# Patent

## Title
Binuclear metal complex, metal complex dye, photoelectric conversion element, and photochemical battery

## Abstract

A novel binuclear metal complex according to the present invention is an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n, wherein M1 and M2, which may be identical or different, represent a transition metal; L1 and L2, which are different, represent a chelate ligand capable of polydentate coordination and two L1s may be different and two L2s may be different; BL represents a bridge ligand having at least two heteroatom-containing cyclic structures, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1 and M2; X represents a counter ion; and n is the number of counter ions needed to neutralize the charge of the complex. And the binuclear metal complex is useful as a metal complex dye.

## Background
This application is the U.S. National Phase under 35 U.S.C. §371 of International Application PCT/JP2005/18289, filed Oct. 3, 2005, which claims priority to Japanese Patent Application No. 2004-290075, filed Oct. 1, 2004, and Japanese Patent Application No. 2004-290076, filed Oct. 1, 2004. The International Application is published under PCT Article 21(2) in a language other than English.
TECHNICAL FIELD
The present invention relates to a novel binuclear metal complex.
The present invention also relates to a metal complex dye having a high absorbance index and improved electron transfer; a photoelectric conversion element comprising an oxide semiconductor photosensitized by the metal complex dye; and a photochemical battery therewith.
BACKGROUND ART
A solar battery is greatly expected to be a clean regenerative energy source, and researches have been conducted for practical application of a monocrystalline-silicon, polycrystalline-silicon or amorphous-silicon solar battery and a solar battery containing a compound such as cadmium telluride and indium-copper selenide. For prevalence of it as a household power source, however, any of these batteries faces many problems to be overcome, including a higher production cost, difficulty in ensuring raw material preparation, difficulty in recycling and difficulty in realizing a larger area. Therefore, there have been proposed solar batteries using an organic material in an attempt to achieve a larger area and a lower cost. However, any of these has a conversion efficiency of about 1%, which falls very short of practical use.
Under such circumstances, Graetzel et al. disclosed a photoelectric conversion element comprising semiconductor particles sensitized by a dye and a solar battery, as well as materials and technique for producing such a solar battery in Nature in 1991 (for example, Nature, Vol. 353, p. 737, 1991 (Non-patent document 1) and Japanese Laid-open Patent Publication No. 1989-220380 (Patent document 1)). The battery is a wet solar battery having a porous titania film sensitized by a ruthenium dye as a working electrode. This solar battery has the advantages that it can be provided as an inexpensive photoelectric conversion element because inexpensive materials can be used without highly purification, and that solar light can be converted into electricity over a wide visible light wavelength range because a dye having broad absorption is used. However, the conversion efficiency must be further improved for practical use, and therefore, it has been desired to develop a dye having a higher absorbance index and absorbing higher wavelength light.
Japanese Laid-open Patent Publication No. 2003-261536 (Patent document 2) by the present applicant has disclosed a mononuclear metal complex containing a dipyridyl ligand, which is a metal complex dye useful as a photoelectric conversion element.
“Current Technology in Dye-sensitized Solar Battery” (CMC Co., LTD., published on May 25, 2001, p. 117) (Non-patent document 2) has disclosed a polynuclear β-diketonate complex dye.
Japanese Laid-open Patent Publication No. 2004-359677 (Patent document 3), which is published on Dec. 24, 2004, has disclosed a polynuclear complex comprising a plurality of metals and a plurality of ligands wherein a bridge ligand (BL) coordinating to the plurality of metals has a coordination structure having a conjugated heterocyclic ring and a coordination structure without a conjugated heterocyclic ring, as a novel polynuclear complex improved in photoelectric conversion function of emitting electrons while receiving energy from active ray such as light.
There has been needed a useful and novel metal complex dye as a photoelectric conversion element.
LIST OF REFERENCES
Patent document 1: Japanese Laid-open Patent Publication No. 1989-220380;
Patent document 2: Japanese Laid-open Patent Publication No. 2003-261536;
Patent document 3: Japanese Laid-open Patent Publication No. 2004-359677;
Non-patent document 1: Nature, Vol. 353, p. 737, 1991;
Non-patent document 2: “Current Technology in Dye-sensitized Solar Battery” (CMC Co., LTD., published on May 25, 2001, p. 117).
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
An objective of the present invention is to provide a novel binuclear metal complex useful as a metal complex dye.
Another objective of the present invention is to provide a dye capable of efficiently photosensitizing semiconductor particles, by polynucleating a metal complex dye to improve absorbance index and by adjusting the direction of electron transition from an electrolytic solution side to a porous semiconductor to achieve a smoother electron transfer. A further objective of the present invention is to provide a photoelectric conversion element having a higher photoelectric conversion efficiency by using such a dye and to provide a photochemical battery comprising the photoelectric conversion element.
Means for Solving the Problems
The present invention relates to an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n,
wherein M1 and M2, which may be identical or different, represent a transition metal;
L1 and L2, which are different, represent a chelate ligand capable of polydentate coordination and two L1s may be different and two L2s may be different;
BL represents a bridge ligand having at least two heteroatom-containing cyclic structures, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1 and M2;
X represents a counter ion; and
n is the number of counter ions needed to neutralize the charge of the complex.
The present invention also relates to the above binuclear metal complex, wherein L1 and L2 represent a chelate ligand capable of bidentate, tridentate or tetradentate coordination.
The present invention also relates to the above binuclear metal complex, wherein L1 and L2 represent a bidentate ligand, which is a bipyridyl, pyridylquinoline, biquinoline or phenanthroline derivative.
The present invention also relates to the above binuclear metal complex, wherein L1 is a ligand substituted with at least one of carboxyl (—COOH) or —COO—.
The present invention also relates to the above binuclear metal complex, wherein BL represents a tetradentate ligand.
The present invention also relates to the above binuclear metal complex, wherein M1 and M2 are independently selected from the group consisting of Group VIII to Group XI transition metals.
The present invention also relates to the above binuclear metal complex, wherein M1 and M2 are independently selected from the group consisting of ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) and iron (Fe).
And furthermore, the present invention relates to a metal complex dye comprising an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n, wherein M1 and M2, which may be identical or different, represent a transition metal;
L1 and L2, which are different, represent a chelate ligand capable of polydentate coordination and two L1s may be different and two L2s may be different;
X represents a counter ion;
n is the number of counter ions needed to neutralize the charge of the complex;
BL represents a bridge ligand having at least two heteroatom-containing cyclic structures, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1 and M2; and
L1 contains a substituent capable of attaching to a semiconductor particle; and
LUMOs are predominantly distributed in (L1)2M1.
The present invention also relates to a photoelectric conversion element comprising semiconductor particles sensitized by the above metal complex dye.
The present invention also relates to the above photoelectric conversion element, wherein the semiconductor particle is selected from the group consisting of titanium oxide, zinc oxide and tin oxide.
The present invention also relates to a photochemical battery comprising the above photoelectric conversion element.
Effect of the Invention
As compared to an existing dye exhibiting a high photoelectric conversion efficiency which is used as a comparative dye, a metal complex dye according to the present invention has a higher absorbance index and an improved short-circuit current density per 1 mol (1 molecule) of a complex. Furthermore, a higher photoelectric conversion efficiency can be achieved by using a dye having an appropriate molecular orbital distribution. A photochemical battery comprising such a photoelectric conversion element is very effective as a solar battery. Additionally, in contrast to an existing dye exhibiting a high photoelectric conversion efficiency, a metal complex dye according to the present invention does not have a —NCS group, which may decompose readily, in the molecule and therefore exhibits high heat resistance.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a 1H-NMR spectrum of the binuclear metal complex (D-1) prepared in Example 1 according to the present invention in dimethyl sulfoxide-d6.
FIG. 2 shows a 1H-NMR spectrum of the binuclear metal complex (D-2) prepared in Example 2 according to the present invention in dimethyl sulfoxide-d6.
FIG. 3 shows a 1H-NMR spectrum of the binuclear metal complex (D-3) prepared in Example 3 according to the present invention in dimethyl sulfoxide-d6.
FIG. 4 shows a 1H-NMR spectrum of the binuclear metal complex (D-4) prepared in Example 4 according to the present invention in dimethyl sulfoxide-d6.
FIG. 5 shows a 1H-NMR spectrum of the binuclear metal complex (D-5) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 6 shows a 1H-NMR spectrum of the binuclear metal complex (D-6) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 7 shows a 1H-NMR spectrum of the binuclear metal complex (D-7) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 8 shows a 1H-NMR spectrum of the binuclear metal complex (D-8) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 9 shows a 1H-NMR spectrum of the binuclear metal complex (D-9) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 10 shows a 1H-NMR spectrum of the binuclear metal complex (D-10) prepared in Example 5 according to the present invention in dimethyl sulfoxide-d6.
FIG. 11 shows a 1H-NMR spectrum of the binuclear metal complex (D-11) prepared in Example 6 according to the present invention in dimethyl sulfoxide-d6.
FIG. 12 shows a 1H-NMR spectrum of the binuclear metal complex (D-12) prepared in Example 7 according to the present invention in dimethyl sulfoxide-d6.
FIG. 13 shows a 1H-NMR spectrum of the binuclear metal complex (D-13) prepared in Example 8 according to the present invention in dimethyl sulfoxide-d6.
FIG. 14 shows a 1H-NMR spectrum of the binuclear metal complex (D-14) prepared in Example 9 according to the present invention in dimethyl sulfoxide-d6.
FIG. 15 shows a 1H-NMR spectrum of the binuclear metal complex (D-15) prepared in Example 10 according to the present invention in dimethyl sulfoxide-d6.
FIG. 16 shows a comparison of UV-visible absorption spectra of the binuclear metal complex dye (D-4) prepared in Example 4 and Comparative dye A.
FIG. 17 shows a comparison of UV-visible absorption spectra of the binuclear metal complex dye (D-11) prepared in Example 6 and Comparative dye A.
FIG. 18 shows a comparison of UV-visible absorption spectra of the binuclear metal complex dye (D-12) prepared in Example 7 and Comparative dye A.
FIG. 19 shows a comparison of UV-visible absorption spectra of the binuclear metal complex dye (D-13) prepared in Example 8 and Comparative dye A.
FIG. 20 is a cross-sectional view showing the configuration of the photochemical battery prepared according to the present invention.
(Description of the Symbols)
1: glass, 2: transparent conductive layer, 3: platinum layer, 4: electrolytic solution, 5: dye-adsorbed porous oxide semiconductor film.
FIG. 21 shows a 1H-NMR spectrum of the binuclear metal complex (D-16) prepared in Example 18 in dimethyl sulfoxide-d6.
FIG. 22 shows a visualized shape of a HOMO (including a next HOMO) orbital in the structure shown in the binuclear metal complex dye (D-4) prepared in Example 4.
FIG. 23 shows a visualized shape of a LUMO (including a next LUMO) orbital in the structure shown in the binuclear metal complex dye (D-4) prepared in Example 4.
FIG. 24 shows a visualized shape of a HOMO (including a next HOMO) orbital in the structure shown in the binuclear metal complex dye (D-16) prepared in Example 18.
FIG. 25 shows a visualized shape of a LUMO (including a next LUMO) orbital in the structure shown in the binuclear metal complex dye (D-16) prepared in Example 18.
FIG. 26 conceptually shows an electron-transition direction in HOMO-LUMO in a preferable binuclear metal complex dye according to the present invention and electron flow within a photochemical battery circuit.
FIG. 27 shows a current-voltage characteristic curve of the photochemical battery produced using the binuclear metal complex dyes (D-4) and (D-16) prepared in Examples 4 and 18, respectively.
FIG. 28 shows a current-voltage characteristic curve of the photochemical battery produced using the binuclear metal complex dyes (D-4) and (D-16) prepared in Examples 4 and 18, respectively.



