japanese version of G6_5_. The electrode 5 is in contact with the counter electrode 4. It is preferable to use a spacer 50 201238968 41468pif or a member, and a preferred example is a Japanese Patent Application Laid-Open No. 2 publication. Gynecological single 7〇, module sealing method compares: use polyisobutylene heat curing 曰4 lacquer resin, photocurable (methyl) propylene women's resin, epoxy resin: ionic polymer resin, flour The method of oxidation of the oxidized material ship, the method of melting the low-melting glass (four) and the like. When glass frit is used, the powder can be glassy to the acrylic tree as a binder. [Examples] Hereinafter, the present invention will be described in detail by way of example, but the present invention is not limited thereto. 1. Preparation of crude purified product of metal complex pigment The crude purified product of the metal complex is prepared by the following method (1) by external heating, (2) by microwave heating, and then purified by 2 . (1) Preparation of crude purified product of externally heated metal complex dye (a) Preparation of crude purified product of metal complex dye D-20 The general formula shown in the above specific example was prepared by the method shown below. A crude purified product of D-20 in the metal complex dye of (]). &lt;Coordination Synthesis&gt; 1-Heptyne Pd2(dba)3 PPh3 d-1-1 d»1*-2 CsHnH C5Hiin d-V3

CsHunCsH^n

51 201238968t &lt;complexation

&lt;ligand synthesis&gt; (1) Preparation of compound d-1-2 25 g of dM, 3.8 g of pd2 (dba) 3, 8 6 g of triphenylphosphine, 2/g of copper iodide, 25.2 g of 1 The heptyne was stirred at room temperature in 7 mL of triethylamine, 5 mL of tetrahydrofuran, and stirred at 8 ° C for 45 hours. After concentration, it was purified by column chromatography to give 264 g of compound d. (ii) Preparation of dl-4 6.7 g of cM-3 was dissolved in 2 mL of tetrahydrofuran (THF) under nitrogen atmosphere at -15 ° C, and 2.5 equivalents of separately adjusted two were added dropwise to dl-3. Lithium isopropyl amide (LDA), stirred for 75 minutes. Then, a solution obtained by dissolving 15 g of d-1-2 in 30 mL of THF was added dropwise, and the mixture was stirred at 〇〇c, and then stirred at room temperature overnight. After concentration, 150 mL of water was added, and the organic layer was washed with brine, and the organic layer was concentrated with 150 mL of dioxane. The obtained crystal was recrystallized from decyl alcohol to give 18.9 g of d-1-4. 52 201238968 41468pif (iii) Preparation of compound d-1-5 · Add 13.2 g of dl-4, 17 g ppTS (p-benzoic acid 0 to bite rust) to 1000 mL of toluene and heat to reflux under nitrogen atmosphere 5 hours. After concentration, the organic layer was concentrated with a saturated aqueous solution of sodium bicarbonate and dichloromethane. The crystals were recrystallized from methanol and m. &lt;Compounding&gt; The metal complex dye D-20 was prepared by external heating and complexation. 3 〇g of d-1 -5 and 1.64 g of d-1 -6 synthesized above were added to 35 mL of DMF (dimethyl decylamine), and stirred at 7 ° C for 9 minutes in a dark room. At this time, it is heated from the outside by an oil bath. Then add 1.3g of d-1-7 and add 270 mL of DMF 'heated for uo minutes under i6 (TC). At this time, heat from the external oil bath. Then add u.25g ammonium thiocyanate and at 1;3 (The mixture was stirred for 2 hours at rc. At this time, it was heated from the outside by an oil bath. After concentration, 3 mL of water was added and filtered, and washed with diethyl ether to obtain a crude purified product of D 2 oxime. (b) Metal complex pigment Preparation of crude purified product of Di〇 The crude purified product of D-10 in the pass metal complex dye shown in the above specific example was prepared by the method shown below. &lt;Coordination Synthesis&gt; By the following method Preparation of compound d-2-5. (i) Preparation of compound d-2-2 25 g of d_2-1 was dissolved in 50 mL of THF and the equivalent of n-butyl (H6 mQl/L) was cooled in an ice bath. Then, 1.5* of dimethylformamide was added dropwise, and the mixture was stirred at room temperature for one hour. The aqueous solution of ammonium chloride was added dropwise, and the liquid separation and extraction were carried out. After concentration, the pressure was reduced to 53. Purification gave 25.6 g of compound d-2-2. (ii) Preparation of d-2-4 In the preparation of the metal complex dye D-20 of (a), the d used for the preparation of d-1-4 -1-2 is replaced by d_2-2, the same Preparation of d-2-4 using d-2-3. (iii) Preparation of compound d-2-5 In the preparation of the metal complex dye D-20 of (4), d- used for the preparation of d-1-5 1-4 was changed to d-2-4, and d-2-5 was prepared in the same manner. &lt;Compounding&gt; The complexation of the metal complex dye D-10 was prepared by external heating. Purified product: The crude purified product of D-10 was prepared in the same manner except that d-1-5 used in the preparation of D-20 in (a) was replaced by d-2-5. nBuLi CeH, S ^—CeH^CHO d-2-1 d-2-2 d-2-3

