WO2007046452A1

WO2007046452A1 - Dye and dye-sensitized solar cell

Info

Publication number: WO2007046452A1
Application number: PCT/JP2006/320809
Authority: WO
Inventors: Yong Wang; Kinji Yamada; Tetsuya Satou
Original assignee: Jsr Corporation
Priority date: 2005-10-19
Filing date: 2006-10-19
Publication date: 2007-04-26
Also published as: TW200728409A

Abstract

Disclosed is a dye which is represented by the general formula (1) below and capable of exhibiting high power generation efficiency. ML1L2X1X2 (1) (In the general formula (1), M represents a group 8-10 element of the long form periodic table; L1 represents a bidentate ligand represented by a certain formula; L2 represents a bidentate ligand represented by the aforementioned certain formula or a formula different from the aforementioned certain formula; and X1 and X2 respectively represent a monovalent atom group or a monodentate ligand.)

Description

Specification

Dye and dye-sensitized solar cell

Technical field

[0001] The present invention relates to a dye and a dye-sensitized solar cell using the same.

Background art

[0002] With increasing interest in energy problems, research on solar cells that can efficiently convert light, particularly sunlight, into electricity has been underway. At present, silicon solar cells using amorphous silicon or polycrystalline silicon are beginning to become popular as solar cells. However, the cost of silicon-based solar cells is high, and high-purity silicon is used, so there are problems in terms of supply. For this reason, there is a limit to the widespread use of silicon-based solar cells in general!

[0003] Since silicon-based solar cells have limitations as described above, in recent years, dye-sensitized solar cells using a dye instead of silicon-based solar cells have attracted attention. In other words, this dye-sensitized solar cell can be used as a raw material as it is without purification of high-purity inexpensive oxide semiconductors such as titanium oxide, which have high power generation efficiency. Therefore, it is expected to be a solar cell having many advantages over silicon-based solar cells (see, for example, Patent Documents 1 and 2).

[0004] Conventionally known dyes used in the above dye-sensitized solar cells include, for example, a dye called ΓΝ719] represented by the following formula (4), and a formula (5) There are dyes called “black dyes”, and these dyes are often used in dye-sensitized solar cells (for example, see Non-Patent Documents 1 and 2).

[0005] [Chemical 1]

[0006] [Chemical 2]

(However, in the above formulas (4) and (5), TBA + represents a tetraptyl ammonium ion) [0007] Patent Document 1: US Pat. No. 4,927,721

Patent Document 2: Pamphlet of International Publication No. 98Z50393

Non-Patent Document 1: Am. Chem. Soc., 115, 6382-6390 (1993) Non-Patent Document 2: Am. Chem. Soc., 123, 1613-1624 (2001) Disclosure of the Invention

[0008] However, the power generation efficiency of the dye-sensitized solar cell is largely dependent on the dye, and the dye-sensitized solar cell using the dye still has sufficient power generation efficiency. Absent. Therefore, development of a dye-sensitized solar cell having sufficient power generation efficiency is required. That is, there is a demand for development of a dye for obtaining a dye-sensitized solar cell capable of obtaining sufficient power generation efficiency.

[0009] As a result of intensive studies to develop the above-described dye and a dye-sensitized solar cell using the dye, the present inventors have found that the dye represented by the following general formula (1) is high. It is extremely useful as a compound that can exhibit power generation efficiency. Dye-sensitized solar cells using this dye are

The inventors have found that the present invention has higher power generation efficiency than conventional dye-sensitized solar cells, and have made the present invention.

That is, the present invention provides the following dye and a dye-sensitized solar cell using the dye.

[0011] [1] A dye represented by the following general formula (1).

[0012] [Chemical 3]

ML ¹ L ² X ¹ X ² (1)

(In the above general formula (1), M is an element of Group 8 to L0 on the long periodic table, L ¹ is a bidentate ligand represented by the following general formula (2), and L ² is It is a bidentate ligand represented by the following general formula (2) or the following general formula (3), and X ¹ and X ² are monovalent atomic groups or monodentate ligands)

[0013] [Chemical 4]

(In the general formula (2), A ¹ is a hydrogen atom, a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof, and R ¹ and R ² are a hydrogen atom or a monovalent organic group. R ³ is a monovalent organic group or a hydrogen atom, one of R ⁴ and R ⁵ is a monovalent organic group, and the other is a monovalent organic group or a hydrogen atom. Each is an integer from 1 to 3)

[0014] [Chemical 5]

(In the above general formula (3), A and a sesame carboxy group, a sulfonic acid group, a phosphoric acid group or a salt thereof, R ⁶ and R ⁷ are a hydrogen atom or a monovalent organic group, m3 and m4 Are each independently an integer from 0 to 3)

[0015] [2] The dye according to [1], wherein M in the general formula (1) is ruthenium.

[0016] [3] In the general formula (2), at least one of R ⁴ and R ⁵ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted group. Or an arylalkyl group or a heteroaromatic group substituted with at least one selected from an unsubstituted alkylthio group, a substituted or unsubstituted alkylamino group, and a substituted or unsubstituted arylol group; The pigment according to 2].

[0017] [4] The dye according to any one of [1] to [3], which is used for a dye-sensitized solar cell.