BEST MODE FOR CARRYING OUT THE INVENTION
In the asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n according to the present invention, M1 and M2 represent a transition metal, preferably a transition metal in Groups VIII to XI. Specifically, ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) or iron (Fe) is preferable. Among them, ruthenium (Ru) and osmium (Os) are preferable, and ruthenium (Ru) is particularly preferable.
M1 and M2 may be identical or different.
L1 and L2 represent a chelate ligand capable of polydentate coordination, preferably a chelate ligand capable of bidentate, tridentate or tetradentate coordination, more preferably a chelate ligand capable of bidentate coordination. Specific examples include derivatives of 2,2′-bipyridine, 1,10-phenanthroline, 2-(2-pyridinyl)quinoline, 2,2′-biquinoline and the like. L1 and L2 are different. Two L1s may be different and two L2s may be also different.
When the binuclear metal complex according to the present invention is a metal complex dye used in a photoelectric conversion element, L1 contains at least one substituent capable of attaching to a semiconductor particle.
Examples of a substituent in L1 capable of attaching to a semiconductor particle include carboxyl (—COOH), amino (—NH2), hydroxy (—OH), sulfate (—SO3H), phosphate (—PO3H2) and nitro (—NO2). Among them, carboxyl (—COOH) is preferable. The hydrogen in a carboxyl group may be replaced with a cation including a quaternary ammonium such as tetrabutylammonium and an alkali metal ion such as sodium ion. Alternatively, the hydrogen may be liberated.
Furthermore, L1 may or may not contain a substituent other than the substituent capable of attaching to a semiconductor particle. Examples of such a substituent include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
When the binuclear metal complex according to the present invention is a metal complex dye used in a photoelectric conversion element, L1 is preferably a ligand in which LUMOs are predominantly distributed in the (L1)2M1 moiety. The phrase, “LUMOs are predominantly distributed in the (L1)2M1 moiety” as used herein means that there are more LUMOs in the (L1)2M1 moiety than in the (L2)2M2 moiety. The structure of the binuclear metal complex where the (L1)2M1 predominantly have LUMOs to which an electron is excited by irradiation with light such as solar light allows smooth electron transfer from an electrolyte to a photoelectric conversion element (anode), thereby obtaining an efficient photochemical battery, when a photochemical battery is produced using a photoelectric conversion element comprising semiconductor particles sensitized by the binuclear metal complex.
An LUMO was calculated using software, Cerius2 or Material Studio. The method was optimized for a metal complex structure by DFT (density functional theory) using the DMol3 module. Suitable exchange correlation functions therefor include, but not limited to, VWN and BLYP methods. A suitable basis function is, but not limited to, DNP.
An energy state was calculated using the obtained structure, and a exchange correlation function therefor is, but not limited to, BLYP and PBE, and a suitable basis function is, but not limited to, DNP.
L1 may be the ligand represented by the following formula (L1-A).




In the above formula, H in —COOH may be liberated. R1, R2, R3, R4, R5 and R6 independently represent hydrogen, alkoxy, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring.
R1 to R6 are preferably hydrogen, alkyl or alkoxy, more preferably hydrogen or alkyl. The alkyl is preferably one containing up to six carbon atoms, more preferably methyl or ethyl. The alkoxy is preferably one containing up to six carbon atoms, more preferably methoxy or ethoxy.
It is also preferable that R2 and R3, R4 and R5, or R1 and R6 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon ring include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
R1 to R6 are particularly preferably hydrogen.
Specific examples of L1 include, but are not limited to, the ligands represented by the following formulas (L1-1) to (L1-4).




In these formulas (L1-1) to (L1-4), the heterocyclic ring and the benzene ring may be substituted with a substituent, and H in —COOH may be liberated. Examples of the substituent include alkyl containing up to six carbon atoms such as methyl and ethyl, and alkoxy containing up to six carbon atoms such as methoxy and ethoxy.
As described above, L2 is a chelate ligand capable of polydentate coordination, preferably a chelate ligand capable of bidentate, tridentate or tetradentate coordination, more preferably a chelate ligand capable of bidentate coordination. Specific examples include derivatives of 2,2′-bipyridine, 1,10-phenanthroline, 2-(2-pyridinyl)quinoline, 2,2′-biquinoline and the like.
L2 may or may not contain a substituent. Examples of the substituent in L2 include alkyl such as methyl and ethyl, aryl such as phenyl and tolyl, alkoxy such as methoxy and ethoxy, and hydroxy (—OH). An electron-donating group is particularly preferable.
L2 may be the ligand represented by the following formula (L2-A).




In the above formula, R11, R12, R13, R14, R15, R16, R17 and R18 independently represent hydrogen, alkoxy, hydroxy, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring.
R11 to R18 are preferably hydrogen, alkyl or alkoxy, more preferably hydrogen or alkyl. The alkyl is preferably one containing up to six carbon atoms, more preferably methyl or ethyl. The alkoxy is preferably one containing up to six carbon atoms, more preferably methoxy or ethoxy.
It is also preferable that adjacent two of R11 to R18 or R11 and R18 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon ring include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
Particularly preferably, R11 to R18 are hydrogen or methyl. Alternatively, it is also particularly preferable that R11 and R18 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent such as methyl, and R12 to R17 are hydrogen or methyl, more preferably hydrogen.
Specific examples of L2 include, but are not limited to, the ligands represented by the following formulas (L2-1) to (L2-4).




In these formulas (L2-1) to (L2-4), the heterocyclic ring and the benzene ring may be substituted with a substituent. Examples of the substituent include alkyl containing up to six carbon atoms, alkoxy containing up to six carbon atoms, phenyl optionally substituted with a substituent such as methyl, and hydroxy.
BL is a bridge ligand and has a heteroatom-containing cyclic structure. The heteroatom contained in the cyclic structure (conjugated heterocyclic ring) is the ligand atom coordinating to M1 and M2. The heteroatom may be, for example, nitrogen, oxygen, sulfur or phosphorus.
BL is preferably a tetradentate ligand. And it is more preferably anionic. BL may or may not have a substituent on the cyclic structure (conjugated heterocyclic ring).
BL may be the ligand represented by the following formula (BL-A).




In the above formula, R31, R32 and R33 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring. R34, R35 and R36 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring.
R31 to R36 are preferably hydrogen, alkyl or alkoxy, more preferably hydrogen or alkyl. The alkyl is preferably one containing up to six carbon atoms, more preferably methyl or ethyl. The alkoxy is preferably one containing up to six carbon atoms, more preferably methoxy or ethoxy.
It is also preferable that adjacent two of R31 to R36 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon ring include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
R31 to R36 are particularly preferably hydrogen or methyl, and R31 to R36 are further preferably hydrogen.
BL may be the ligand represented by the following formula (BL-B).