C6H13 CeH”

CeH13

54 201238968 41468pif rn Preparation of crude purified product of microwave-fused metal complex pigment (4) Preparation of crude purified product of complex dye D-20, 3,0 g of compound d-1_5 and i.64 g D-1-6 Add 35mL DMF ν Λ曰 to Zhongzhao microwave (frequency 2.45GHz) and stir at 10°C at 10°C. Add 1.3 g of d-1-7 and add 270 mL DMF. ^ Waves are heated at 16 ° C for a few minutes. Niigata 14.25 g thiocyanide was stirred by the above microwave at 13 ° C for 1 。. After concentration, 3 (8) m of water was added and filtered, and the mixture was washed with diethyl ether to give a crude purified product. (b) Preparation of crude purified product of metal complex dye D1 _ - external heating was changed to microwave heating (conditions are the same as (2) (a)), and in addition, 2.5 § 〇_1 获得 was obtained in the same manner. Crude purified material. 2. Preparation of a metal complex dye composition containing a metal complex dye of the formula (5) and/or a metal complex dye of the formula (6) and a metal complex dye (1) Metal using external heating Preparation of complex pigment composition -1. The crude purified product of the metal complex dye D-20 obtained in (l) (a) is dissolved in a methanol solution with tetrabutylammonium hydroxide (TBAOH). Column purification of Sephadex LH-20 (trade name manufactured by GE Healthcare). The fraction of the main layer was recovered and concentrated, and then cerium nitrate was added to obtain a precipitate. After filtration, it is washed with water and diethyl ether, and the metal complex dye containing the general formula (5) and the metal complex dye of the general formula (6) having D-17 as a main component are mismatched. Pigment composition. When purifying the tube, 50 g of the carrier liquid is used for 2 〇〇mg of the crude purified product, and the number of times of performing the column purification is changed to i to 4 times, and the metal complex dye containing the general formula (5) is obtained. At least one metal complex dye composition of the metal complex dye of the formula (6) (Example 4). 55 201238968

