WO2008056567A1 - Novel amino group-containing aromatic compound, and sensitizing dye for photoelectric conversion, containing the aromatic compound - Google Patents

Abstract

This invention provides an aromatic compound containing an amino group at its end represented by formula (1): (1) wherein R1, R2, R4, and R5 each independently represent a hydrogen atom or an optionally substituted monovalent organic residue, provided that R1 and R2 together may form a ring and R1 and/or R2, together with X, may form a ring; and R3 represents an anchor group which can be linked to an inorganic porous material having semiconductor properties. By virtue of the specific partial structure, the above aromatic compoud has a broad absorption band in a visible range and can be used as photofunctional materials, particularly sensitizing dyes for photoelectric conversion. In particular, the use of the aromatic compound in dye-sensitized photoelectric conversion batteries can realize the provision of photoelectric conversion batteries having high photoelectric conversion efficiency and high stability.

Description

 Specification

 Novel amino group-containing aromatic compound and photoelectric conversion sensitizing dye containing the aromatic compound

 Technical field

 The present invention relates to a novel amino group-containing aromatic compound and a sensitizing dye for photoelectric conversion using the same

The present invention relates to a photoelectric conversion material using the same, a photoelectric conversion electrode, and a photoelectric conversion solar cell using the same.

 Background art

 [0002] At present, energy relies heavily on fossil fuels typified by oil, coal, and natural gas. In addition, carbon dioxide emissions inevitably remain a problem when obtaining energy from fossil fuels, and there is a problem with a large environmental burden.

 [0003] Recently, solar power generation has attracted more attention due to these concerns. At present, silicon solar cells using monocrystalline or polycrystalline crystalline silicon or amorphous silicon, some of which are compounds using gallium or arsenic. Although there is a lot of development and research on semiconductor solar cells, there is still a need for overcoming various problems such as manufacturing costs. On the other hand, many proposals have been made for solar cells using photosensitizing dyes! / However, conversion efficiency is low and durability is poor! / And! / was there.

Under such circumstances, there was a report by Graetzel et al. In 1991 (Non-patent Document 1), and photoelectric conversion electrodes and photoelectric conversion batteries using an inorganic semiconductor porous material photosensitized with a dye attracted attention. I was bathed. The photoelectric conversion element described in this report is manufactured using a relatively inexpensive inorganic oxide semiconductor such as titanium oxide, and it is possible to obtain a photoelectric conversion element at a lower cost than a general-purpose silicon solar cell. Have sex. However, at present, high photoelectric conversion efficiency cannot be obtained unless it is a ruthenium-based sensitizing dye, so that the cost of the dye is low and the number of Clarks is low, so there remains a problem in their stable supply. On the other hand, development of organic dyes has been actively conducted, but it has been realized because of low conversion efficiency. Not yet commercialized. In addition, a dye having a specific acrylic acid moiety or a sensitizing dye having an amide derivative has been disclosed (see Patent Document 1, Patent Document 2, and Patent Document 3), but it cannot be said that it has sufficient performance! /, It was a thing.

[0005] Patent Document 1: Pamphlet of International Publication No. 02/011213

 Patent Document 2: JP 2004-143355 A

 Patent Document 3: Japanese Patent Laid-Open No. 2005-097561

 Non-Patent Document 1: Brian O'Regan, Mich ael Graetzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal Ti02 film (A low-cost, high-efficiency solar cell) cell based on dye—sensitized colloidal titanium dioxide films ”, Nature, UK, October 1991, Vol. 353, p. 737—740

 Disclosure of the invention

 Problems to be solved by the invention

The present invention aims to provide a novel amino group-containing aromatic compound having a wide absorption band in the visible region and useful as a sensitizing dye for photoelectric conversion used in a dye-sensitized photoelectric conversion battery. And Further, a photoelectric conversion material obtained by connecting an inorganic porous substance exhibiting semiconductor characteristics and this sensitizing dye for photoelectric conversion, a photoelectric conversion electrode obtained by laminating this photoelectric conversion material on a transparent electrode, and the photoelectric conversion electrode and electrolyte An object of the present invention is to provide a photoelectric conversion battery comprising a layer and a conductive counter electrode.

 Means for solving the problem

[0007] As a result of intensive efforts to solve the above problems, the present inventors have found that a compound having a specific partial structure is useful as a sensitizing dye for photoelectric conversion. That is, the present invention provides an aromatic compound containing an amino group at the terminal represented by the following formula (1).