In the above formula, R41 and R42 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring. R43 and R44 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring.
R41 to R44 are preferably hydrogen, alkyl or alkoxy, more preferably hydrogen or alkyl. The alkyl is preferably one containing up to six carbon atoms, more preferably methyl or ethyl. The alkoxy is preferably one containing up to six carbon atoms, more preferably methoxy or ethoxy.
It is also preferable that R41 and R42 or R43 and R44 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon ring include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
R41 to R44 are particularly preferably hydrogen or methyl, and R41 to R44 are further preferably hydrogen. It is also particularly preferable that R41 and R42 or R43 and R44 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent such as methyl.
Among the ligands represented by the above formula (BL-B), the ligand represented by the following formula (BL-C) is preferable.




In the above formula, R51, R52, R53 and R54 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring. R55, R56, R57 and R58 independently represent hydrogen, or substituted or unsubstituted hydrocarbon, or alternatively, two or more of these together with the carbon atoms to which they are bound may form a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aliphatic hydrocarbon ring.
R51 to R58 are preferably hydrogen, alkyl or alkoxy, more preferably hydrogen or alkyl. The alkyl is preferably one containing up to six carbon atoms, more preferably methyl or ethyl. The alkoxy is preferably one containing up to six carbon atoms, more preferably methoxy or ethoxy.
It is also preferable that adjacent two of R51 to R58 together with the carbon atoms to which they are bound form a six-membered aromatic hydrocarbon ring which may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon ring include alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy.
R51 to R58 are particularly preferably hydrogen or methyl, and R51 to R58 are further preferably hydrogen.
Specific examples of BL include, but are not limited to, the ligands represented by the following formulas (BL-1) to (BL-4).




In these formulas (BL-1) to (BL-4), the heterocyclic ring and the benzene ring may be substituted with a substituent. Examples of the substituent include alkyl containing up to six carbon atoms, alkoxy containing up to six carbon atoms. Alternatively, adjacent two of the carbon atoms on the benzene ring in the formula (BL-4) may form a new benzene ring which may be substituted with a substituent.
In the case of a metal complex dye used in a photoelectric conversion element, BL is preferably the ligand represented by the above formula (BL-3) or (BL-4).
(L1)2M1(BL)M2(L2)2(X)n may contain water or an organic solvent as a crystal solvent. Examples of the organic solvent include DMSO, acetonitrile, DMF, DMAC and methanol. There are no particular restrictions to the number of crystal solvents.
X is a counter ion, which is an anion when the complex [(L1)2M1(BL)M2(L2)2] is a cation, while being a cation when the complex [(L1)2M1(BL)M2(L2)2] is an anion. N is the number of counter ions needed to neutralize the charge of the complex.
When the counter ion is an anion, specific examples of X include hexafluorophosphate, perchlorate, tetraphenylborate, tetrafluoroborate, trifluoromethanesulfonate, thiocyanate, sulfate and nitrate ions, as well as halide ions such as chloride and iodide ions.
When the counter ion is a cation, specific examples of X include ammonium ion, tetrabutylammonium ion, alkali metal ions such as sodium ion, and proton.
A particularly preferable metal complex dye is the above metal complex in which L1 is a ligand represented by the above formula (L1-1) (including that in which H in —COOH is liberated and that in which the heterocyclic ring and the benzene ring have further a substituent); L2 is a ligand represented by the above formula (L2-1) or (L2-2) (including that in which the heterocyclic ring and the benzene ring have a substituent); BL is a ligand represented by the above formula (BL-3) or (BL-4) (including that in which the heterocyclic ring and the benzene ring have a substituent); and M1 and M2 are independently selected from the group consisting of ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) and iron (Fe).
Specific examples of an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n according to the present invention include, but are not limited to, those represented by the following formulas (D-1) to (D-16).



















A metal complex according to the present invention can be prepared by reference to the process cited in literatures such as Inorganic Chemistry, Vol. 17 (9), pp. 2660-2666, 1978 and Journal of the American Chemical Society, Vol. 115, pp. 6382-6390, 1993.
A metal complex (L1)2M1(BL)M2(L2)2(X)n according to the present invention may be prepared, for example, by reacting two mononuclear metal complexes (L1)2M1Cl2 and (BL)M2(L2)2 which are synthesized as described below.
A mononuclear metal complex (L1)2M1Cl2 in which L1 is a ligand represented by the above formula (L1-1) and M1 is Ru (M1C-1) can be prepared as shown in the following synthetic scheme.




In the above synthetic scheme, a complex in which L1 has a substituent other than carboxyl and a complex in which M1 is a transition metal other than Ru can be synthesized in a similar way.
A mononuclear metal complex (L1)2M1Cl2 in which L1 is a ligand represented by the above formula (L1-4) and M1 is Ru (M1C-2) can be prepared as shown in the following synthetic scheme.




In the above synthetic scheme, a complex in which L1 has a substituent other than carboxyl and a complex in which M1 is a transition metal other than Ru can be synthesized in a similar way.
On the other hand, a mononuclear metal complex (BL)M2(L2)2 can be prepared as shown in the following synthetic scheme.




In the above synthetic scheme, H2BL represents the state where two heteroatoms (nitrogen, and so on) in BL are protonated.
Any of complexes in which BL is a ligand represented by any of the above formulas (BL-1) to (BL-4) (including those having a substituent) and any of complexes in which L2 is a ligand represented by any of the above formulas (L2-1) to (L2-4) (including those having a substituent) can be synthesized as shown in this synthetic scheme. For a complex in which BL is a ligand represented by the above formula (BL-1) (including that having a substituent), the latter reaction step using NaOMe can be omitted, and M2(L2)2Cl2 and BL may be reacted to give (BL)M2(L2)2.
(L1)2M1Cl2 (M1C) and (BL)M2(L2)2 (M2C) thus synthesized can be reacted as shown in the following synthetic scheme to give (L1)2M1(BL)M2(L2)2(X)n.