[0018] [5] A dye-sensitized solar cell using the dye according to any one of [1] to [3]. According to the present invention, a dye capable of producing a dye-sensitized solar cell having high power generation efficiency, and a dye-sensitized solar cell using the dye can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described. However, the present invention is not limited to the following embodiment, and is within the scope of the gist of the present invention. Based on the above, it should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

[0021] [1] Dye:

One embodiment of the dye of the present invention is represented by the following general formula (1). The details will be described below.

[0022] [Chemical 6]

ML ¹ L ² X ¹ X ² (1)

[0023] [Chemical 7]

(In the general formula (2), A ¹ is a hydrogen atom, a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof, and R ¹ and R ² are a hydrogen atom or a monovalent organic group. R ³ is a monovalent organic group or a hydrogen atom, one of R ⁴ and R ⁵ is a monovalent organic group, and the other is a monovalent organic group or a hydrogen atom. Each is an integer from 1 to 3) [0024] [Chemical 8]

(In the above general formula (3), A ² and A ³ are a carboxy group, a sulfonic acid group, a phosphoric acid group or a salt thereof, R ⁶ and R ⁷ are a hydrogen atom or a monovalent organic group, m 3 And m4 are each independently an integer of 0 to 3)

[0025] With such a configuration, there is an advantage that high power generation efficiency can be exhibited when it is desired to use the dye-sensitized solar cell.

[0026] [1 1] L ¹ in general formula (1):

L ¹ in the general formula (1) is a bidentate ligand represented by the general formula (2). In the general formula (2), A ¹ is a hydrogen atom, a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof. Among these, a hydrogen atom, a carboxy group, or a salt thereof is preferable. More preferably, it is a hydrogen atom.

[0027] When A ¹ is a salt, specific examples of counter force thione include ammonia ion, dimethylammonium ion, jetylammonium ion, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, Examples thereof include tetrabutyl ammonium ion, sodium ion, potassium ion, and the like.

[0028] R ¹ in the general formula (2) is a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Among these, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. Ml represents an integer of 1 to 3.

[0029] In the general formula (2), R ² is a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 40 carbon atoms or an alkoxy group. Among these, an alkyl group having 1 to 24 carbon atoms is preferable. M2 is an integer from 1 to 3 Represents.

[0030] R ² is not particularly limited as long as it is a monovalent organic group, but when A ¹ is a hydrogen atom, it is a monovalent organic group other than a carboxyl group, a sulfonic acid group, and a phosphoric acid group. It is preferable.

[0031] R ³ in the general formula (2) is a monovalent organic group or a hydrogen atom. Of these, an alkyl group or a hydrogen atom is preferred, and a methyl group, an ethyl group, or a hydrogen atom is particularly preferred. One of R ⁴ and R ⁵ in the general formula (2) is a monovalent organic group, and the other is a hydrogen atom or a monovalent organic group. Preferably, at least one of R ⁴ and R ⁵ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, substituted or unsubstituted An unsubstituted alkylamino group and a substituted or unsubstituted arylyl group, an aryl group or a heteroaromatic group substituted with at least one selected group. Particularly preferred are, for example, organic groups represented by the following general formulas (6-1) and (6-2). By using R ⁴ and R ⁵ as substituents as described above, there is an advantage that a dye that can be used in a dye-sensitized solar cell having higher power generation efficiency can be obtained.

[0032] [Chemical 9]

Ar X (6-1)

(In the above general formula (6-1), Ar is a divalent aromatic hydrocarbon group or heteroaromatic group, X is a sulfur atom, oxygen atom or single bond, R ⁸ is a substituted or unsubstituted alkyl group, Or substituted or unsubstituted aryl group, wherein Ar is a divalent aromatic hydrocarbon group or heteroaromatic group, and one of R ⁹ and R ^1C> is substituted or unsubstituted. An alkyl group, or a substituted or unsubstituted aryl group, and the other is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group) [0033] Ar in the general formulas (6-1) and (6-2) is a divalent aromatic hydrocarbon group or a heteroaromatic group. Examples of the aromatic ring in the divalent aromatic hydrocarbon group or heteroaromatic group include a benzene ring, a naphthalene ring, an indene ring, and a furan ring. Of these, a group represented by the following formula (6-3) is particularly preferred.

[0034] [Chemical 10]

In general formula (6-1), R ⁸ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among these, an alkyl group, a phenyl group, a naphthyl group, or an alkoxyalkyl group is preferable. The carbon number of R ⁸ is preferably 1 to 50, particularly preferably 1 to 12. X in the general formula (6-1) is a sulfur atom, an oxygen atom or a single bond. In general formula (6-2), R ⁹ and R ^1C> are one of a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the other is a hydrogen atom, a substituted or unsubstituted alkyl group. Or a substituted or unsubstituted aryl group. Among these, one is preferably an alkyl group or a phenyl group, and the other is preferably a hydrogen atom, an alkyl group, or a phenyl group.

[0036] In the general formula (2), one of R ⁴ and R ⁵ is a group represented by the general formula (6-1), the other is a hydrogen atom, and the general formula (6— It is particularly preferred that X in 1) is an oxygen atom or an R ⁸ cation group.