I (1) (the crude purified product of the obtained metal complex dye D_10 is purified in the same manner, and the metal complex dye of the formula (5) and the metal of the formula (6) having D_u as a main component are obtained. At least one metal complex dye composition of the complex dye (Examples 5 to 8). Further, the obtained metal complex dye composition is further dissolved in a decyl alcohol solution together with tetrabutylammonium hydroxide. Adding 0.1 N ceric nitrate solution to pH=〇, and obtaining at least one metal of the metal complex dye of the formula (5) and the metal complex dye of the formula (6) having D1〇 as a main component The complex pigment composition (Examples 9 to 12). (2) Preparation of the metal complex dye composition by microwave heating is compared with (1), and 1(2) is purified in the same manner as (1) ( a) a crude purified product of the obtained metal complex dye D 2 制备 prepared by microwave heating, and a metal complex dye containing the general formula (5) and a metal of the general formula (6) which are mainly composed of CM7 At least one metal complex dye composition of the material dyes (Comparative Examples 1 to 3). Further, the metal obtained by purifying the ruthenium in the same manner is entangled. a crude product of the dye D-10, and at least one of the metal complex dye containing the formula (5) and the metal complex dye of the formula (6) having d-u as a main component The pigment composition (Comparative Examples 5 to 7). Further, the obtained metal complex dye composition was further dissolved in a decyl alcohol solution together with tetrabutyl hydride, and a N ceric nitrate solution was added dropwise until PH = a metal complex dye composition containing at least a metal complex compound of the formula (5) and a metal complex dye of the formula (6) having D-10 as a main component (Comparative Example) 9~11). (3) Preparation of metal complex pigment by HPLC fractionation. Purification by HPLC 1. (1) (4) The crude purified product was firstly dissolved in a decyl alcohol solution of sulphuric acid tetra 56 201238968 41468pif butylammonium. And then use the Shiseido CapceU Pak UG120 Hungarian mmx25〇mm LC fractionation column purification solvent composition to set methanol / water == 85 / 15 ~ 95 / 5. After the main layer of the fraction is recovered and concentrated A precipitate was obtained by adding 0.2 hydrazine nitrate, and after filtration, it was washed with water and diethyl ether to obtain 3.2 g of a metal complex dye D represented by the general formula (1). -17 (Comparative Example 4) The structure of the obtained metal complex dye D-17 was confirmed by nuclear magnetic resonance (NMR) measurement and liquid chromatography-mass spectrometry (LC-MS). b-NMR pMSO-d6, 働MHz) : Aromatic zone 5 (ppm): 9.37 (1H, d), 9.11 (1H, d), 9.04 (1H, s), 8.89 (2H), 8.74 (1H, s), 8.26 (1H, d), 8.10 -7.98 (2H), 7.85-7.73 (2H), 7.60 (1H, d)? 7.45-7.33 (2H), 7.33-7.12 (5H, m), 6.92 (1H, d) MS-ESI m/z : 1023.143 (M+H)+ The obtained metal complex dye D-17 (Comparative Example 8) was dissolved in tetrahydrocarbamate: water = 63:37 (0.1% trifluoroacetic acid) to prepare a concentration of 8 5 μιη〇1/ [The solution was measured by spectroscopic absorption using a U-4100 spectrophotometer (product manufactured by Hitachi, Ltd.), and the absorption maximum wavelength was 568 nm. Similarly, the metal complex dye D-11 (Comparative Example 8) was also purified by HPLC using the crude purified product obtained from LU) (b). MS-ESI m/z: 1003.2 (M+H)+ then 'dissolved in THF: water=63:37 (0.1% trifluoroacetic acid) to prepare a solution of 8.5 μιηοΙ/L, using U-4100spectroph〇t〇meter (manufactured by Hitachi, Ltd.) The spectral absorption measurement was carried out, and the absorption maximum wavelength was 566 nm. The obtained metal complex dye D-11 was dissolved in a decyl alcohol solution together with tetrabutylammonium hydroxide, and 0.1 N ceric nitrate solution was added dropwise until pH=〇, and 57 201238968 t Τ Λ I v/w L/li was obtained. - D-10 (Comparative Example 12). MS-ESI m/z: 1003.2 (M+H)+ then 'dissolved in THF:water=63:37 (0.1% trifluoroacetic acid) to prepare a solution of concentration 8.5 μιηοΙ/L' U-4100 spectrophotometer (manufactured by Hitachi, Ltd.) The spectroscopic absorption measurement was carried out, and the absorption maximum wavelength was 571 nm. 3. Measurement of the content ratio of the metal complex dye of the formula (5) and/or the metal complex dye of the formula (6) in the metal complex composition according to the following (a) to (b) 2. The metal complex dye ' contained in the obtained metal complex dye composition was determined and its content was determined. The values are shown in Table 1. (a) Measurement by high performance liquid chromatography The obtained metal complex pigment composition was subjected to HPLC measurement under the following conditions. The content ratio of the metal complex dye of the formula (5) and/or the metal complex dye of the formula (6), together with the LC-MS measurement results described later, is identified by identifying a metal complex having a CN ligand. The compound was obtained. (Measurement conditions for high performance liquid chromatography (HPLC))