式（1)において、

R²、 R⁴および R⁵は、それぞれ独立して、水素原子、または置 換基を有していてもよい 1価の有機残基である。ここで、 R¹および R²は共同して環を 形成してもよい。また、 R¹および/または R²は、 Xと共同して環を形成してもよい。 R³ は、半導体特性を示す無機多孔質物質と連結し得るアンカー基である。 Xは、 2価の 芳香族炭化水素基、または 2個以上の 2価の芳香族炭化水素基の組合せである。該 2価の芳香族炭化水素基は、置換基を有していても良ぐ 2個以上の環が縮合してい てもよい。 Yは 2価の芳香族炭化水素基である。該 2価の芳香族炭化水素基は、置換 基を有していても良く、 2個以上の環が縮合していてもよい。 Zは、 2価の芳香族複素 環基、 2価の芳香族炭化水素基、 2価の不飽和炭化水素基、およびこれらの組合せ である。 2価の芳香族複素環基、 2価の芳香族炭化水素基および 2価の不飽和炭化 水素基は置換基を有していても良ぐ該 2価の芳香族複素環基および 2価の芳香族 炭化水素環基は 2個以上の環が縮合していても良い。ただし、 Xからアンカー基 ま で π共役系を形成する構造である。また Xおよび Υの少なくとも一方は、一つ以上の フッ素原子で置換された 2価の芳香族炭化水素基である。 mは、；!〜 3の整数である 。 nは 0または 1の整数である。式（1)中の二重結合は、シス トランス異性体のいず れを生じさせるものであってもよ!/、。 [Chemical 1]

In equation (1),

R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic residue optionally having a substituent. Here, R ¹ and R ² may jointly form a ring. R ¹ and / or R ² may form a ring together with X. R ³ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor properties. X is a divalent aromatic hydrocarbon group or a combination of two or more divalent aromatic hydrocarbon groups. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed. Y is a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed. Z is a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, a divalent unsaturated hydrocarbon group, or a combination thereof. A divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group and a divalent unsaturated hydrocarbon group may have a substituent, and the divalent aromatic heterocyclic group and divalent aromatic group may be substituted. In the aromatic hydrocarbon ring group, two or more rings may be condensed. However, this structure forms a π-conjugated system from X to the anchor group. Also, at least one of X and Υ is a divalent aromatic hydrocarbon group substituted with one or more fluorine atoms. m is an integer from! n is an integer of 0 or 1. The double bond in formula (1) may give rise to any of the cis-trans isomers! /.

 [0008] X in the formula (1) may be a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a biphenylene group or a terfenylene group, each of which may have a substituent. preferable. Furthermore, a phenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group, each of which may have a substituent, are preferable.

[0009] In the formula (1), R ³ is preferably a carboxyl group, a phosphoric acid group or a sulfonic acid group.

[0010] In the formula (1), R ¹ , R ² , R ⁴ , and R ⁵ may be a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic group which may have a substituent. Group heterocyclic group, or a halogen atom, cyano group, isocyano group, thiocyanate group, isothiocyanate group, nitro group, hydroxyl group, mercapto group, amino group, amide group, or the following formula (2) It is preferably a group.

[Chemical 2]

In the formula (2), A ¹ and A ² are each independently ◯, NH or S. B is a carbonyl group, a thiocarbonyl group, a sulfiel group or a sulfonyl group. o and p are each independently 0 or 1. R ⁶ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, or a halogen atom, a cyano group, an isocyano group or a thiocyanate group. , An isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, or an amide group.

[0011] R ⁴ in formula (1) is preferably an electron-attracting group, particularly preferably a cyano group, an ester group, an amide group or a perfluoroalkyl group! / ,.

[0012] In the formula (1), R ³ is preferably a carboxyl group.

 [0013] It is preferable that Y in the formula (1) is a 1,4-phenylene group which may have a substituent.

 [0014] X in the formula (1) is preferably a 1,4-phenylene group which may have a substituent.

 [0015] The present invention also provides a sensitizing dye for photoelectric conversion, comprising an aromatic compound containing an amino group at the terminal represented by the formula (1).

[0016] The photoelectric conversion sensitizing dye may further include a photosensitizing dye other than the aromatic compound containing an amino group at the terminal represented by the formula (1).