[0037] In the bidentate ligand represented by the general formula (2), when A ¹ is a carboxy group (hereinafter sometimes referred to as "first embodiment"), for example, the following formula (7-1) ) To (7-22). Note that the configuration around the double bond of the substituted bur group (one R ³ C = CR ⁴ R ⁵ ) in the above general formula (2) is either a trans isomer or a cis isomer with no particular restrictions. Also good. Further, the dye of the present invention may include a trans isomer, a cis isomer, and both of them. Of these, many are in the trans form. [0038] [Chemical 11]

[0040] [Chemical 13]

[0042] [Chemical 15]

[0044] [I 匕 17]

(7-20) (7-21) (7-22)

[0046] The dye of the present invention is first characterized by having a bidentate ligand represented by the general formula (2). Second, the bidentate ligand represented by the general formula (2) is characterized in that it has a substituted vinyl group in one pyridine ring of the biviridine skeleton. The substituted vinyl group in the general formula (2) can be introduced into the biviridine skeleton using, for example, the Wittig reaction.

[0047] For example, a phosphonium chloride derivative is synthesized by a reaction represented by the formula (8). Next, as shown in the formula (9), a bidentate ligand represented by the general formula (2) is obtained by reacting the synthesized phosphomuchloride derivative with a bipyridine compound having a carbonyl group or an aldehyde group. Can be synthesized.

[0048] [Chemical 19] R ⁵ R

CH CI ^ CH P + Ph ₂ C ( ⁸⁾

R FT

[0049] [Chemical 20]

[0050] In the formulas (8) and (9),! /, ~, Ml and m2 are respectively in the general formula (2)! ^ ~ Corresponds to 5, 5, and m2, PPh is triphenylphosphine, nBuLi is n-butyllithium

Three

Means. A ¹ in the general formula (2) is a carboxy group, a sulfonic acid group, a phosphoric acid group or a salt thereof, and A ¹ in the formula (9) is the same, but a carboxy group, a sulfonic acid group, or a phosphoric acid It is also preferred that the group is a group protected with a protecting group. Alternatively, a group that easily becomes a carboxy group, a sulfonic acid group, or a phosphoric acid group by oxidation or the like, or a group that protects these groups is preferably A ¹ in Formula (9). These groups can be converted into a carboxy group, a sulfonic acid group or a phosphoric acid group by deprotection and acid after completion of the reaction represented by the formula (9).

[0051] In addition, the bidentate ligand represented by the general formula (2) may be represented by the following formula (7) when A ¹ is a hydrogen atom (hereinafter sometimes referred to as "second embodiment"). — 23) to (7- 43) The compound which has is mentioned. The configuration of the substituted bur group (one R ³ C = CR ⁴ R ⁵ ) in the general formula (2) is not particularly limited with respect to the configuration of the trans isomer or cis isomer. Also good. Further, the dye of the present invention may include a trans isomer, a cis isomer, and both of them. Of these, many are in the trans form. That is, the bidentate ligand represented by the general formula (2) has a substituted bur group in one pyridin ring in the biviridine skeleton, and a carboxy group, a sulfonic acid group, and a phosphorus group in the other pyridine ring. A structure having an organic group other than an acid group is preferable. Thus, by having a substituted beryl group, high power generation efficiency can be obtained because the adsorption efficiency is increased. In addition, since the other pyridine ring has an organic group other than a carboxy group, a sulfonic acid group, and a phosphoric acid group, electron leakage to the electrolyte solution is prevented, so that there is an advantage that higher power generation efficiency can be obtained. is there.

[0052] [Chemical 21]

[0053] [Chemical 22]

(7-32) (7-33) (7-34) [0056] [Chemical 25]

(7-35) (7-36) (7-37)

[0057] [Chemical 26]

(7- 38) (7-39) (7 -40)

[0058] [Chemical 27]

(7-41) (7-42) (7-43)

[0059] When A ¹ is a hydrogen atom, the bidentate ligand represented by the general formula (2) is a substituted bull group in the general formula (2) using, for example, a dehydration reaction of alcohol. It can be synthesized by introducing it into the biviridine skeleton. For example, first, a biviridine derivative alcohol is synthesized. Next, the synthesized biviridine derivative alcohol is dehydrated using a salt by a reaction as shown in formula (10) to form olefin. In this way, the bidentate ligand represented by the general formula (2) can be synthesized. Even if A ¹ is other than a hydrogen atom, as shown in Synthesis Example 3 to be described later, this method can be used to synthesize by ^first introducing a substituted vinyl group and then introducing the substituent A ^1. Can do.

[0060] [Chemical 28]

• · ( Ten )

[0061] In Expression ^{(10), R ^ R 5} , ml and m2 are each in the general formula (2)! ^ ¹ ~! ^ ⁵ , ml and m2 are supported.

[0062] [1 ^2] - general formula (1) in L ^2:

L ² in the general formula (1) is a bidentate ligand represented by the general formula (2) or the general formula (3). General formula (2) has the above-described configuration. A ² and A ³ in the general formula (3) are each independently a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof. Among these, a carboxy group or a salt thereof is preferable. In the case where A ² and A ³ are salts, the same ions as those mentioned as specific examples of the counter counter force thione of A ¹ described above can be preferably used as the force counter cation.