The above metal complex may be used as a metal complex dye, and semiconductor particles sensitized by the metal complex dye can be used to produce a photochemical battery.
A photoelectric conversion element according to the present invention comprises semiconductor particles sensitized by the above metal complex dye. More specifically, semiconductor particles sensitized by the above metal complex dye are fixed on an electrode.
A conductive electrode is preferably a transparent electrode formed on a transparent substrate. Examples of a conducting agent include metals such as gold, silver, copper, platinum and palladium; indium oxide-based compounds, typified by tin-doped indium oxide (ITO); tin oxide-based compounds, typified by fluorine-doped tin oxide (FTO); and zinc oxide-based compounds.
Examples of a semiconductor particle include titanium oxide, zinc oxide, tin oxide and the like. Alternative examples may include indium oxide; niobium oxide; tungsten oxide; vanadium oxide; composite oxide semiconductors such as strontium titanate, calcium titanate, barium titanate and potassium niobate; cadmium or bismuth sulfide; cadmium selenide or telluride; and gallium phosphide or arsenide. The semiconductor particles may be preferably made of an oxide, particularly preferably titanium oxide, zinc oxide or tin oxide or a mixture comprising at least one of these.
A primary particle size of the semiconductor particles is not limited, but is generally 1 to 5,000 nm, preferably 2 to 500 nm, particularly preferably 5 to 300 nm.
A photochemical battery according to the present invention has the above photoelectric conversion element. More specifically, it has the above photoelectric conversion element of the invention and a counter electrode as electrodes and an electrolyte layer between them. At least one of the electrode used in the photoelectric conversion element of the invention and the counter electrode is a transparent electrode.
The counter electrode acts as a cathode when it is combined with the photoelectric conversion element to form a photochemical battery. Although a substrate having a conductive layer may be used as a counter electrode like the above conductive electrode, such a substrate is not necessarily required when a metal plate itself is used. Examples of a conducting agent used in the counter electrode include metals such as platinum and carbon and conductive metal oxides such as fluorine-doped tin oxide.
The electrolyte (oxidation-reduction pair) may be selected from any known materials without limitations. Examples of a usable electrolyte include a combination of iodine and an iodide (for example, metal iodides such as lithium iodide and potassium iodide, or iodides of a quaternary ammonium compound such as tetrabutylammonium iodide, tetrapropylammonium iodide, pyridinium iodide and imidazolium iodide); a combination of bromine and a bromide; a combination of chlorine and a chloride; a combination of an alkylviologen and a reductant thereof; quinone/hydroquinone; transition metal ion pair such as iron (II)/iron (III) ions, copper (I)/copper (II) ions, manganese (II)/manganese (III) ions, and cobalt (II)/cobalt (III) ions; a combination of complex ions such as ferrocyanide/ferricyanide, cobalt (II) tetrachloride/cobalt (III) tetrachloride, cobalt (II) tetrabromide/cobalt (III) tetrabromide, iridium (II) hexachloride/iridium (III) hexachloride, ruthenium (II) hexacyanide/ruthenium (III) hexacyanide, rhodium (II) hexachloride/rhodium (III) hexachloride, rhenium (III) hexachloride/rhenium (IV) hexachloride, rhenium (IV) hexachloride/rhenium (V) hexachloride, osmium (III) hexachloride/osmium (IV) hexachloride, and osmium (IV) hexachloride/osmium (V) hexachloride; a complex formed with a transition metals such as cobalt, iron, ruthenium, manganese, nickel and rhenium, and a conjugated heterocyclic ring and derivative thereof such as bipyridine and derivative thereof, terpyridine and derivative thereof, and phenanthroline and derivative thereof; a complex of cyclopentadiene or derivative thereof and a metal such as ferrocene/ferrocenium ion, cobaltocene/cobaltocenium ion, and ruthenocene/ruthenocenium ion; and porphyrin compounds. A preferable electrolyte is a combination of iodine and lithium iodide or an iodide of a quaternary ammonium compound. The electrolyte may be a solution in an organic solvent, a molten salt, a so-called gel electrolyte in which the electrolyte is impregnated in a polymer matrix, or a solid electrolyte.
A photochemical battery according to the present invention can be produced by any of conventional processes.
For example, on a transparent electrode is applied a semiconductor particle paste such as an oxide, which is then calcined to form a thin film of the semiconductor particles. When the semiconductor-particle thin film is titania, calcination is carried out at a temperature of 450° C. and a reaction time of 30 minutes. This transparent electrode with the thin film is immersed in a dye solution for supporting the dye, to produce a photoelectric conversion element. Then, the photoelectric conversion element is combined with a transparent electrode on which platinum or carbon has been vapor-deposited as a counter electrode, and an electrolyte solution is interposed between them to produce a photochemical battery according to the present invention.
A binuclear metal complex according to the present invention may be also used as a material for an electron transport layer in an organic EL.
EXAMPLES
The present invention will be more specifically described with reference to the following examples. However, the present invention is not limited to these Examples.
For identification of structure, elemental analyses were conducted using YanacoMT-5 (Yanagimoto Mfg. Co., Ltd.) or Micro Coder JM10 (J-SCIENCE LAB Co., Ltd.), and 1H-NMR spectra were measured using AL-400 type FT-NMR (JEOL Ltd.).
Example 1
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)2Ru(BiIm)Ru(bpy)2](ClO4)2 (D-1)
1. Synthesis of a Mononuclear Metal Complex (H2dcbpy)2RuCl2 (M1C-1)
Under nitrogen atmosphere, in a 500 mL three-necked flask were placed commercially available RuCl3.3H2O (2.53 g, 9.68 mmol), H2dcbpy (4.50 g, 18.4 mmol) and 300 mL of N,N-dimethylformamide, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 45 minutes. After cooling down, the mixture was filtered, and the resulting filtrate was evaporated under vacuum to dryness. The resulting residue was washed with acetone/diethyl ether (1:4), 300 mL of 2 mol/L hydrochloric acid was added, and the mixture was stirred with ultrasonic for twenty minutes and then stirred for two hours without ultrasonic. After stirring, an insoluble material was collected by filtration and washed with 2 mol/L hydrochloric acid, acetone/diethyl ether (1:4) and diethyl ether. After drying under vacuum, 5.75 g of M1C-1 was obtained (yield: 85%).




2. Synthesis of a Mononuclear Metal Complex (BiIm)Ru(bpy)2 (M2C-1)

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(bpy)2Cl2 (0.501 g, 0.96 mmol) prepared as described in Inorg. Synth., vol. XXIV, 291 (1986), 2,2′-biimidazole (BiImH2) (0.156 g, 1.16 mmol) prepared as described in J. Chem. Soc., 4790 (1961) and 50 mL of ethanol/water (1:1), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 30 minutes. After cooling down, the mixture was filtered, and ethanol in the resulting filtrate was evaporated under vacuum. To the resulting aqueous solution was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. After collecting the precipitate by filtration, it was washed with water and recrystallized from methanol. After collecting the precipitated crystals by filtration, they were washed with cold methanol and diethyl ether. After drying under vacuum, 0.575 g of [(BiImH2)Ru(bpy)2](PF6)2 was obtained (yield: 70%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(BiImH2)Ru(bpy)2](PF6)2 (0.505 g, 0.59 mmol) thus prepared and 30 mL of methanol, and to the mixture was added dropwise 1.48 mL of a 4 mol/L solution of sodium methoxide in methanol. The suspension was refluxed for 30 minutes, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol and diethyl ether. After drying under vacuum, 0.251 g of a dark brown powder was obtained.
Next, under nitrogen atmosphere, in a 20 mL Schlenk flask were placed 0.139 g of the dark brown powder thus obtained and 5 mL of methanol, and to the mixture was added 0.5 mL of a 4 mol/L solution of sodium methoxide in methanol, and again refluxed for one hour. After the mixture cooled down, the insoluble material was collected by filtration, and washed with cold methanol and diethyl ether. After drying under vacuum, 96.8 mg of M2C-1 was obtained.




3. Synthesis of D-1

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (83.9 mg, 0.12 mmol) and 60 mL of ethanol/water (2:1), and then 0.5 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-1 (78.1 mg, 0.13 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After the mixture cooled down, a small amount of the insoluble material was removed by filtration, and ethanol in the filtrate was evaporated under vacuum. To the resulting aqueous solution was added dropwise a 0.5 mol/L aqueous perchloric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous perchloric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.110 g of D-1 was obtained (yield: 66%). The elemental analysis results were in good agreement with the values of a trihydrate.
Elemental Analysis
Observed: C:43.50, H:3.50, N:12.30
Calculated: C:43.30, H:3.10, N:12.10.
1H-NMR spectrum of the complex is shown in FIG. 1.
Example 2
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiIm)Ru(bpy)2](PF6) (D-2)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (62.4 mg, 0.090 mmol) and 30 mL of ethanol/water (1:1), and 0.4 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-1 (58.4 mg, 0.097 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After cooling down, the mixture was filtered and ethanol in the filtrate was evaporated under vacuum. To the resulting aqueous solution was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 49.3 mg of D-2 was obtained (yield: 41%). The elemental analysis results were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:44.60, H:3.50, N:12.60
Calculated: C:44.50, H:3.20, N:12.40.
1H-NMR spectrum of the complex is shown in FIG. 2.
Example 3
Synthesis of a Binuclear Metal Complex
[(H2dcbiq)(Hdcbiq)Ru(BiIm)Ru(bpy)2](PF6) (D-3)
1. Synthesis of a Mononuclear Metal Complex (H2dcbiq)2RuCl2 (M1C-2)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed RuCl2(DMSO)4 (0.468 g, 0.97 mmol) prepared as described in J. Chem. Soc., Dalton Trans. 204 (1973), commercially available K2dcbiq (0.91 g, 1.92 mmol) and 40 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 3 minutes. After cooling down, the mixture was filtered, and to the resulting filtrate was added dropwise 0.1 mol/L nitric acid to pH 2.5. The precipitated complex was collected by filtration, and washed with nitric acid at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.72 g of M1C-2 was obtained (yield: 83%).




2. Synthesis of D-3

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-2 (96.0 mg, 0.11 mmol) and 100 mL of ethanol/water (1:1), and then 0.45 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-1 (70.8 mg, 0.12 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After cooling down, the mixture was filtered, and ethanol in the filtrate was evaporated under vacuum. The resulting suspension was filtered, and to the filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 95.2 mg of D-3 was obtained (yield: 60%). The elemental analysis results were in good agreement with the values of an anhydride.
Elemental Analysis
Observed: C:54.30, H:3.20, N:11.40
Calculated: C:53.59, H:2.93, N:11.36.
1H-NMR spectrum of the complex is shown in FIG. 3.
Example 4
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiBzIm)Ru(bpy)2](PF6) (D-4)
1. Synthesis of a Mononuclear Metal Complex (BiBzIm)Ru(bpy)2 (M2C-2)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(bpy)2Cl2 (0.505 g, 0.97 mmol), 2,2′-bibenzimidazole (BiBzImH2) (0.343 g, 1.46 mmol) prepared as described in Inorg. Chem., 34, 5979 (1995) and 20 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 5 minutes. After the mixture cooled down, 20 mL of water was added to precipitate the unreacted bibenzimidazole. After filtration, to the resulting filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and then washed with water and recrystallized from methanol. After collecting the precipitated crystals by filtration, they were washed with cold methanol and diethyl ether. After drying under vacuum, 0.905 g of [(BiBzImH2)Ru(bpy)2](PF6)2 was obtained (yield: 96%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(BiBzImH2)Ru(bpy)2](PF6)2 (0.877 g, 0.90 mmol) thus prepared and 30 mL of methanol, and to the mixture was added dropwise 1.8 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for one hour, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with water, cold methanol and diethyl ether. After drying under vacuum, 0.587 g of M2C-2 was obtained (yield: 96%).