[0017] The present invention also provides a photoelectric conversion material obtained by linking the above-described sensitizing dye for photoelectric conversion and an inorganic porous material exhibiting semiconductor characteristics.

[0018] The present invention also provides a photoelectric conversion material characterized by using a co-adsorbent in combination with the above-described sensitizing dye for photoelectric conversion.

[0019] The inorganic porous material exhibiting the above semiconductor characteristics is preferably composed of an inorganic oxide.

 [0020] The present invention also provides a photoelectric conversion electrode obtained by laminating the above photoelectric conversion material on a transparent electrode.

[0021] The present invention also provides a photoelectric conversion battery comprising the photoelectric conversion electrode, the electrolyte layer, and the conductive counter electrode. The invention's effect

 [0022] Since the amino group-containing aromatic compound of the present invention has a specific partial structure, it has a wide absorption band in the visible region, and can be used as an optical functional material, particularly a sensitizing dye for photoelectric conversion. In particular, when used for a dye-sensitized photoelectric conversion battery, a photoelectric conversion battery having high photoelectric conversion efficiency and high stability can be provided.

 In addition, the energy level of HOMO and LUMO can be easily adjusted by selecting specific substituents, so that the desired performance can be achieved in accordance with other materials that make up the dye-sensitized photovoltaic cell. Can do.

 Brief Description of Drawings

 FIG. 1 is a schematic diagram of a test sample of a photoelectric conversion cell used in a photoelectric conversion test of an example.

 Explanation of symbols

[0024] 1: Glass substrate

 2: Transparent electrode layer

 3: Platinum electrode layer

 4: Titanium oxide porous layer (adsorbed sensitizing dye for photoelectric conversion)

 5: Electrolyte

 6: Spacer made of resin film

 7: Measuring lead

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

 In the present specification, when it is described as “may have a substituent”, the substituent specifically includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. Or a halogen atom, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, an amide group, or a monovalent group represented by the following formula (2) is there.

[Chemical 3]

In the formula (2), A ¹ and A ² are each independently ◯, NH or S. B is a carbonyl group, a thiocarbonyl group, a sulfiel group or a sulfonyl group. o and p are each independently 0 or 1. R ⁶ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, or a halogen atom, a cyano group, an isocyano group or a thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

 The novel amino group-containing aromatic compound of the present invention is an amino group-containing compound having a specific partial structure, specifically, a terminal amino group-containing compound represented by the following formula (1):

[Chemical 4]

In the formula (1), R ¹ , R ² , R ⁴ and IT are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. Here, R ¹ and R ² may jointly form a ring. R ¹ and / or R ² may form a ring together with X. R ³ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor properties. X is a divalent aromatic hydrocarbon group or a combination of two or more divalent aromatic hydrocarbon groups. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed. m is an integer of 1 to 3. n is an integer of 0 or 1. Y is a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed. Z is a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, a divalent unsaturated hydrocarbon group, or a combination thereof. The divalent aromatic heterocyclic group, the divalent aromatic hydrocarbon group, and the divalent unsaturated hydrocarbon group have a substituent! /, The divalent aromatic heterocyclic group and In the divalent aromatic hydrocarbon ring group, two or more rings may be condensed. However, it is a structure that forms a π-conjugated system from X to the anchor group R ³ . In addition, at least one of X and Υ is divalent substituted with one or more fluorine atoms. Is an aromatic hydrocarbon group. The double bond in formula (1) may give rise to any of the cis-trans isomers! /.

[0027] First, X in formula (1) will be described. X represents a divalent aromatic hydrocarbon group or a combination of two or more divalent aromatic hydrocarbon groups. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed. Further, when it has a substituent, two or more substituents may be bonded to each other to form a ring. In addition, R ¹ and / or R ² forces S and X may form a ring. Specifically, the combination of two or more divalent aromatic hydrocarbon groups is a structure in which two or more divalent aromatic hydrocarbon groups are directly connected.

 [0028] Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and the like, each of which may have a substituent. Examples of the group having a structure in which a divalent aromatic hydrocarbon group is directly connected include a biphenylylene group and a terfylene group. X is particularly preferably a 1,4-phenylene group which may have a substituent.

 [0029] Y has a substituent! /, May be! /, And is a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent. The divalent aromatic hydrocarbon group may have a monocyclic structure or a condensed ring structure in which two or more rings are condensed. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and the like, and a 1,4-phenylene group is particularly preferable.