In the general formula (3), R ⁶ and R ⁷ are a hydrogen atom or a monovalent organic group. Examples of the organic acid include an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Among these, a hydrogen atom or a methyl group is preferable. M3 and m4 in the general formula (3) are each independently an integer of 1 to 3.

[0064] Note that L ¹ and L ² are bidentate ligands in which L ¹ is represented by the general formula (2), and L ² is the general formula (2) or the general formula (3). As long as it is a bidentate ligand represented, there is no particular limitation! The case where both of the forces L ¹ and L ² are represented by the above general formula (2) is also a preferred embodiment. In order to obtain good power generation efficiency, it is preferable to have a carboxyl group as a substituent. Therefore, when both L ¹ and L ² are represented by the above general formula (2), it is preferable that the first mode (A ¹ in the general formula (2) is a carboxy group). ,.

[0065] [1 3] —M in general formula (1):

M in the general formula (1) is an element of group 8 to 10 on the long periodic table. Examples of this element include iron, cobalt, nickel, ruthenium, osmium, iridium, platinum and the like. Among these, ruthenium is preferable.

[0066] [1 4] X ¹ and X ² in the general formula (1):

X ¹ and X ² in the general formula (1) are a monovalent atomic group or a monodentate ligand. Examples of the monovalent atomic group or monodentate ligand include atomic groups or ligands represented by the following formulas (11) to (17).

[0067] [Chemical 29]

C (1 5) 0H: (1 6)

For example, R ¹¹ in the general formula (12) is preferably an alkyl group having 1 to 6 carbon atoms. Ar in the general formulas (13) and (17) is an aryl group having 6 to 12 carbon atoms. Preferably there is. X ¹ and X ² in the general formula (1) are preferably those represented by the above general formula (2) (isothiocyanate) among the above atomic groups or ligands!

[0069] For example, as described above, the dye of the present invention can be synthesized by synthesizing a ligand according to the formula (8) and the formula (9) or the formula (10), and then “Nat. Mater. 2, 402-407 (2003) ”.

[0070] [2] Dye-sensitized solar cell:

The dye-sensitized solar cell of the present invention can suitably use the dye of the present invention. The dye-sensitized solar cell of the present invention may have at least a cathode, an anode facing the cathode, and an electrolyte held between the cathode and the anode. The cathode may have an oxide thin film electrode in which the above-described dye is chemically adsorbed on a transparent conductive glass. Here, examples of the transparent conductive glass include tin oxide and indium-tin oxide (ΙΤΟ).

[0071] Examples of the material constituting the oxide thin film electrode include titanium oxide, niobium oxide, zinc oxide, tin oxide, tungsten oxide, and indium oxide. Of these, titanium oxide, niobium oxide, and tin oxide are preferred, and titanium oxide is particularly preferred. There is no limitation on the method of forming the oxide thin film electrode. For example, oxide fine particles to be an oxide thin film electrode are formed, suspended in an appropriate solvent, and applied onto transparent conductive glass. A method of heating after removing the solvent can be employed.

[0072] In order to adsorb the dye of the present invention to the oxide thin film electrode, an appropriate method can be adopted. For example, a transparent conductive film having an oxide thin film electrode on the surface obtained as described above can be used. It can be carried out by immersing the glass in a solution containing the pigment of the present invention. Examples of the solvent that can be used here include jetyl ether, acetonitrile, ethanol, and the like. The concentration of the dye solution is preferably 0.1 to: LOmmolZL. As the soaking time, 0.5 to: LOO time is preferred 2 to 50 hours is more preferred. The temperature during the immersion is preferably 0 to 100 ° C, more preferably 10 to 50 ° C.

[0073] The anode is not particularly limited as long as it has electrical conductivity. For example, a material obtained by adhering a small amount of platinum or conductive carbon on transparent conductive glass can be suitably used. The As the electrolyte, for example, a solution containing a redox system, a solid, or an ionic liquid can be used. Specific examples thereof include, for example, a system using the following reaction of iodine (shown by Formula 18) as a redox system, and an electrolyte solution containing, for example, acetonitrile or propio-tolyl as a solvent. .

I "+ 2e" = 3I "+ I (18)

3 2

Example

[0074] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0075] (Synthesis of ligand)

(Synthesis Example 1):

4, 4, 1-dimethyl 1, 2, 2, 1-biviridine l lg was dissolved in 300 ml of tetrahydrofuran. Separately, 35 ml of lithium diisopropylamide solution (concentration 1.8 M, mixed solvent of tetrahydrofuran Z heptane Z ethylbenzene) and 3 ml of tetrahydrofuran were mixed and kept at −78 ° C. To this solution, a tetrahydrofuran solution of 4,4′dimethyl-2,2′biviridine was added dropwise over 75 minutes while stirring at 78 ° C. under a nitrogen atmosphere. After completion of dropping, the mixture was further stirred for 15 minutes. Subsequently, the temperature was raised to 0 ° C over 15 minutes with stirring, and then maintained at 0 ° C for 60 minutes. The mixture was stirred while maintaining a temperature of 0 ° C under a nitrogen atmosphere, and 88 ml of tetrahydrofuran solution containing 7.5 ml of p-methoxybenzaldehyde was added dropwise over 60 minutes. Thereafter, the mixture was stirred for 120 minutes. Next, while stirring under a nitrogen atmosphere, the temperature was raised to room temperature over 90 minutes, and further stirred at room temperature for 12 hours.