Equipment used: System controller SCL-10AVP Column oven CTO-10ASVP Detector SPD-10AVVP Deaerator DGU-14AM Liquid supply unit LC-10ADVP (product name manufactured by Shimadzu Corporation) Column ·· YMC-PackODS-AM, model number AM-312 size 150x6.0 mmI.D. (manufactured by YMC Co., Ltd. Japan) Flow rate: 0.75 mL/min Eluent: THF/water = 63/37 containing 〇·ΐ% triacetic acid 58 201238968 41468pif Temperature :40°C Detection wavelength: 254 nm (b) Identification of metal complex pigment in metal complex pigment composition. Measurement of LC-MS of metal complex pigment composition to identify metal complex pigment composition A structure containing a metal complex pigment. LC-MS was carried out by the following method. (Measurement conditions of LC-MS)

Device: Applied Biosystems QSTAR pulser (trade name), Applied Biosystems, Inc. Ionization method: ESI-posi Detection method: TOF-MS Column: YMC-Pack ODS-AM, Model AM-312 Size 150x6.0 mml.D. (Manufactured by YMC Co" Ltd. Japan) Flow rate: 0.75 mL/min

Dissolved solution. THF/water = 63/37 contains 〇·1%^ gas acetic acid Temperature: 40°C The metal complex compound composition containing D-17 as a main component is a metal complex of the formula (5) The detection of the substance dye and the formula (6) has the following structure. Further, the acid-based counter ion was detected as a proton by the inclusion of trifluoroacetic acid in the eluent. In the metal complex composition, the counter ion may be proton or tetrabutylammonium. 59 201238968 'Tl'tuopif

CeHn C$H”

C5H„

959.194 (M+H)+ 515 nm MS-ESI m/z : 991.163 (M+H)+ Maximum absorption wavelength: 542 nm The composition of the metal complex with D-ll as the main component and D1〇 The metal complex dye of the formula (5) and the formula (6) contained in the metal complex dye composition of the component were all detected as follows. Further, the ion pair of the acidic group is detected as a proton by the trifluoroacetic acid in the eluate, but the counter ion in the metal complex composition may be a proton or a tetrabutylammonium. C6H13