[0030] Z in the formula (1) is a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, a divalent unsaturated hydrocarbon group, or a combination thereof. A divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group and a divalent unsaturated hydrocarbon group may have a substituent. The divalent aromatic heterocyclic group and divalent aromatic group may be substituted. The aromatic hydrocarbon ring group may have two or more condensed rings. However, it is a structure that forms a π-conjugated system from X to the anchor group R ³ .

[0031] Specific examples of combinations of cyclic groups include a structure in which two or more divalent aromatic heterocyclic groups are directly connected, and a structure in which two or more divalent aromatic hydrocarbon groups are directly connected. A structure in which one or more divalent aromatic heterocyclic groups and one or more divalent aromatic hydrocarbon groups are directly connected, and two or more divalent aromatic heterocyclic groups are divalent unsaturated. Two or more structures connected by hydrocarbon groups A structure in which the above divalent aromatic hydrocarbon groups are linked by a divalent unsaturated hydrocarbon group, or one or more divalent aromatic heterocyclic groups and one or more divalent aromatics Examples include a structure in which a hydrocarbon group is linked by a divalent unsaturated hydrocarbon group. However, in the case of a structure linked by a divalent unsaturated hydrocarbon group, a π electron of a divalent aromatic heterocyclic group and an aromatic hydrocarbon group and a π electron of a divalent unsaturated hydrocarbon group Is a conjugated structure.

[0032] Examples of the divalent aromatic heterocyclic group include an optionally substituted chainylene group and thienochainylene group, preferably 2, 5 chainylene group, 2, 5 Thienoche diene group and the like.

 Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group, each of which may have a substituent. In addition, examples of the group having a structure in which a divalent aromatic hydrocarbon group is directly connected include a biphenylene group and a terfenylene group.

 The divalent unsaturated hydrocarbon group includes “one CH = CH”, “one CH = CH—CH = CH—”, “one CH = CH—CH = CH—CH = CH”, “one CH = CH— Conjugated chain linking groups such as “C≡C one”, or cyclic linking groups having an unsaturated bond such as 1-cyclohexene 1,2-ylene, 1-cyclopentene 1,2-ylene, and the chain linking group. For example, a structure in which a group is combined with.

[0033] The terminal amino group-containing aromatic compound of the present invention represented by the formula (1) is suitable as a sensitizing dye for photoelectric conversion used in a dye-sensitized photoelectric conversion battery.

 The solar radiation spectrum reaching the ground is scattered or absorbed by the upper atmosphere surrounding the earth and is distributed at about 300 to 3000 nm. Here, in the dye-sensitized photoelectric conversion cell, the absorption wavelength region where sunlight can be converted into electric energy is considered to be effective in the range of 300 to 1200 nm due to the effects of the semiconductor electrode potential and the redox potential of the electrolyte. . Furthermore, the irradiance of sunlight, which is mainly visible in the visible region, is 400 to 8 OOnm, which is 55% of the total solar energy.

Therefore, the ability to use solar energy efficiently by using a dye having a wide and wide absorption band in the visible region as a sensitizing dye for photoelectric conversion for a dye-sensitized photoelectric conversion battery. S becomes Kanakura. Furthermore, the energy level of the highest occupied orbit (hereinafter abbreviated as HOMO) and lowest unoccupied orbit (hereinafter abbreviated as LUMO) of the dye greatly affects the performance of the dye-sensitized solar cell. The HOMO energy level (one-electron oxidation potential) of the dye is required to be lower than the redox potential of the electron transport agent in the electrolyte, and the energy level (one-electron oxidation potential). The reduction potential is required to be higher than the semiconductor conduction band! Since the optimum energy level is a great balance between the pigment and the individual components that are affected, it is thought that an appropriate energy difference from each pigment is required (Ashraful Islam, Hideki Sugihara). , Hidenori Arakawa, “Molecular Design of ruthenium (II) polypyridyl photosensitizers lor efficient nanocrystalline TiO solar cell”, Journal of Photochemist ry and Photo biology A: Chemistry).

 [0035] Originally, energy levels such as HOMO and LUMO are highly dependent on the skeleton. To tune the energy level to the optimal position, the power to change the skeleton, and by extending or shortening the π-conjugated system Will respond. In general, it is known that when the π-conjugated system is lengthened, the HOMO energy level increases and the LUMO energy level decreases. There is a limit to tuning the energy level to the optimum position by simply expanding or contracting the HOMO and LUMO energy levels of the dye.