Tetrahydrofuran was distilled off under reduced pressure at room temperature, 300 ml of dichloromethane and 500 ml of ion-exchanged water were added and stirred, and then the aqueous layer and the organic layer were separated. The aqueous layer was extracted twice with 300 ml of dichloromethane, the extract and the organic layer were mixed, washed twice with 300 ml of ion-exchanged water, and dried by adding 22 g of magnesium sulfate. After drying, magnesium sulfate was filtered off, dichloromethane was distilled off under reduced pressure at room temperature, and further dried under reduced pressure at room temperature to obtain 2 lg of a yellow solid. This solid was purified using a silica gel column under the conditions described later to obtain 9.8 g of product. This product was analyzed by ¹ H-NMR and found to be 4- [2- (4-methoxyphenyl) 2 -hydroxyethyl] -4'-methyl-2,2'-biviridine. — The result of NMR is shown below.

[0077] — NMR (CDCL, 298K, 300ΜΗζ, δ (ppm)); δ = 8.52 (t, 2Η), 8. 25

Three

(d, 2Η), 7.26 (m, 2Η), 7.10 (t, 2Η), 6.88 (d, 2Η), 4.96 (d, 1Η), 3.81 (m, 3Η, Me), 3.07 (m, 2H), 2.42 (d, 3H, Me), 2.22 (s, 1H)

[0078] [Silica gel column purification conditions]:

Silica gel lOOg was packed into a 200 ml column and the column was filled with black mouth form. The above yellow solid was dissolved in 50 ml of black mouth form and applied to the above column. After developing with black mouth form, the volume was developed with 90.5 / 7.5 black mouth form Z methanol solvent and fractionated.

[0079] 4 [2- (4-methoxyphenyl) 2 hydroxyethyl] —4,1-methyl-2,2, bipyridine, and l lg ammonium p-toluene sulfonate synthesized as described above were used. Dissolved in 2000 ml of toluene. The above solution was heated to reflux at 90 ° C. for 11 hours under a nitrogen atmosphere, and then returned to room temperature over 60 minutes. After washing with 600 ml of ion-exchanged water, it was dried with 14 g of magnesium sulfate. Next, magnesium sulfate was filtered off, toluene was distilled off under reduced pressure, and dried under reduced pressure at room temperature to obtain 4.5 g of a yellow powder. This product was deduced by ¹ H-NMR and found to be 4-methyl-4 ′-(4-methoxystyryl) 2,2′-biviridine. The result of NMR is shown below.

[0080] — NMR (CDCL, 298K, 270ΜΗζ, δ (ppm)); δ = 8.61 (d, 1Η), 8. 57

Three

(d, 1Η), 8.49 (s, 1Η), 8.26 (s, 1Η), 7.51 (d, 2Η), 7.41 (d, 1Η), 7.35 (m, 1Η) 7.16 (d, 1Η), 7.01 (d, 1Η), 6.93 (d, 2Η), 3.82 (s, 3Η, Me), 2.46 (s, 3H, Me)

[0081] (Synthesis Example 2)

To 27 g of 2,2, -biviridine-4,4, -dicarboxaldehyde and 73 g of p-toluenesulfonic acid monohydrate was added 2500 ml of black mouth form and stirred. To this solution, a solution prepared by adding 500 ml of chloroform to 13 g of 2,2 dimethyl-1,3 propanediol was added dropwise, stirred at room temperature for 12 hours, and allowed to stand for another 2 days. A saturated aqueous sodium carbonate solution was added to the reaction solution, followed by extraction with black mouth form. The organic layer is washed with water, dried over magnesium sulfate, and concentrated with an evaporator to give 2, 2, -biviridine-4, 1 (5, 5 dimethyl). (Chillyl-1,3 dioxa 2 cyclohexyl) 4 32 g of a mixture containing carboxaldehyde was obtained. This was used in the next reaction without purification.

[0082] Separately, 2000 ml of toluene was added to 172 g of 4-methoxybenzyl chloride and 262 g of triphenylphosphine, and the mixture was refluxed at 120 ° C for 12 hours under a nitrogen atmosphere. After allowing to cool, the resulting solid was collected by filtration, washed with toluene, and further vacuum dried to obtain 222 g of methoxybenzyl phosphate chloride.

[0083] 200 ml of anhydrous tetrahydrofuran was added under nitrogen atmosphere to 20.9 g of methoxybenzylphosphonium chloride synthesized as described above. While maintaining this solution at 0 ° C. in a nitrogen atmosphere, 31 ml of a hexane solution of n-butyllithium (concentration 1.6 M) was added dropwise and stirred at 0 ° C. for 2 hours. This solution was cooled to -78 ° C, and the mixture containing 2,2, -biviridine-4,-(5,5-dimethyl 1,3 dioxa-2 cyclohexyl) 4 carboxaldehyde synthesized above 14. to Og A solution containing 2000 ml of tetrahydrofuran was added dropwise, and the mixture was stirred at 78 ° C. for 2 hours and at room temperature for 12 hours. After the reaction, 150 ml of water was added, concentrated with an evaporator, and extracted with dichloromethane. The organic layer is washed with water, dried over magnesium sulfate, and concentrated with an evaporator to give 4- (5,5 dimethyl-1,3 dioxa-2-cyclohexyl) -4,1- (4-methoxystyryl) -2,2, -830 mg of a mixture containing biviridine was obtained.