〇βΗ13

MS-ESI m/z ' 971.194 (M+H)+ 939.223 (M+H)+ Absorption maximum wavelength: 540 nm 513 nm 4. Evaluation of the solubility of pigment in solution 201238968 41468pif Make the metals shown in Table 1 wrong The pigment composition 12 mg was dissolved in a mixed solvent of 50 mL of hydrazine and 50 mL of decyl alcohol in a dark room, and the mixture was stirred at 25 ° C for 15 minutes with a stirring wing to obtain a pigment solution. The amount of the metal complex dye represented by the formula (1) in the solution was quantified using the HPLC apparatus used in the above method. The dissolved amount is 11.0 mg or more and 12.0 mg or less is marked as A, 10.0 mg or more and less than 11_〇mg is marked as Β, 9·〇mg is less than 1 〇〇 is marked as C, and less than 9.0 mg is marked as D, where a and B To be qualified. 5. Evaluation of Adsorption of Pigment on Semiconductor Microparticle Electrode (Production of Semiconductor Microparticle Electrode) A fluorine-doped tin oxide was formed on a glass substrate by a sputtering method as a transparent conductive film, and the transparent conductive film was divided by laser cutting. 2 parts. Next, 32 g of anatase-type titanium oxide (manufactured by Aer〇sil Co., Ltd., Japan) was blended in a 100 mL mixed solvent containing water and acetonitrile in a volume ratio of 4:1, and a mixing regulator was used for the rotation/revolution type. Disperse and mix uniformly to obtain a semiconductor fine particle dispersion. This dispersion was applied to a transparent conductive film at 500. (The semiconductor microparticle electrode was produced by heating down. A dispersion containing Si〇2 particles and rutile-type titanium oxide having a mass ratio of 4〇:6〇 was produced in the same manner, and the dispersion was applied onto the light-receiving electrode. The insulating porous body was formed by heating at 500 ° C, and a carbon electrode was formed as a counter electrode. Next, the glass substrate on which the above-mentioned insulating porous body was formed was immersed in an ethanol solution of the metal complex dye composition of Table 1 for 12 hours. The sensitized pigment glass was immersed in a 4.tributylphosphonium (tetra) 1Q% ethanol solution for 30 minutes, then washed with ethanol and naturally dried. The thus obtained photosensitive | thickness was 10 / mi, and the coating amount of the semiconductor fine particles was 2 〇. g/m2. 9 201238968 wa * v/vr^/ΐί (Adsorption evaluation) 2 3 cm 2 of the semiconductor fine particle electrode produced by the above method was bubbled in each dye solution for 3 minutes in the dark to 40 C. 〇% tba〇h The sterol solution was subjected to dye desorption of the semiconductor fine particle electrode after the dye adsorption, and the initial adsorption amount of each dye was quantified by HPLC. The amount of the solution t dissolved was determined by the same method as the HPLC used in the above method. Adsorption amount! (4) The upper time scale is A '0·9 mg or more and less than μ mg is B, 〇 above ^〇.9mg^C>^〇.7mg^D^tA^B^^〇6. Photoelectric conversion efficiency evaluation of photoelectric conversion elements ( Production of semiconductor microparticle electrode) In the sputtering method, the oxygen is tilted as a transparent conductive film on a glass plate, and the transparent conductive film is divided into two parts by a sputtering process. The volume ratio is 4: 32 g of anatase-type titanium oxide (p_25 (product name) manufactured by Nippon Aerosil Co., Ltd.) was mixed with water and acetonitrile in _mL mixed solvent, and uniformly dispersed by a rotation/revolution type mixing shoe to obtain a semiconducting m. Recording the dispersion. The dispersion is applied to a transparent conductive film and heated at 50 ° C to produce a semiconductor microparticle electrode. Continue to produce a ruthenium particle with a mass ratio of rutile in the same manner. The sub-ship was coated on the above-mentioned light-receiving electrode, and an insulating porous body was formed by heating at 5 〇 0 ^, and a carbon electrode was formed as a counter electrode. In the dye solution shown in Table 1 prepared in 4', it was formed: Insulating porous body of glass substrate dip 12 small. Will be dyed with sensitized color = glass in 4: tertiary butyl (four) brain After immersing in the alcohol solution for % minutes, it was washed with ethanol and dried naturally. The thickness of the photosensitive layer obtained in this way was 62 201238968 41468pif was 10 μm 'the coating amount of the semiconductor fine particles was 2〇g/m 2 . Then, the semiconductor fine particles were separated. A 50 μm thick thermoplastic polyolefin resin sheet is disposed opposite to the platinum sputtered FTO substrate, and the tree portion is thermally melted to fix the two plates. Further, the liquid injection port is opened from the platinum sputtering electrode side in advance. The electrolyte solution was injected and filled between the electrodes, and the peripheral portion and the electrolyte injection port were sealed with an epoxy-based sealing resin. A silver paste was applied to the current collecting terminal portion