2. Synthesis of D-4

Under nitrogen atmosphere, in a 300 mL three-necked flask were placed M1C-1 (0.509 g, 0.73 mmol) and 100 mL of ethanol/water (1:1), and then 3.2 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-2 (0.522 g, 0.77 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 30 minutes. After the mixture cooled down, a small amount of the insoluble material was removed by filtration, and ethanol in the filtrate was evaporated under vacuum. The resulting suspension was filtered, and to the filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.873 g of D-4 was obtained (yield: 85%). The elemental analysis results were in good agreement with the values of a dihydrate.
Elemental Analysis
Observed: C:49.07, H:3.29, N:11.89
Calculated: C:49.23, H:3.06, N:11.88.
1H-NMR spectrum of the complex is shown in FIG. 4.
Example 5
Synthesis of D-5, D-6, D-7 D-8, D-9 and D-10
D-5, D-7, D-8, D-9 and D-10 were prepared as described in the synthetic process for D-4 in Example 4, substituting an acid corresponding to a counter anion for a 0.5 mol/L aqueous hexafluorophosphoric acid solution and an aqueous hexafluorophosphoric acid solution at pH 2.5, respectively. Since D-6 does not have any corresponding acid, it was prepared by using a 0.5 mol/L aqueous hydrochloric acid solution and an aqueous hydrochloric acid solution at pH 2.5, and adding sodium tetraphenylborate in a molar amount 10 times as much as M1C-1 before adding dropwise the 0.5 mol/L aqueous hydrochloric acid solution. The structures of D-5, D-6, D-7, D-8, D-9 and D-10 were also identified by elemental analysis and 1H-NMR spectrometry.
The elemental analysis results for D-5 were in good agreement with the values of a trihydrate.
Elemental Analysis
Observed: C:50.66, H:3.26, N:12.18
Calculated: C:50.66, H:3.30, N:12.22.
The elemental analysis results for D-6 were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:60.15, H:3.81, N:10.34
Calculated: C:60.59, H:4.15, N:10.34.
The elemental analysis results for D-7 were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:48.87, H:3.04, N:11.60
Calculated: C:48.69, H:3.26, N:11.55.
The elemental analysis results for D-8 were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:49.40, H:3.10, N:11.85
Calculated: C:49.56, H:3.37, N:11.96.
The elemental analysis results for D-9 were in good agreement with the values of a hexahydrate.
Elemental Analysis
Observed: C:49.46, H:3.34, N:12.41
Calculated: C:49.61, H:3.66, N:12.97.
The elemental analysis results for D-10 were in good agreement with the values of a dihydrate.
Elemental Analysis
Observed: C:49.70, H:3.23, N:11.89
Calculated: C:49.86, H:3.10, N:12.03.
1H-NMR spectra for D-5, D-6, D-7, D-8, D-9 and D-10 are shown in FIGS. 5, 6, 7, 8, 9 and 10, respectively.
Example 6
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiBzIm)Ru(phen)2](PF6) (D-11)
1. Synthesis of a Mononuclear Metal Complex (BiBzIm)Ru(phen)2 (M2C-3)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(phen)2Cl2 (0.509 g, 0.90 mmol) prepared as described in Inorg. Synth., vol. XXIV, 291 (1986), 2,2′-bibenzimidazole (BiBzImH2) (0.252 g, 1.08 mmol) and 50 mL of ethanol/water (1:1), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 30 minutes. After cooling down, the mixture was filtered, and ethanol in the resulting filtrate was evaporated under vacuum. The resulting suspension was filtered, and to the filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and then washed with water and recrystallized from methanol. After collecting the precipitated crystals by filtration, they were washed with cold methanol and diethyl ether. After drying under vacuum, 0.545 g of [(BiBzImH2)Ru(phen)2](PF6)2 was obtained (yield: 62%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(BiBzImH2)Ru(phen)2](PF6)2 (0.483 g, 0.49 mmol) thus prepared and 20 mL of methanol, and to the mixture was added dropwise 0.95 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for one hour, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol, water and diethyl ether. After drying under vacuum, 0.334 g of M2C-3 was obtained (yield: 91%).




2. Synthesis of D-11

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (0.106 g, 0.15 mmol) and 60 mL of ethanol/water (2:1), and 0.61 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-3 (0.114 g, 0.15 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After the mixture cooled down, a small amount of the insoluble material was removed by filtration, and ethanol in the filtrate was evaporated under vacuum. The resulting suspension was filtered, and to the filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.173 g of D-11 was obtained (yield: 76%). The elemental analysis results were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:49.60, H:3.10, N:11.20
Calculated: C:49.67, H:3.16, N:11.21.
1H-NMR spectrum of the complex is shown in FIG. 11.
Example 7
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiBzIm)Ru(big)2](PF6) (D-12)
1. Synthesis of a Mononuclear Metal Complex (BiBzIm)Ru(big)2 (M2C-4)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(biq)2Cl2 (0.228 g, 0.33 mmol) prepared as described in Inorg. Synth., vol. XXIV, 291 (1986), 2,2′-bibenzimidazole (BiBzImH2) (0.153 g, 0.65 mmol) and 10 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 5 minutes. After the mixture cooled down, 10 mL of water was added to precipitate the unreacted bibenzimidazole. After filtration, to the resulting filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and washed with water and diethyl ether. After drying under vacuum, 0.242 g of [(BiBzImH2)Ru(biq)2](PF6)2 was obtained (yield: 64%).
Subsequently, under nitrogen atmosphere, in a 20 mL Schlenk flask were placed [(BiBzImH2)Ru(phen)2](PF6)2 (0.205 g, 0.18 mmol) thus prepared and 20 mL of methanol, and to the mixture was added dropwise 0.43 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for 1.5 hours, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol, water and diethyl ether. After drying under vacuum, 0.140 g of M2C-4 was obtained (yield: 81%).




2. Synthesis of D-12

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (75.4 mg, 0.11 mmol) and 40 mL of N,N-dimethylformamide/water (3:1), and then 0.45 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-4 (0.114 g, 0.12 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After cooling down, the mixture was filtered, and the resulting filtrate was evaporated under vacuum to dryness. To the resulting residue was added 30 mL of water, and the insoluble material was removed by filtration. To the resulting filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.143 g of D-12 was obtained (yield: 82%). The elemental analysis results were in good agreement with the values of a dihydrate.
Elemental Analysis
Observed: C:55.00, H:3.40, N:10.50
Calculated: C:55.02, H:3.18, N:10.41.
1H-NMR spectrum of the complex is shown in FIG. 12.
Example 8
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiBzIm)Ru(dmbpy)2](PF6) (D-13)
1. Synthesis of a Mononuclear Metal Complex (BiBzIm)Ru(dmbpy)2 (M2C-5)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(dmbpy)2Cl2 (1.00 g, 1.79 mmol) prepared as described in Inorg. Synth., vol. XXIV, 291 (1986), 2,2′-bibenzimidazole (BiBzImH2) (0.49 g, 2.09 mmol) and 40 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 5 minutes. After the mixture cooled down, 40 mL of water was added to precipitate the unreacted bibenzimidazole. After filtration, to the resulting filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and washed with water and diethyl ether. After drying under vacuum, 1.58 g of [(BiBzImH2)Ru(dmbpy)2](PF6)2 was obtained (yield: 89%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(BiBzImH2)Ru(dmbpy)2](PF6)2 (1.00 g, 1.01 mmol) thus prepared and 30 mL of methanol, and to the mixture was added dropwise 1.9 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for one hour, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol, water and diethyl ether. After drying under vacuum, 0.74 g of M2C-5 was obtained (yield: 95%).




2. Synthesis of D-13

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (0.204 g, 0.29 mmol) and 50 mL of ethanol/water (1:1), and then 1.2 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-5 (0.228 g, 0.29 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After cooling down, the mixture was filtered, and ethanol in the filtrate was evaporated under vacuum. The resulting suspension was filtered, and to the filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.366 g of D-13 was obtained (yield: 87%). The elemental analysis results were in good agreement with the values of an anhydride.
Elemental Analysis
Observed: C:51.80, H:3.40, N:11.50
Calculated: C:51.89, H:3.30, N: 11.71.
1H-NMR spectrum of the complex is shown in FIG. 13.
Example 9
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(TMBiBzIm)Ru(bpy)2](PF6) (D-14)
1. Synthesis of a Mononuclear Metal Complex (TMBiBzIm)Ru(bpy)2 (M2C-6)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(bpy)2Cl2 (0.508 g, 0.98 mmol), 5,6,5′,6′-tetramethyl-2,2′-bibenzimidazole (TMBiBzImH2) (0.343 g, 1.18 mmol) prepared as described in Inorg. Chem., 34, 5981-5982 (1995) and 20 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 5 minutes. After the mixture cooled down, 20 mL of water was added to precipitate the unreacted TMBiBzImH2. After filtration, to the resulting filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and washed with water and diethyl ether. After drying under vacuum, 0.969 g of [(TMBiBzImH2)Ru(bpy)2](PF6)2 was obtained (yield: 99%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(TMBiBzImH2)Ru(bpy)2](PF6)2 (0.93 g, 0.93 mmol) thus prepared and 30 mL of methanol, and to the mixture was added dropwise 1.9 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for one hour, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol, water and diethyl ether. After drying under vacuum, 0.58 g of M2C-6 was obtained (yield: 81%).