[0084] 4 was synthesized by the above (5, 5-dimethyl-1, 3 Jiokisa 2 cyclohexyl) one _4, one _{(4-methoxy-styryl)} one _2, _2, - Bibirijin the mixture 814mg containing p- Torue Nsuruhon acid pyrid -15 mg of acetone, 160 ml of acetone and 40 ml of water were added and refluxed at 100 ° C for 12 hours. After the reaction, the mixture was concentrated with an evaporator and extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated by an evaporator to obtain 440 mg of a mixture containing 2,2′bibilidine- ₄ , ( ₄ -methoxystyryl) -4 carboxaldehyde.

[0085] This mixture of 2, 2, 1 biviridine and 1, 4- (4-methoxystyryl) 4-carboxaldehyde was added to a solution obtained by adding 12 ml of ethanol to 420 mg, and a solution obtained by adding 3 ml of water to 255 mg of silver nitrate. did. To this solution, 6 ml of sodium hydroxide aqueous solution (concentration 1M) was added dropwise and stirred at room temperature for 12 hours. The reaction solution is filtered and concentrated with an evaporator. Hydrochloric acid was added to adjust the pH to 3, followed by extraction with dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, and concentrated with an evaporator to obtain 242 mg of a solid. This solid was purified using an ion exchange column and a silica gel column to obtain 185 mg of a product. This product was analyzed by ¹ H-NMR and found to be 2, 2, 1 biviridine, 1-, 4- (4-methoxystyryl) 4 strength rubonic acid.

[0086] (Synthesis Example 3)

Another synthesis method of 2,2′-biviridine mono 4 ′-(4-methoxystyryl) 4-carboxylic acid synthesized in Synthesis Example 2 is described below. First, 4-methyl-4 ′-(4-methoxystyryl) 2,2′-biviridine was synthesized in the same manner as in Synthesis Example 1. 6.7 g of this 4-methyl-4 ′ (4-methoxystyryl) -2,2, -biviridine was dissolved in 67 ml of dimethylformamide and kept at 150 ° C. To this solution, 7.7 g of butoxybisdimethylaminomethane was added dropwise under a nitrogen atmosphere, and the above solution was heated to reflux at 150 ° C for 10 hours under a nitrogen atmosphere, and then returned to room temperature over 60 minutes. 50 ml was added.

[0087] 50 ml of dichloromethane and 50 ml of ion-exchanged water were added and stirred, and then the aqueous layer and the organic layer were separated. The aqueous layer was extracted twice with 50 ml of dichloromethane, the extract and the organic layer were mixed, washed twice with 100 ml of saturated brine, and dried by adding lg of magnesium sulfate. After drying, magnesium sulfate was filtered off, dichloromethane and dimethylformamide were distilled off under reduced pressure at room temperature, and further dried under reduced pressure at room temperature to obtain 8.5 g of a yellow solid. The powder was reprecipitated with dichloromethane-hexane solution and purified to obtain 6.7 g of the product. The product was analyzed by ¹ H-NMR and found to be 4- (N, N, 1 dimethylaminovinyl) 4, 1 (4-methoxystyryl) -2, 2, 1 biviridine. I understood. The results of H-NMR are shown below.

[0088] — NMR (CDCL, 298K, 270ΜΗζ, δ (ppm)); δ = 8.59 (d, 1Η), 8. 46

Three

(s, 1Η), 8.29 (d, 1Η), 8.09 (s, 1Η), 7.71 (d, 2Η), 7.61 (d, 1Η), 7.49 (d, 1Η) 7.33 (d, 1Η), 7.17 (d, 1Η), 7.03 (d, 1Η), 6.94 (d, 2Η), 5.10 (d, 1Η), 3.86 ( s, 6Η, Me), 2.93 (s, 3H, Me)

[0089] 4- (N, N, -dimethylaminovinyl) -4,-(4-methoxystyryl) -1,2,2, monobiviridine synthesized as described above was dissolved in 300 ml of tetrahydrofuran. It was. This solution To the solution, 200 ml of a sodium periodate aqueous solution (concentration: 0.35 M) was added dropwise over 75 minutes, and the mixture was stirred at room temperature for 8 hours.

[0090] The formed precipitate was filtered off, and tetrahydrofuran was distilled off under reduced pressure at room temperature. After adding 10 Oml of dichloromethane and stirring, the aqueous layer and the organic layer were separated. The aqueous layer was extracted twice with 100 ml of dichloromethane, the extract and the organic layer were mixed, washed twice with 100 ml of saturated brine, and dried by adding lg of magnesium sulfate. After drying, magnesium sulfate was filtered off, dichloromethane was distilled off under reduced pressure at room temperature, and further dried under reduced pressure at room temperature to obtain 5.5 g of a yellow solid. The product was analyzed by ¹ H-NMR and found to be 4 carbaldehyde -4 ′-(4-methoxystyryl) 2,2′-biviridine. The results of NMR are shown below.