to prepare a photoelectric conversion element. The electrolytic solution was a decyloxypropionitrile solution using dimercaptopropylimidazolium rust (0.5 m〇1/L) and iodine (0.1 mol/L). (Evaluation of Photoelectric Conversion Element) Light of a 500 W xenon lamp (manufactured by Ushio Electric Co., Ltd.) was passed through a 5ι 5 filter (manufactured by Oriel) and a sharp cut filter (Kenk〇L_42) to prepare a UV-free simulation. sunshine. The light intensity was 89 mW/cm2. An alligator clip is attached to each of the conductive glass plate and the platinum vapor-deposited glass plate of the photoelectrochemical cell, and each of the alligator clips is connected to a current-voltage measuring device (Keithley SMU238 type (trade name)). The simulated sunlight is irradiated from the side of the conductive glass plate, and the generated electricity is measured by a current-voltage measuring device. The photoelectrochemical cell conversion efficiency determined thereby is 9.0% or more and is marked as A, 8.0% or more and less than 9.0% is marked as B, 7.0% or more and less than 8.0% is marked as C, and less than 7.0% is marked as D 'where A and B are To be qualified. 63 201238968 Table 1 Metal complex dye (*) Content of pigment (%) of the formula (5) Content of pigment of the formula (6) (%) Method for purification of metal complex dye production method Adsorption t —.—. Conversion efficiency Example 1 D-17(0.5) 0.4 0.1 External heating (oil bath) Sephadex LH-20 BBB Example 2 D-17(2.0) 1.8 0.2 External heating (oil bath) Sephadex LH-20 AAA Example 3 D-17(4.1) 3.6 0.4 External heating (oil bath) Sephadex LH-20 A-A — Example 4 D-17(5_0) 4.5 0.5 External heating (oil bath) Sephadex LH-20 AA· — A Example 5 Dl 1 (0.5 0.4 0.1 External heating (oil bath) Sephadex LH-20 BB &quot; — B Example 6 D-ll(1.8) 1.6 0.2 External heating (oil bath) Sephadex LH-20 AAA Example 7 Dl 1 (3.8) 3.5 0.3 External heating (oil) Bath) Sephadex LH-20 A - A Example 8 Dl 1 (4.8) 4.4 0.4 External heating (oil bath) Sephadex LH-20 AA - A Example 9 0-10 (0.5) 0.4 0.1 External heating (oil bath) Sephadex LH-20 B ---- B Example 10 D-10(1.9) 1.7 0.2 External heating (oil bath) SephadexLH-20 BB ----- B Real Example 11 D-10(3.5) 3.2 0.3 External heating (oil bath) Sephadex LH-20 AA .··· A Example 12 D-10(4_9) 4.5 0.4 External heating (oil bath) Sephadex LH-20 AA ——. A comparison Example 1 D-17(5.3) 4.7 0.6 Microwave Heating Sephadex LH-20 AB~ — c Comparative Example 2 D-17(5.5) 5.0 0.5 Microwave Heating. SephadexLH-20 AC &quot; ---- D Comparative Example 3 D-17 (7.0) 6.3 0.7 Microwave heating Sephadex LH-20 A c D Comparative Example 4 Dl 7(0) 0 0 External heating (oil bath) HPLC preparation DD ΊΓ Comparative Example 5 D-ll(5.3) 4.7 0.6 Microwave heating Sephadex LH-20 AB c Comparative Example 6 Dl 1 (5.7) 5.0 0.7 Microwave Heating Sephadex LH-20 A cn Comparative Example 7 Dl 1 (6.9) 6.1 0.8 Microwave Heating Sephadex LH-20 A c —^_ n Comparative Example 8 Dl 1(0) 0 0 External Heating (oil bath) HPLC preparation DD - n Comparative Example 9 D-10 (5.3) 4.6 0.7 Microwave heating Sephadex LH-20 AB r Comparative Example 10 D-10 (5.6) 5.0 0.6 Microwave heating Sephadex LH-20 ACD Comparative Example 11 D- 10(7_l) 6.2 0.9 Microwave heating Sephadex LH-20 AC ----- ΤΛ Comparative Example 12 D-10(0) 0 0 External heating (oil bath) HPLC preparation DD &quot; ---- D (*) brackets It is understood from Table 1 that the general formula (5) and the formula (6) contain a quasi-C%). When the metal complex dye represented by the formula (5) or (6) is too large, there is a problem in photoelectric conversion efficiency. When the color of the metal complex is too small, the amount of the pigment dissolved, the amount of adsorption, and the photoelectric conversion efficiency are also problematic. On the other hand, the metal complex dye composition of the present invention can satisfy any of the characteristics. When the content of the metal complex dye represented by the formula (5) or (6) is large, the solubility tends to increase; and the content of the metal complex &gt; 5 (%) tends to decrease the amount of adsorption. The case is estimated to be the general formula (5) or (6). The low conversion efficiency metal complex pigment preferentially adsorbs, resulting in conversion yield. 64 201238968 41468pif The present invention is as described above with respect to its embodiment, but unless otherwise specified It is to be understood that the invention is not limited to the details of the invention, and is intended to be construed in a broad scope. The present application claims priority to Japanese Patent Application No. 2011-054802, filed on Jan. 11, 2011, which is hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an embodiment of a photoelectric conversion element manufactured according to the present invention. [Description of main component symbols] 1 : Conductive support 3: Charge transport layer 5 : Light-receiving electrode 10 : Photoelectric conversion element 22 : Semiconductor fine particle 2 : Photoconductor layer 4 : Counter electrode 6 : External circuit 21 : Sensitized dye 100 : Photoelectrochemistry battery