 As a method for designing a dye structure satisfying these requirements, it can be proposed to introduce an appropriate number of fluorine atoms at an appropriate position in the compound represented by the formula (1). This makes it possible to tune energy levels such as HOMO and LUMO. These compounds are suitable as sensitizing dyes for dye-sensitized photoelectric conversion batteries.

[0036] X and Y in the formula (1) are preferably an aromatic hydrocarbon group which may have a substituent. The aromatic hydrocarbon group is particularly preferably a 1,4-phenylene group, preferably a phenylene group, a naphthylene group or an anthrylene group capable of conjugation from the terminal amino group to the anchor group. Particularly preferred as X and Y are 1,4 phenylene groups substituted by fluorine atoms. More preferred is the case where the 1,4-phenylene group is substituted with 1 or 2 fluorine atoms. The reason why these groups are preferred as X and Y is to synthesize The acquisition of starting materials for the In addition, the introduction of fluorine atoms into the X and Y aromatic hydrocarbon groups has the effect of changing the HOMO energy level and LU MO energy level of the dye. HOMO and LUMO energy levels can be adjusted by selecting to. HOMO and LUMO energy levels can be easily obtained by performing cyclic voltammetry (hereinafter abbreviated as “CV”), which is one of the electrochemical measurement methods. The HOMO energy level of a substance is almost equivalent to a one-electron oxidation potential, and the LUMO energy level is almost equivalent to a one-electron reduction potential. By introducing an appropriate number of fluorine atoms into the compound represented by the formula (1) at an appropriate position, the values of the one-electron oxidation potential and the one-electron reduction potential are shifted, so that they are adjusted to optimum values. Is possible.

[0037] Z in the formula (1) is conjugated with a ring group such as a phenyl group, a chain group, or a thieno diylene group, which may have a substituent, or a ring group as shown below. A structure in which a chain linking group is combined is preferable. In the structure below, Y is written on the side that binds to Y. (Fn) means that one or more fluorine atoms may be substituted. Each ring group may have a substituent! /, Or may be! /, But preferably a hydrogen atom or a fluorine atom. The reason why these groups are preferable as Z is that it is easy to expand the absorption region and adjust the absorption maximum, and the raw materials are easily available and synthesis is easy.

[Chemical 5]

Next, RR ⁴ and R ⁵ in the formula (1) will be described.

R ¹ , R ² , R ⁴ and R ⁵ are each independently a monovalent organic residue which may have a hydrogen atom or a substituent. Here, R ¹ and R ² may jointly form a ring. R ¹ and / or R ² may form a ring together with X.

[0039] Specific examples of the monovalent organic residue of R ¹ , R ² , R ^4, and R ⁵ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, each of which may have a substituent. Or an aromatic heterocyclic group, or a halogen atom, cyano group, isocyano group, thiocyanate group, isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group, amide group, or the following formula (2) Represented Group.

 [Chemical 6]

— A no. B-fA ² R ⁶

 (2)

In the formula (2), A ¹ and A ² are each independently ◯, NH or S. B is a carbonyl group, a thiocarbonyl group, a sulfiel group or a sulfonyl group. o and p are each independently 0 or 1. R ⁶ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, or a halogen atom, a cyano group, an isocyano group or a thiocyanate group. , Isothiocyanate group, nitro group, hydroxy group, mercapto group, amino group or amide group.

[0040] Here, the monovalent aliphatic hydrocarbon group means a monovalent aliphatic hydrocarbon group having 1 to 40 carbon atoms, and has a linear structure, a branched structure, or a cyclic structure. It may have a unsaturated bond. The monovalent aliphatic hydrocarbon group may have a substituent, and one or more carbon atoms may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom. Specific examples of the monovalent aliphatic hydrocarbon group include an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, and an alkoxy group.