2. Synthesis of D-14

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (0.102 g, 0.15 mmol) and 60 mL of N,N-dimethylformamide/water (5:1), and then 0.62 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-6 (0.115 g, 0.16 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 25 minutes. After cooling down, the mixture was filtered, and the resulting filtrate was evaporated under vacuum to dryness. To the resulting residue was added 50 mL of water, and the insoluble material was removed by filtration. To the resulting filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.145 g of D-14 was obtained (yield: 67%). The elemental analysis results were in good agreement with the values of a dihydrate.
Elemental Analysis
Observed: C:50.62, H:3.53, N:11.35
Calculated: C:50.61, H:3.49, N:11.42.
1H-NMR spectrum of the complex is shown in FIG. 14.
Example 10
Synthesis of a Binuclear Metal Complex
[(H2dcbpy)(Hdcbpy)Ru(BiBzIm)Os(bpy)2](PF6) (D-15)
1. Synthesis of a Mononuclear Metal Complex (BiBzIm)Os(bpy)2 (M2C-7)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Os(bpy)2Cl2 (0.501 g, 0.87 mmol) prepared as described in Inorg. Chem., 27, 3195 (1988), BiBzImH2 (0.613 g, 2.62 mmol) and 20 mL of ethylene glycol, and the mixture was refluxed under irradiation with 2.45 GHz microwave for 5 minutes. After the mixture cooled down, 20 mL of water was added to precipitate the unreacted BiBzImH2. After filtration, to the resulting filtrate was added an aqueous solution of NH4PF6 to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and washed with water and diethyl ether. After drying under vacuum, 0.790 g of [(BiBzImH2)Os(bpy)2](PF6)2 was obtained (yield: 87%).
Subsequently, under nitrogen atmosphere, in a 50 mL Schlenk flask were placed [(BiBzImH2)Os(bpy)2](PF6)2 (0.77 g, 0.74 mmol) thus prepared and 30 mL of methanol, and to the mixture was added dropwise 1.45 mL of a 28% solution of sodium methoxide in methanol. The suspension was refluxed for one hour, and then cooled to room temperature. The insoluble material was collected by filtration, and washed with cold methanol, water and diethyl ether. After drying under vacuum, 0.51 g of M2C-7 was obtained (yield: 89%).




2. Synthesis of D-15

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (0.101 g, 0.15 mmol) and 40 mL of N,N-dimethylformamide/water (3:1), and then 0.61 mL of a 1 mol/L aqueous sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-7 (0.168 g, 0.22 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 15 minutes. After cooling down, the mixture was filtered, and the resulting filtrate was evaporated under vacuum to dryness. To the resulting residue was added 30 mL of water, and the insoluble material was removed by filtration. To the resulting filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.172 g of D-15 was obtained (yield: 79%). The elemental analysis results were in good agreement with the values of a dihydrate.
Elemental Analysis
Observed: C:46.80, H:3.30, N:10.90
Calculated: C:46.31, H:2.88, N:11.17.
1H-NMR spectrum of the complex is shown in FIG. 15.
Example 11
Absorption Spectral Measurement
For each of D-4, D-11, D-12, D-13 and the following Comparative dye A as an existing mononuclear metal complex dye (N3dye, a ruthenium organic complex from Kojima Chemicals Co., Ltd.), an ethanol solution was prepared at a concentration of 3×10−5 mol/L, and was subjected to measurement using a UV-visible absorption spectrum at a wavelength of 250 nm to 800 nm (JASCO Corporation, V-570). The results are shown in FIGS. 16, 17, 18 and 19.




As seen from FIGS. 16, 17, 18 and 19, all of the binuclear metal complex dyes of the present invention have an absorption wavelength range similar to that of Comparative dye A as an existing dye exhibiting a high photoelectric conversion efficiency, and have a further higher absorbance index. It is, therefore, very preferable to use a binuclear metal complex dye of the present invention in a photochemical battery because it absorbs more light to be converted into a photocurrent.
Example 12
1. Preparation of a Porous Titania Electrode
Preparation of a Porous Titania Electrode (T-1)
To 5.0 g of a 30 wt % titania microparticle dispersed slurry (Titan Kogyo KK., 20 nm microparticles) were added 0.2 mL of acetylacetone, 1 mL of a 2 wt % hydroxyethylcellulose solution and 1 mL of a 10 wt % aqueous solution of polyoxyethyleneoctyl phenyl ether, and the mixture was stirred with ultrasonic for one hour to prepare a titania paste, which is paste A. Separately, 3.0 g of titania microparticles were mixed with 7 mL of nitric acid at pH 0.7, and to the resulting mixture were added 0.2 mL of acetylacetone, 0.2 mL of a surfactant and polyethylene glycol having a molecular weight of 20,000, and the mixture was stirred with ultrasonic for one hour to prepare a titania paste, which is paste B. First, paste A was applied onto a transparent conductive glass electrode (from Asahi Glass Co., Ltd.) by a 100 μm doctor blade while masking a part of the electrode. Next, the resulting film was dried at room temperature, and then paste B was applied as described for paste A except using a 70 μm doctor blade to form a double-layered film. After drying, the film was calcined at 450° C. for 30 minutes to prepare a 1 cm2 porous titania electrode (T-1).
Preparation of a Porous Titania Electrode (T-2)
A titania paste SP-100 from Showa Denko KK. was applied onto a transparent conductive glass electrode (from Asahi Glass Co., Ltd.) by a 200 μm doctor blade while masking a part of the electrode. The applied film was air-dried at room temperature for 5 minutes, and then calcined at 450° C. for 30 minutes to prepare a 1 cm2 porous titania electrode (T-2).
Preparation of a Porous Titania Electrode (T-3)
3.0 g of titania microparticle was dispersed in 7 g of nitric acid at pH 0.7. To the paste was added 0.2 mL of acetylacetone and 0.2 mL of 10% Triton X as a surfactant. Next, to the mixture was added 1.2 g of polyethylene glycol having a molecular weight of 20,000 and finally 1 mL of ethanol, and then the paste was stirred and dispersed with ultrasonic for 15 minutes. This process of stirring with ultrasonic was repeated four times to prepare a paste. The resulting paste was applied onto a transparent conductive glass electrode (from Asahi Glass Co., Ltd.) by a 100 μm doctor blade while masking a part of the electrode. The resulting film was aged under the atmosphere of 25° C. and 60% for 10 minutes, and the aged film was calcined at 450° C. for 30 minutes. The cooled film was again subjected to the same process for forming a double-layered film to prepare a 1 cm2 porous titania electrode (T-3).
2. Preparation of a Dye-Adsorbed Porous Titania Electrode
Preparation of D-1, D-2 or Comparative Dye A Adsorbed Porous Titania Electrodes
A porous titania electrode (T-1) was immersed in a saturated dye solution of each of D-1 and D-2 in ethanol/dimethyl sulfoxide (95:5) (less than 3×10−4 mol/L) at 50° C. for 15 hours. Next, it was washed with ethanol and dried to give a dye-adsorbed porous titania electrode.
A Comparative dye A-adsorbed porous titania electrode was prepared as described above, except immersion in a 3×10−4 mol/L ethanol solution at 50° C. for 4 hours.
Preparation of D-4, D-11, D-13, D-14 or Comparative Dye A Adsorbed Porous Titania Electrodes
A porous titania electrode (T-2) was immersed in a saturated dye solution of each of D-4, D-11, D-13 and D-14 in t-butanol/acetonitrile (1:1) (less than 3×10−4 mol/L) at 30° C. for 10 hours. Next, it was washed with acetonitrile and dried to give a dye-adsorbed porous titania electrode.
A Comparative dye A-adsorbed porous titania electrode was prepared as described above, except that a 3×10−4 mol/L solution in t-butanol/acetonitrile (1:1) was used.
Preparation of D-4, D-5, D-6, D-7, D-8. D-9 or D-10 Adsorbed Porous Titania Electrodes
A porous titania electrode (T-3) was immersed in a saturated dye solution of each of D-4, D-5, D-6, D-7, D-8, D-9 and D-10 in t-butanol/acetonitrile (1:1) (less than 3×10−4 mol/L) at 30° C. for 20 hours. Next, it was washed with acetonitrile and dried to give a dye-adsorbed porous titania electrode.
3. Preparation of a Photochemical Battery
A dye-adsorbed porous titania electrode thus obtained was combined with a platinum plate (counter electrode). Then, a solution of lithium iodide, iodine, 4-t-butylpyridine and 1,2-dimethyl-3-propylimidazolium iodide dissolved in 3-methoxypropionitrile to 0.1, 0.05, 0.5 and 0.6 mol/L, respectively as an electrolytic solution was infiltrated into a gap between these electrodes by capillary action to prepare a photochemical battery. FIG. 20 shows the structure of the photochemical battery prepared in this example.
4. Determination of Photoelectric Conversion Efficiency
The photoelectric conversion efficiency of the photochemical battery thus prepared was determined under irradiation with artificial solar light at 100 mW/cm2 using a solar simulator (from EKO Instruments Co., Ltd.). Tables 1 and 2 summarize the photoelectric conversion efficiency for each dye. Table 3 shows the short-circuit current density per mol and the photoelectric conversion efficiency for D-4 and Comparative dye A.