65 S

Claims (1)

201238968 HIHOOpif VII. Patent application range 1. A metal complex dye complex, including a metal complex dye represented by the following formula (1) and a formula (5) The metal complex dye and/or the metal complex dye represented by the following formula (6); the area of the formula (5) measured by HPLC (high performance liquid chromatography) at 254 nm The content ratio of the metal complex dye and the metal complex dye represented by the formula (6) is 〇5 to 5%, M (LV) ml (LL2) m2 (zx) 2 (CIi). M3 In the formula (1) 2(1), 'Μι denotes a metal atom, the mountain is a hexyl group represented by the following formula (2), and LL is a 2-dentate ligand represented by the following formula (3), 1, m2矣1 1 · 71 * The acid group and the isocyanate group are at least 2 iso-sulfuryl groups, and the opposite ion is ion-on-charge. The number is the number of the table = the number of ions is to be neutralized by the ions, R ,v* R&quot; R2' R12 general formula (2) General formula (3) 66 201238968 41408pif [In the general formula (3), nl and n2 independently represent an integer of 0 to 3, and Y1 and γ2 independently represent a hydrogen atom or a 7-heteroaryl group of the following formula (4). However, Αι·1 and Ar2 independently represent a heteroaryl group represented by the following formula (4): R3' Formula (4) [In the formula (4), R31 to R33 are independently 矣+ and κ Γ two (four), a pyridyl group, an alkoxy group or an alkynyl group, at least one of R31 to R33 is a ruthenium, alkoxy or alkynyl group; X is a sulfur _R4'R4 is a gas atom, a stilbene group , aryl Mi (LLi) ml (LL2) m2 (Zl) (CN) · (cil) 'm3 General formula (5) [In the general formula (5), Μ 1,! ^1,]^ 7l μ has the same meaning as in the formula (1)], CI, 仏1112 and m3 of the formula (6) Ml(LLl)ml(LL2WCN)2 · (cil)m3 [in the formula (6), 71 ρτ1 has the same meaning as in the general formula (1)]. 2. CI, na, m2, and m3 2. For example, the patented mine image, wherein the general formula m is composed of the metal complex pigment described in the first item, and LL2 is represented by the following general formula (7): 67 201238968 General formula (7) [In the general formula (7), 'R41~; R43 and R5, and R53 independently represent a halogen atom, an alkyl group, an alkoxy group or an alkynyl group; at least i of which are alkyl groups, alkoxy groups; R51 At least one of R53 is an alkyl group, an alkoxy group or an alkynyl group; X1 and X2 are each independently a sulfur atom, an oxygen atom, a selenium atom or NR7, and R7 is a nitrogen atom, an alkyl group, an aryl group or a heterocyclic group. ]. 3. The metal complex dye oxime product according to claim 2, wherein X1 and X2 in the formula (7) are sulfur atoms. 4. The metal ruthenium dye composition according to any one of claims 1 to 3 wherein the metal complex dye represented by the formula (1) is represented by the following formula (8): In the formula (8), R61 and R62 A2 independently represent a carboxyl group or The pigment composition, wherein the metal complex dye represented by π 地地 and metal ^ ' (5) is described in detail. 5. For example, the scope of the patent patent is 68 201238968 41468pif (9) represents: The metal complex dye represented by the formula (6) is represented by the following formula [In general formula (9), R71 and only 72 R independently represents an alkyl group, an alkoxy group or an alkynyl group, and A5 and A independently represent a fluorenyl group or a salt thereof; in the formula (10), R73 and R74 independently represent an alkyl group, an alkoxy group or a block group, and A and A are independently slow. Base or its salt]. The metal complex dye composition according to any one of claims 1 to 5, wherein the metal complex dye represented by the formula (5) is represented by the following formula (11). The metal complex dye which is not represented by the formula (6) is represented by the following formula (12): 69 201238968 H-l^OOpif [In the formulae (11) and (12), R81 to R84 independently represent an alkynyl group; and A13 to A16 independently represent a carboxyl group or a salt thereof]. 