[0041] As the monovalent aliphatic hydrocarbon group, more specifically, a methyl group, an ethyl group, an n-propylene group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butynole group, or 1-pentyl group. Group, 1-hexyl group, 1-heptyl group, 1-octyl group, 2-ethynole, 1-hexyl group and! /, An alkyl group having 1 to 8 carbon atoms; 1 propenyl group, isopropenyl group , Linole group, 1-butur group, 2 butur group, 3 butur group, 2 methylolene 1 propenyl group, 2 methyl-2-propenyl group, alkenyl group having 2 to 4 carbon atoms; ethur group, 1 propynyl group, 2— C2-C4 alkynino groups such as propynyl group, 1-butulyl group, 2-butulyl group, 3-butulyl group, 1-methyl-3 propynyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl C3-C10 saturated cycloalkyl group such as syl group, cyclopentyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group; 2 cyclopentene 1-yl group, 2 cyclohexene — 1-yl group 3-7 carbon atoms Of unsaturated cycloalkyl groups. [0042] Examples of the monovalent aromatic hydrocarbon group include an aromatic hydrocarbon group having a monovalent monocyclic structure or a condensed ring structure, or a monovalent ring-assembled aromatic hydrocarbon group. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a triphenyl group, a pyrenyl group, and the like S can be mentioned. In addition, the monovalent aromatic hydrocarbon group may be bonded to the skeleton of the formula (1) via an oxygen atom, a sulfur atom or a nitrogen atom. Examples thereof include a phenoxy group and a naphthyloxy group.

 [0043] Preferred monovalent aromatic hydrocarbon groups are a phenyl group, an o tolyl group, an m tolyl group, a p tolyl group, an o anisol group, an m anisol group, a p anisol group, a 1 naphthyl group, and a 2-naphthyl group. 9 Monovalent aromatic hydrocarbon groups having 6 to 14 carbon atoms such as phenanthryl group.

 [0044] Examples of the monovalent aromatic heterocyclic group include an aromatic heterocyclic group having a monovalent monocyclic structure or a condensed ring structure, or a monovalent ring-aggregating aromatic heterocyclic group. Specifically, 2-furyl group

, 3 furyl group, 2 cenyl group, 3 cenyl group, 2 serenyl group, 3 selenyl group,

1 pyrrolyl group, 2 pyrrolyl group, 3 pyrrolyl group, 2 pyridinole group, 3 pyridyl group, ₄ pyridinole group, _2- quinolinole group, _3- quinolinole group, 4-quinolinole group, _5- quinolinole group, 6

—Quinolinole group, 7 quinolinole group, 8 quinolinole group, 1 isoquinolinole group, 2 quinoxalyl group, 2 benzofuryl group, 2 benzochinyl group, 2 thienocenyl group, 3 thienoce binolele group, 2 selenoselenyl group, 3 selenoselenyl group, 2 selenoselenyl group Group, 2 thiazothiazoyl group and the like.

 [0045] Preferable monovalent aromatic heterocyclic groups include a 2-cenyl group, a 2-selenyl group, a 2-benzozenyl group, a 2-benzoselenyl group, a 2-thienocenyl group, a 2-selenoselenole group, and a 2-ditchenyl group! /, An aromatic heterocyclic group having 4 to 12 carbon atoms;

[0046] Examples of the aliphatic hydrocarbon group in which R ¹ and R ² jointly form a cyclic structure include a divalent linking group S. Preferred examples of the divalent linking group include saturated alkylene groups having 4 to 6 carbon atoms such as a tetramethylene group, a pentamethylene group, and a hexamethylene group. For example, in the case of a pentamethylene group, the ring formed by R ¹ and R ² and the nitrogen atom of the amine moiety of formula (1) forms a piperidine ring.

[0047] Further, for example, an aliphatic hydrocarbon group in which R ¹ and R ² jointly form a cyclic structure is penta In the case of a methylene group in which the carbon atom is substituted with an oxygen atom, the ring force formed by R ¹ and R ² and the nitrogen atom of the amine moiety of formula (1) forms a morpholine ring, etc. Become.

[0048] The aromatic hydrocarbon group in which R ¹ and R ² jointly form a cyclic structure is a divalent linking group or a ring assembly composed of an aromatic hydrocarbon group having a single ring structure or a condensed ring structure. A divalent linking group consisting of an aromatic hydrocarbon group can be mentioned. Specific examples of such a divalent linking group include a 2,2,1-biphenylene group, a Ph—S—Ph group, a 4,5-phenanthrylene group, and the like, and preferably a 2,2′-biphenyl group. A ren group.

[0049] The aromatic heterocyclic group in which R ¹ and R ² jointly form a cyclic structure is a divalent linking group or ring assembly composed of an aromatic heterocyclic group having a monocyclic structure or a condensed ring structure. A divalent linking group composed of an aromatic heterocyclic group is exemplified. Specific examples of such a divalent linking group include 3, 3′-biche diylene group.