[0091] 'H-NMRCDMSO-d, 298K, 270ΜΗζ, δ (ppm)); δ = 9.61 (s, 1Η), 8

6

84 (s, 1mm), 8.81 (d, 1mm), 8.67 (d, 1mm), 8.53 (s, 1mm), 7.80 (d, 1mm), 7.64 (d, 2Η), 7.63 (d, 1Η), 7.58 (d, 1Η), 7.21 (d, 1Η), 6.96 (d, 2Η), 3.75 (s, 3Η, Me)

[0092] Four-one carbaldehyde 4, 1, 1- (4-methoxystyryl) 1, 2, 2, -biviridine synthesized as described above was mixed with 150 ml of 95% ethanol. To this suspension, 30 ml of an aqueous silver nitrate solution (concentration 0.06 M) was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 30 minutes. Further, 75 ml of an aqueous sodium hydroxide solution (concentration: 1M) was added dropwise over 45 minutes, and the mixture was stirred at room temperature for 2 hours.

[0093] Ethanol was distilled off under reduced pressure at room temperature, 1000 ml of a 6% dimethylformamide aqueous solution was added and stirred, and then the pH was adjusted to 3 with hydrochloric acid (concentration 1M). The resulting precipitate was collected by filtration and further dried under reduced pressure at room temperature to obtain 5.6 g of a black solid. This solid was purified using a silica gel column under the following conditions, and further purified by reprecipitation with a dimethylformamide-toluene solution to obtain 1.4 g of a product. When this product was analyzed by ¹ H-NMR, this product was found to be 4 carboxyl-4, 1 (4-methoxystyryl) -2, 2, 2-biviridine (2, 2, 1 biviridine 1 4,-(4 -Methoxystyryl) 4-carboxylic acid). Yeah! The result of NMR is shown below.

[0094] 'H-NMRCDMSO-d, 298K, 270ΜΗζ, δ (ppm)); δ = 8.85 (s, 1Η), 8

6

83 (d, 1mm), 8.66 (d, 1mm), 8.54 (s, 1mm), 7.86 (d, 1mm), 7.66 (d, 2mm), 7 64 (d, 1H), 7.60 (d, 1H), 7.25 (d, 1H), 6.99 (d, 2H), 3.78 (s, 3H, Me

)

[0095] (Synthesis of dye)

(Example 1):

4-methyl 4 '-(4-methoxystyryl) obtained in Synthesis Example 1 above was added to a solution of N, N-dimethylformamide 7 5mL added to 150mg dimer (Pcymene) ruthenium (II) dimer. ) -2, 2,-Biviridine 149mg was added. The mixture was stirred at 60 ° C. for 4 hours under a nitrogen atmosphere, 121 mg of 2,2′-biviridine-4,4′-dicarboxylic acid was added, and the mixture was refluxed at 150 ° C. for 4 hours. Thereafter, 483 mg of potassium thiocyanate was added, and the mixture was further refluxed at 150 ° C. for 4 hours. After standing to cool, the mixture was concentrated by an evaporator, 45 mL of water was added, and the pH was adjusted to 2.5 by adding dilute nitric acid while stirring at room temperature. The resulting precipitate was collected by filtration and purified using a Sephadex LH-20 column (commercially available, manufactured by Amersham Biosciences) to obtain 121 mg of product. — Analysis by NMR revealed that this product was represented by the following formula (19) (yield 32%). This compound is designated “T2”. 'Η-Ν MR results are shown below.

[0096] — NMR (DMSO—d, 298Κ, 270ΜΗζ, δ (ppm)); δ = 9.45 (d, 2Η), 9

6

09 (m, 2Η), 8.96 (d, 1Η), 8.83 (d, 1Η), 8.69 (d, 1Η), 8.55 (d, 1Η), 8.28 (m, 2Η), 7.91 (t, 1Η), 7.85 (d, 1Η), 7.78 (m, 2Η), 7.72 (m, 1Η), 7.61 (m, 1Η), 7. 29 (m, 2Η), 3.82 (d, 3Η, Me)

[0097] [Chemical 30]

[Example 2]:

2,2, -biviridine-4,-(4) obtained in Synthesis Example 2 above was added to a solution obtained by adding 5 mL of N, N-dimethylformamide 7 to 153 mg of dimer (p-cymene) ruthenium (II) dichloride. —Methoxystyryl) — A dye represented by the following formula (20) was synthesized in the same manner as in Example 1 except that 166 mg of 4-carboxylic acid was added. 118 mg of dye was obtained and the yield was 29%. This compound is designated “T1”.

[0099] [Chemical 31]

[0100] (Example 3):

2, 2, -biviridine-4,-(4-) obtained in Synthesis Example 3 above was added to a solution of 153 mg of N, N-dimethylformamide 7 in 153 mg of dimer (p-cymene) ruthenium (II) dichloride. A dye was synthesized in the same manner as Example 1 except that 166 mg of methoxystyryl) -4-carboxylic acid was added. 118 mg of dye was obtained and the yield was 29%. This compound is referred to as “Tla”. In addition, the pigment | dye of a present Example has a structure represented by the said Formula (20).