7. A method for producing a metal complex dye of the following formula (1), comprising: a metal complex dye comprising the following formula (13) by external heating and a general formula (14) The temperature of the mixture of the compounds is increased; M1(LL1)ml(LL2)m2(Z2)m4 · (CI1)^ General formula (13) [In the formula (13), Μ1, LL1, LL2, Cl1, ml and The meaning of m2 is the same as in the general formula (1); Z2 is a 1-dental or 2-dentate ligand; m4 represents an integer of u, when Z2 is a dental ligand, m4 represents 2, and Z2 is a 2-dentate ligand. M4 represents 1; is an integer above ]] MUQCN Formula (14) Formula (1) · (CIi)c [In the formula (1), Μ1 represents a metal atom, Ll1 2dentate ligand, ll2 is as follows The formula represented by the following formula (2) represented by the formula (3), m2 represents 1, m3 is 1 or 2; ^ table 2 tooth ligand; ml thiocyanate, isocyanate group and The incompatible group of the isoselenocyano group is selected from the group of isotopes, which means that the ions are neutralized by the ions of 201238968 41468pif ions. R'2 Rn R2' R22 Formula (2), in formula (2) 'R~R 4 and R21~R24 independently represent acid atoms, R11~R14 and R21~P24H soil X-, orphan: 3⁄4 wind, R21 p24tb , R may be the same or different; wherein, one of R11 to R14 R is an acidic group or a salt thereof] In the formula (3) t, in the above 3), 'nl,,, n2 independently represent an integer of 0 to 3, and γ1 and Y2 are independent of each other: 虱; sub- or the following general-purpose filament, but A is not The heteroaryl group represented by the formula (4) and the r-independent A R31 rM formula (4) [in the formula (4), r3i to r33 groups, s + in R31 to R33 represent a gas atom, a silk, An alkoxy group or an alkyne atom, an oxygen material, or a residue or a residue; X is a sulfur or a heterocyclic group]. ', or 1^1^4, 〆 is a hydrogen atom, an alkyl group, an aryl group. 8. As in the patent application range, the metal complex dye described in the seventh item is in the general formula (1). The general formula (7) represents: 71 201238968., [In the formula (7), 'R41 to R43 and rm to R53 independently represent a hydrogen atom, an alkyl group, an alkoxy group or a group; and at least one of R41 to R43 is a stilbene group, a silk group or a block group 2; R51~ At least one of R53 + is a silk, :oxy or alkynyl group; X1 and X2 are each independently a sulfur atom, an oxygen atom, a lithiate atom or NR7, and R7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group] The method for producing a metal complex dye according to the invention of claim 8, wherein the oxime and oxime 2 in the formula (7) are sulfur atoms. ί 如 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾 巾Formula (15), the general formula (M) is represented by the following general formula (I6): [In the general formulae (8) and (I5), R6i, R62, R9i, and R92 independently represent a hydrogen atom, a pyridyl group, an alkoxy group or a fast group 'Αι~A4 independently represent a carboxyl group or a salt thereof; in the formula (16) M12 represents an inorganic or organic ammonium ion, a proton or an alkali metal ion]. The method for producing a metal complex dye according to any one of claims 7 to 9 wherein the formula (1) is represented by the following formula (17), a formula ( 13) is represented by the following general formula (18), and the general formula (14) is represented by the following formula (1 = table) General formula (17) Formula (18) Formula (19) [In the formulae (17) and (18), R101, R102, R1U independently represent an alkynyl group, and A9 to A12 independently represent a carboxyl group or a salt thereof; In (19), Mu represents 'machine or organic ammonium ion, proton or alkali metal ion'. (12) A photoelectric conversion element using the metal complex dye composition according to any one of the above claims as a sensitizing dye. A metal complex dye produced by the method for producing a metal complex dye according to any one of claims 7 to 11, wherein the metal complex dye is produced. A photoelectrochemical cell, which is provided with a photoelectric conversion element according to any one of the preceding claims. 73