[0050] As R ¹ and R ² , carbon number;! To 4 alkyl groups and 6 to 6 carbon atoms; preferred carbon number of 14 monovalent aromatic hydrocarbon groups for ease of synthesis, etc .; ! ~ 4 alkyl groups are particularly preferred.

[0051] R ⁴ and R ⁵ are preferably a hydrogen atom, a halogen atom, or a monovalent organic residue having 1 to 20 carbon atoms. Here, the monovalent organic residue is preferably substituted. R

 4 and R are particularly preferably a hydrogen atom or an electron withdrawing group.

 Five

[0052] The electron withdrawing group here means a group having a value larger than the substituent constant σ force SO of NO, Met. Specific examples of the electron withdrawing group for R ⁴ and R ⁵ include cyano group, carboxyl group, acyl group, honoreminore group, aryloxycarbonyl group, alkyloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group. And alkylsulfifer groups, arylenosulfifer groups, nitro groups, perfluoroalkyl groups, and the like. However, the electron withdrawing group is not limited to these.

 [0053] Examples of the acyl group include a acetyl group, a propionyl group, a bivaloyl group, an attalyloyl group, a methacryloyl group, a benzoyl group, a toluoyl group, and a cinnamoyl group.

[0054] Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a 4 fluorophenyloxycarbonyl group, and the like. [0055] Examples of the alkylsulfonyl group include a mesyl group, an ethylsulfonyl group, a propylsulfonanol group, a trifluorosulfonyl group, a nonafluoro-t-butylsulfonyl group, and the like.

 [0056] Examples of the arylsulfonyl group include a benzenesulfonyl group and a toluenesulfonyl group.

 [0057] Examples of the alkyl sulfier group include a methyl sulfier group, an ethyl sulfier group, and an open pyrsulfier group.

[0058] Examples of arylsulfier groups include phenylsulfiel groups, toluylsulfier groups, and the like.

 [0059] The perfluoroalkyl group is an alkyl group in which all hydrogen atoms substituted on carbon atoms are fluorine-substituted, and the number of carbon atoms is preferably 1-20. Perfluoroalkyl groups contain oxygen and sulfur atoms!

Among these, as R ⁴ , a cyan group is preferable because of ease of synthesis and electron withdrawing strength. R ⁵ is preferably a hydrogen atom or a cyan group.

[0061] R ³ is an anchor group that can be linked to an inorganic porous material exhibiting semiconductor characteristics. As the inorganic porous material exhibiting such semiconductor characteristics, specifically, particles obtained by making porous an inorganic oxide exhibiting semiconductor characteristics such as titanium oxide, tin oxide, and zinc oxide are used. Therefore, the anchor group widely includes groups that can be connected to the porous inorganic oxide particles. Such an anchor group is preferably a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like. Among these, a carboxyl group is particularly preferable because it can be easily connected to porous inorganic oxide particles.

The carboxyl group, sulfonic acid group, phosphoric acid group and the like may be combined with a cation to form a salt for the purpose of enhancing solubility. Examples of cations that can form salts include ammonium ions, alkali metal ions, and alkaline earth metal ions. Ammonium ions include tetraalkylammonium ions typified by tetramethylammonium ions. Examples of alkali metal ions include sodium ions, potassium ions, and lithium ions. Examples of alkaline earth metal ions include magnesium ions and calcium ions. [0062] m in the formula (1) is an integer of 1 to 3. M is preferably 1 because of ease of synthesis and stability of the compound.

[0063] n in the formula (1) is an integer of 0 or 1. If 0 is Z is absent, carbon atom and Y bonded with R ⁵ means that the direct connection. From the viewpoint of elongation of a conjugated system in which 0 is preferable from the viewpoint of ease of synthesis, 1 is preferable.

[0064] Specific examples of the aromatic compound containing an amino group at the terminal of the present invention represented by the formula (1) are shown below. However, these are for the purpose of illustration, and aromatic compounds containing an amino group at the end of the present invention are not limited thereto.

[0065] Specific examples of the aromatic compound containing an amino group at the terminal of the present invention represented by the formula (1) are shown below. However, these are for the purpose of illustration, and aromatic compounds containing an amino group at the end of the present invention are not limited thereto.

 For convenience, the X, Y, and Z ring groups in formula (1) are abbreviated as follows. The direction of the ring group is the same as that applied to formula (1). For example, in the case of X, the left side is bonded to the nitrogen atom bonded to R R, and the right side is the carbon of the group represented by (CH = CH)

 It will bond to 1 2 m elementary atoms.