TABLE 1








Photoelectric



Porous titania
conversion



electrode
efficiency (%)




















D-1
T-1
1.8



D-2
T-1
2.6



D-4
T-2
4.6



D-11
T-2
4.4



D-13
T-2
3.7



D-14
T-2
2.8



Comparative dye A
T-1
4.1



Comparative dye A
T-2
4.3




















TABLE 2








Photoelectric



Porous titania
conversion



electrode
efficiency (%)




















D-4
T-3
5.4



D-5
T-3
4.9



D-6
T-3
3.3



D-7
T-3
4.4



D-8
T-3
4.2



D-9
T-3
4.7



D-10
T-3
4.3




















TABLE 3







Short-circuit current
Photoelectric



density
conversion efficiency



(×108 mA/mol · cm2)
(×107%/mol)


















D-4
2.2
8.6


Comparative dye A
1.4
5.4









As seen from Table 1, metal complex dyes D-4 and D-11 of the present invention exhibit a higher photoelectric conversion efficiency than Comparative dye A. As seen from Table 2, the complexes of the present invention which is the same as metal complex dye D-4 except a counter anion (D-5, D-6, D-7, D-8, D-9 and D-10) exhibit a high photoelectric conversion efficiency. As seen from Table 3, the metal complex dye of the present invention has an improved short-circuit current density per molecule and an improved photoelectric conversion efficiency in comparison with Comparative dye A, which demonstrate that the metal complex dye of the present invention has an improved photoelectric conversion ability.
Example 13
Evaluation of Dyes for Thermal Stability
D-4, D-11, D-13 and Comparative dye A were evaluated for their thermal stability from a temperature of generation of a decomposition gas component under an artificial air (He: 80%+O2: 20%) by TG-MS analysis. TG analysis was conducted using Thermo plus TG8120 (from Rigaku Corporation) under the conditions of a temperature increase rate: 10° C./min and an artificial-air flow rate: 100 mL/min, and injection into an MS apparatus carried out at a transfer-line temperature of 200° C. MS spectra were obtained using a mass spectrometer QP-5000 complex system (from Shimadzu Corporation) under the conditions of an inlet temperature: 250° C., an interface temperature: 300° C., an ionization method: El (70 eV) and a mass scanning range: 10 to 300.
Table 4 shows an initiation temperature of generation of a gas component derived from a ligand which generates when each dye is thermally decomposed.










TABLE 4







Gas
Initiation temperature of



component
gas generation (° C.)




















D-4
CO2
280



D-11
CO2
300



D-13
CO2
280



Comparative dye A
CO2
250



Comparative dye A
SO2
240










As seen from Table 4, an initiation temperature of generation of CO2 which is considered to be a gas component derived from a carboxyl group (—COOH) is higher by 30° C. in any of the binuclear metal complexes of the present invention compared with Comparative dye A. Furthermore, generation of SO2 which is considered to be a gas component derived from an isothiocyanato group (—NCS) was observed at a temperature lower than a decomposition temperature of a carboxyl group for Comparative dye A, while no other gas components were observed in a temperature range lower than the decomposition temperature of a carboxyl group for the binuclear metal complexes of the present invention. A binuclear metal complex of the present invention is, therefore, very preferable because of its high thermal stability due to less decomposable sites.
Example 14
Preparation of a Dye-Adsorbed Porous Titania Electrode
A porous titania electrode in which the binuclear metal complex dye (D-4) of the present invention obtained in Example 4 was adsorbed was prepared. The procedure will be described below.
Preparation of a Porous Titania Electrode
To 5.0004 g of a 30 wt % titania microparticle dispersed slurry (Titan Kogyo KK., 20 nm microparticles) were added 0.2 mL of acetylacetone, 1 mL of a 2 wt % hydroxyethylcellulose and 1 mL of a 10 wt % aqueous solution of polyoxyethyleneoctyl phenyl ether, and the mixture was stirred with ultrasonic for one hour to prepare a titania paste, which was paste A. Separately, 2.9997 g of titania microparticles were mixed with 7 mL of nitric acid at pH 0.7, and to the resulting mixture were added 0.2 mL of acetylacetone, 0.2 mL of a surfactant and polyethylene glycol having a molecular weight of 20,000, and the mixture was stirred with ultrasonic for one hour to prepare a titania paste, which was paste B. Paste A was applied onto a transparent conductive glass electrode by a doctor blade using a 50 μm spacer to prepare a film. After drying the film at room temperature, paste B was applied to the film in a similar way, which was dried and calcined at 450° C. for 30 minutes to prepare 1 cm2 and 5 cm2 porous titania electrodes.
Next, a saturated solution of the binuclear metal complex dye of the present invention (D-4) obtained in Example 4 in ethanol (3×10−4 mol/L or less) was prepared as a dye solution, in which was then immersed the electrodes at 50° C. for 15 hours. After the immersion, they were washed with ethanol and dried under a nitrogen stream to give 1 cm2 and 5 Cm2 dye-adsorbed porous titania electrodes.
Comparative Example 1
1 cm2 and 5 cm2 dye-adsorbed porous titania electrodes were prepared as described in Example 14, except using a 3×10−4 mol/L dye solution of Comparative dye A represented by the above formula (A) in ethanol as a dye.
Example 15
Determination of the Amount of Dye Adsorption
The amount of an adsorbed dye was determined for each of 5 cm2 dye-adsorbed porous titania electrodes obtained in Example 14 and Comparative Example 1. The procedure will be described below.
A dye was desorbed by immersing a dye-adsorbed porous titania electrode in a 0.01 mol/L solution of sodium hydroxide in ethanol/water (1:1) overnight. The amount of dye adsorption per 1 cm2 was calculated from an absorption spectrum of the resulting desorption solution (by JASCO Corporation, V-570). Table 5 summarizes the results on an adsorption amount for each of the binuclear metal complex dye (D-4) obtained in Example 4 and Comparative dye A.










TABLE 5








Dye-adsorption amount



Metal complex dye
(10−8 mol/cm2)









D-4
6.5



Comparative dye A
8.8










Example 16
Preparation of a Photochemical Battery
There will be described a procedure for preparing a photochemical battery.
A 1 Cm2 dye-adsorbed porous titania electrode prepared in Example 14 or Comparative Example 1 was combined with a platinum plate (counter electrode). Then, a solution of lithium iodide, iodine, 4-t-butylpyridine and 1,2-dimethyl-3-propylimidazolium iodide dissolved in 3-methoxypropionitrile to 0.1, 0.05, 0.5 and 0.6 mol/L, respectively as an electrolytic solution was infiltrated into a gap between these electrodes by capillary action to prepare a photochemical battery.
Example 17
Evaluation of a Photochemical Battery
A photochemical battery was evaluated by irradiating the photochemical battery obtained in Example 16 with artificial solar light at 100 mW/cm2 using a solar simulator (from EKO Instruments Co., Ltd.). Table 6 summarizes the property values for each of the binuclear metal complex dye of the present invention (D-4) obtained in Example 4 and Comparative dye A. Jsc and Voc in Table 6 represent a short-circuit current density per 1 mol of a metal complex dye and an open voltage, respectively. The short-circuit current densities per 1 mol of dye were calculated from the results in Table 5.











TABLE 6








Jsc
Voc



Metal complex dye
(105 A · mol−1 · cm−2)
(V)









D-4
1.72
0.71



Comparative dye A
1.49
0.66










As seen from Table 6, a short-circuit current density per molecule is higher in the binuclear metal complex dye of the present invention (D-4) obtained in Example 4 compared with Comparative dye A, which demonstrate unambiguously that the binuclear metal complex dye of the present invention has an improved photoelectric conversion ability.
Example 18
Synthesis of a Binuclear Metal Complex
[(Hdcbpy)2Ru(bpm)Ru(bpy)2](PF6)2 (D-16)
1. Synthesis of a Mononuclear Metal Complex [(bpm)Ru(bpy)2](PF6)2 (M2C-8)
Under nitrogen atmosphere, in a 100 mL three-necked flask were placed Ru(bpy)2Cl2 (0.216 g, 0.42 mmol) prepared in Example 1, 2,2′-bipyrimidine (bpm) (0.133 g, 0.84 mmol) and 40 mL of ethanol/water (1:1), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 30 minutes. After the mixture cooled down, an aqueous solution of NH4PF6 was added to precipitate a complex as a salt of counter anion PF6−. The precipitate was collected by filtration, and then washed with water and recrystallized from acetone/diethyl ether. After collecting the precipitated crystals by filtration, they were washed with diethyl ether. After drying under vacuum, 0.259 g of M2C-8 was obtained (yield: 71%).