[0101] (Example 4):

4-Carboxyl 4 '-(4-methyoxystyryl) obtained in Synthesis Example 3 above was added to a solution obtained by adding 5 mL of N, N-dimethylformamide 7 to 150 mg of dimer (P-cymene) ruthenium (II) dimer. ) -2, 2,-Biviridine 159mg was added. This mixture was placed under a nitrogen atmosphere. After stirring at 60 ° C for 4 hours, 159 mg of 4 ol-poxylulu 4'-one (4-methoxystyryl) -2,2, -biviridine obtained in Synthesis Example 1 above was added, and the mixture was added at 150 ° C. Reflux for hours. Thereafter, a dye represented by the following formula (21) was synthesized in the same manner as in Example 1. 118 mg of dye was obtained, and the yield was 29%. This compound is designated “T3”. — The NMR results are shown below.

[0102] — NMR (DMSO— d, 298 Κ, 270 ΜΗζ, δ (ppm)); δ = 9. 44 6. 96 (m

6

, 24Η), 3.82 (d, 6Η, Me)

[0103] [Chemical 32]

[0104] (Production of dye-sensitized solar cell) (Example 5):

In a mixed medium of 0.4 mL of acetylylacetone and 20 mL of ion-exchanged water, 12 g of titanium oxide fine particles and 0.2 g of dispersant Triton X-100 (commercially available, manufactured by Aldrich) are added, and the dispersion liquid is added. Prepared. This dispersion was applied onto a 1 mm thick conductive glass substrate (made of tin oxide, resistance = 10 Ω Ζ «η ² ), heated in air at 500 ° C for 1 hour, and titanium oxide on the surface. A conductive glass substrate for cathode having a thin film was obtained. This glass substrate was immersed in a solution of acetonitrile = butanol (volume ratio: 1Z1) containing the dye “T2” obtained in Example 1 at a concentration of 0.4 mmol ZL at 23 ° C. for 24 hours. Next, the conductive glass substrate for a cathode was pulled up and naturally dried for 2 hours to make this conductive glass substrate a cathode. On the other hand, apart from the cathode conductive glass substrate, an anode conductive glass substrate (thickness lmm, tin oxide, resistance = 10 Ω = «η ² ) is prepared, and platinum is deposited on this glass substrate. The anode was used.

[0105] Furthermore, an electrolyte solution containing 0.1 ImolZL iodine and 0.5 molZL lithium iodide in acetonitrile was prepared. The surface of the cathode having the titanium oxide thin film and the surface of the anode on which platinum is deposited face inward, face each other at a distance of 0.1 mm, and sandwich the electrolyte solution therebetween (dye-sensitized solar cell) Battery cell).

[0106] (Evaluation of dye-sensitized solar cell):

With respect to the dye-sensitized solar cell manufactured as described above, when the solar simulator “XC-100BJ (manufactured by Celic)” was used to irradiate pseudo-sunlight with an illuminance of lOOOWZm ² , the power generation efficiency was measured. It was confirmed that it was%.

[Example 6]:

A dye-sensitized solar cell (dye-sensitized solar cell) was produced in the same manner as in Example 5 except that the dye “T1” obtained in Example 2 was used, and the power generation efficiency was evaluated. It was confirmed that the dye-sensitized solar cell of this example had a power generation efficiency of 8.1%.

[0108] (Example 7):

A dye-sensitized solar cell (dye-sensitized solar cell) was produced in the same manner as in Example 5 except that the dye “Tla” obtained in Example 3 was used, and the power generation efficiency was evaluated. It was confirmed that the power generation efficiency of the dye-sensitized solar cell of this example was 8.6%. [Example 8]:

A dye-sensitized solar cell (dye-sensitized solar cell) was produced in the same manner as in Example 5 except that the dye “T3” obtained in Example 4 was used, and the power generation efficiency was evaluated. The dye-sensitized solar cell of this example was confirmed to have a power generation efficiency of 8.4%.

[0110] (Comparative Example 1):

Dye sensitization was performed in the same manner as in Example 5 except that a commercially available dye “Ν 719” (manufactured by Solaronix) was used as the dye having the structure represented by the above formula (4) instead of the dye “Τ 2”. A solar cell was produced and evaluated in the same manner as in “Evaluation of dye-sensitized solar cell” in Example 5. As a result, it was confirmed that the power generation efficiency was 6.1%.

Industrial applicability

[0111] Since the dye of the present invention and the dye-sensitized solar cell using this dye are excellent in power generation efficiency, they can be applied to various fields as a dye for solar cells and a solar cell.

Claims

Claims Dye represented by the following general formula (1). [Chemical 1] ML1 L2 X1 X2 (1)

[Chemical 2]

[Chemical 3]

(3)

[2] The dye according to claim 1, wherein M in the general formula (1) is ruthenium.

[3] In the general formula (2), at least one of R ⁴ and R ⁵ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted The alkylthio group, a substituted or unsubstituted alkylamino group, and a substituted or unsubstituted arylylamino group, an arylene group substituted with at least one selected group or a heteroaromatic group according to claim 1 or 2. Pigment.

[4] The dye according to any one of claims 1 to 3, which is used for a dye-sensitized solar cell.

[5] A dye-sensitized solar cell using the dye according to any one of claims 1 to 3.