2. Synthesis of D-16

Under nitrogen atmosphere, in a 100 mL three-necked flask were placed M1C-1 (0.102 g, 0.15 mmol) and 40 mL of ethanol/water (1:1), and 0.6 mL of a 1 mol/L sodium hydroxide solution was added dropwise to give a solution. To the solution was added M2C-8 (0.135 g, 0.15 mmol), and the mixture was refluxed under irradiation with 2.45 GHz microwave for 10 minutes. After cooling down, the mixture was filtered, and ethanol in the resulting filtrate was evaporated under vacuum to dryness. The resulting suspension was filtered, and to the filtrate was added dropwise a 0.5 mol/L aqueous hexafluorophosphoric acid solution to pH 2.5. The precipitated complex was collected by filtration, and washed with an aqueous hexafluorophosphoric acid solution at pH 2.5, acetone/diethyl ether (4:1) and diethyl ether. After drying under vacuum, 0.108 g of D-16 was obtained (yield: 42%). The elemental analysis results were in good agreement with the values of a tetrahydrate.
Elemental Analysis
Observed: C:41.30, H:3.40, N:10.90
Calculated: C:41.06, H:2.92, N:11.05.
1H-NMR spectrum of the complex is shown in FIG. 21.
Example 19
Quantum Chemical Calculation for a Binuclear Metal Complex Dye
A binuclear metal complex model was structurally optimized by quantum chemical calculation. The software used was Material Studio 2.0. A calculation method was a density functional theory (DFT), where an exchange correlation function was VWN and a basis function system was DNP. For simplifying calculation, an effective core potential approximation was used. (In the structural optimization, a convergence condition to energy was 10−5 a.u. or less. In terms of SCF performed in the structural optimization calculation, a convergence condition to energy was 10−6 a.u. or less.)
For the complex model obtained from the above structural optimization, an energy state was calculated by quantum chemical calculation. A calculation method was a density functional theory. And a specific exchange correlation function was BLYP. A basis function system was DNP. Furthermore, for simplifying calculation, an effective core potential approximation was used. (In terms of SCF calculation, a convergence condition to energy was 10−6 a.u. or less, and the condition was imposed that an electron occupation number for each state was an integer from 0 to 2 both inclusive.)
For the above results, FIG. 22 shows a visualized shape of a HOMO (including a next HOMO) orbital in the structure shown in the binuclear metal complex dye of the present invention (D-4) prepared in Example 4; FIG. 23 shows a visualized shape of a LUMO (including a next LUMO) orbital in the structure shown in the binuclear metal complex dye (D-4); FIG. 24 shows a visualized shape of a HOMO (including a next HOMO) orbital in the structure shown in the binuclear metal complex dye (D-16) prepared in Example 18; and FIG. 25 shows a visualized shape of a LUMO (including a next LUMO) orbital in the structure shown in the binuclear metal complex dye (D-16). The visualization was performed under the conditions of Iso-Value=±0.03 using the software, Material Studio 2.0. FIG. 26 conceptually shows an electron-transition direction in HOMO-LUMO in an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n wherein L1, M1, BL, M2, L2 and X are as defined above; and electron flow within a photochemical battery circuit. In FIG. 26, X is omitted.
As shown in FIG. 26, a HOMO and a LUMO preferably have such an orbital configuration that a direction of electron transition in HOMO-LUMO is identical to a direction of electron flow within a photochemical battery circuit. As seen from FIGS. 22 and 23, these two directions are identical in the binuclear metal complex dye (D-4) of the present invention; while as seen from FIGS. 24 and 25, these two directions are not identical in the binuclear metal complex dye (D-16) prepared in Example 18. It can be, therefore, understood that the binuclear metal complex dye (D-4) of the present invention allows smoother electron transfer, thereby obtaining an efficient photochemical battery.
Comparative Example 2
For the binuclear metal complex dye (D-16) prepared in Example 18, a photochemical battery was prepared and the photoelectric conversion efficiency was determined as described in Example 12, except substituting a saturated solution of a dye in ethanol for a saturated solution of a dye in ethanol/dimethyl sulfoxide (95:5) in the preparation of D-1, D-2 or Comparative dye A adsorbed porous titania electrodes. Table 7 shows the results on a photoelectric conversion efficiency and FIG. 27 shows a current-voltage characteristic curve. A photoelectric conversion efficiency and a current-voltage characteristic curve for D-4 obtained in Example 12 are also shown in Table 7 and FIG. 27, respectively.









TABLE 7







Photoelectric conversion



efficiency (%)



















D-4
4.6



D-16
<0.1










Table 7, FIG. 27 and the results of Example 19 show that the binuclear metal complex dye (D-4) of the present invention with a proper HOMO-LUMO orbital configuration is significantly improved in photochemical battery properties as compared with the binuclear metal complex dye (D-16) prepared in Example 18 with an improper HOMO-LUMO orbital configuration.
Comparative Example 3
For the binuclear metal complex dye (D-16) prepared in Example 18, a photochemical battery was evaluated as described in Example 17, after preparing a 1 cm2 dye-adsorbed porous titania electrode as described in Example 14 and preparing a photochemical battery as described in Example 16. Table 8 shows the results on a photoelectric conversion efficiency (η) and FIG. 28 shows a current-voltage characteristic curve. The results on a photoelectric conversion efficiency (η) and a current-voltage characteristic curve for the binuclear metal complex dye (D-4) of the present invention prepared in Example 17 are also shown in Table 8 and FIG. 28, respectively.










TABLE 8







Metal complex dye
η (%)



















D-4
4.0



D-16
<0.1










Table 8, FIG. 28 and the results of Example 19 show that the binuclear metal complex dye (D-4) of the present invention prepared in Example 4 with a proper HOMO-LUMO orbital configuration is significantly improved in photochemical battery properties as compared with the binuclear metal complex dye (D-16) prepared in Example 18 with an improper HOMO-LUMO orbital configuration.

## Claims

1. An asymmetric binuclear metal complex represented by the general formula: (L1)2 M1(BL)M2(L2)2(X)n 
wherein M1 and M2, which may be identical or different, represent ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) or iron (Fe);
L1 represents a ligand represented by the formula (L1-A):




wherein H in —COOH may be liberated; and
R1, R2, R3, R4, R5 and R6 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, R2 and R3, R4 and R5, or R1 and R6 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound;
L2 represents a ligand represented by the formula (L2-A):




wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, adjacent two of R11to R18 or R11to R18 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound;
and two L1s may be different and two L2s may be different;
BL represents a bridge ligand represented by the formula (BL-C):




wherein R51, R52, R53 and R54 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, adjacent two of R51 to R54 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound; and
R55, R56, R57 and R58 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, adjacent two of R55 to R58 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1 and M2;
X represents a counter ion; and
n is the number of counter ions needed to neutralize the charge of the complex.

2. The binuclear metal complex as claimed in claim 1, wherein L1is a ligand represented by the formula (L1-1) or (L1-4):



wherein the heterocyclic ring may be substituted; and H in —COOH may be liberated.

3. The binuclear metal complex as claimed in claim 1, wherein L2 is a ligand represented by any of the formulas (L2-1), (L2-2) and (L2-4):



wherein the heterocyclic ring and the benzene ring may be substituted.

4. The binuclear metal complex as claimed in claim 1, wherein BL is a ligand represented by the formula (BL-4):



wherein the heterocyclic ring and the benzene ring may be substituted.

5. The binuclear metal complex as claimed in claim 1, wherein L1 is a ligand represented by the above formula (L1-1) or (L1-4);
L2 is a ligand represented by any of the above formulas (L2-1), (L2-2) and (L2-4);
BL is a ligand represented by formula (BL-4)





and
M1 and M2 are independently selected from the group consisting of ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) and iron (Fe).

6. A semiconductor-sensitizing dye comprising an asymmetric binuclear metal complex represented by the general formula: (L1)2M1(BL)M2(L2)2(X)n,
wherein M1and M2, which may be identical or different, represent ruthenium (RU), osmium (Os), cobalr (Co), nickel (Ni), copper (Cu) or iron (Fe);
L1 represents a ligand represented by the formula (L1-A):




wherein H in —COOH may be liberated; and
R1, R2, R3, R4, R5 and R6 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, R2 and R3, R4 and R5, or R1 and R6 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound;
L2 represents a ligand represented by the formula (L2-A):




wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6carbon atoms, or alternatively, adjacent two of R11 to R18 or R11 to R18 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound;
and two L1s may be different and two L2s may be different;
X represents a counter ion;
n is the number of counter ions needed to neutralize the charge of the complex;
BL represents a bridge ligand represented by the formula (BL-C):




wherein R51, R52, R53 and R54 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, adjacent two of R51 to R54 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound; and
R55, R56, R57 and R58 independently represent hydrogen, alkyl containing 1 to 6 carbon atoms, or alkoxy containing 1 to 6 carbon atoms, or alternatively, adjacent two of R55 to R58 may form a substituted or unsubstituted six-membered aromatic hydrocarbon ring together with the carbon atoms to which they are bound, the heteroatoms contained in the cyclic structures being ligand atoms coordinating to M1and M2.

7. The semiconductor-sensitizing dye as claimed in claim 6, wherein
L1is a ligand represented by the above formula (L1-1);
L2 is a ligand represented by the above formula (L2-1) or (L2-2);
BL is a ligand represented by formula (BL-4)





and
M1 and M2 are independently selected from the group consisting of ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni), copper (Cu) and iron (Fe).

8. The semiconductor-sensitizing dye as claimed in claim 6, wherein LUMOs are predominantly distributed in (L1)2M1.