 In the structural formula, when Fn is described, it means that the ring group is substituted with one or more fluorine atoms! /.

[0066] [Chemical 7]

[0067] また、下記の表で記載された化合物の骨格構造として、各表の前に構造式を記載 した。

[0067] Further, as the skeleton structure of the compounds described in the following table, the structural formula is described before each table.

[0068] [Chemical 8

[table 1]

[0069] [Chemical 9]

 [Table 2]

[0070] [Chemical 10]

 [Table 3]

[Chemical 11]

 n

[Table 4]

[0072] [Chemical 12]

[Table 5]

[0073] [Chemical 13]

[Table 6]

[表 7]

[0074] [Chemical 14]

[Table 7]

 [0075] [Chemical 15]

[Table 8]

 [0076] [Chemical 16]

[Table 9]

The sensitizing dye for photoelectric conversion of the present invention is characterized by comprising an aromatic compound containing an amino group at the terminal represented by the formula (1). That is, what used the aromatic compound which has an amino group at the terminal represented by Formula (1) of this invention as a sensitizing dye for photoelectric conversions of this invention. Is a sensitizing dye for photoelectric conversion.

 The sensitizing dye for photoelectric conversion of the present invention is used for other photosensitization in order to compensate for sunlight absorption in a region that cannot be covered by an aromatic compound containing an amino group at the terminal represented by the formula (1). It may further contain pigments.

 Other sensitizing dyes used for such purposes include, for example, cyanine dyes, melocyanin dyes, mercurochrome dyes, xanthene dyes, porphyrin dyes, phthalocyanine dyes, azo dyes, coumarin dyes, and the like. Can be mentioned. Metal complex dyes such as ruthenium complex dyes can also be used as other sensitizing dyes of the present invention.

 The photoelectric conversion material of the present invention is formed by linking the above-described sensitizing dye for photoelectric conversion of the present invention and an inorganic porous material exhibiting semiconductor characteristics via an anchor group. Examples of the inorganic porous material used when forming the photoelectric conversion material include titanium oxide, tin oxide, zinc oxide, niobium oxide, indium oxide, tungsten oxide, and tantalum oxide. These may be used in combination of two or more inorganic compounds. Among these, preferable examples include titanium oxide and tin oxide, and titanium oxide is particularly preferable.

 [0079] The photoelectric conversion electrode of the present invention is formed by laminating the photoelectric conversion material of the present invention obtained by the above procedure on a transparent electrode. Here, the transparent electrode can be obtained by forming a transparent conductive film on a transparent substrate. Examples of the transparent substrate include a glass substrate and a resin substrate. Examples of the glass include quartz glass, soda lime glass, borosilicate glass, and lead glass. Examples of the resin substrate include polyethylene terephthalate and polyethylene naphthalate.

 As a method of forming a conductive film on the surface of a transparent substrate, a metal oxide (ITO) composed of indium oxide and tin oxide or the like is deposited on the substrate surface by a method such as vapor deposition, or tin oxide. And a method of forming a film by doping with fluorine.

[0080] The photoelectric conversion electrode of the present invention is formed by laminating the photoelectric conversion material of the present invention obtained by the above procedure on a transparent electrode. Here, regarding the method of laminating the photoelectric conversion material on the transparent electrode and the transparent electrode, for example, as the method of laminating the photoelectric conversion material of the present invention on the transparent electrode, the layer of the inorganic porous material is disposed on the transparent electrode. Made into sensitized colors here And a method of adsorbing element. In order to produce a layer of an inorganic porous material on a transparent electrode, the inorganic porous material is dispersed by adding an appropriate solvent or polymer and further an appropriate additive, and a paste is formed on the transparent electrode. A method of drying or sintering after coating is mentioned. A commercially available product may be used as the paste of the inorganic porous material. Examples of the solvent to be dispersed include water, alcohol solvents, amine solvents, ketone solvents, and hydrocarbon solvents. Examples of the coating method include spin coating, screen printing, dipping, and squeegee. As the drying and baking temperature of the substrate coated with the inorganic porous material paste, the lower limit is a temperature at which the solvent can be removed, and the upper limit is a temperature at which dissolution of the substrate does not occur. It is preferable that the temperature is such that the adhesion between the electrode and the transparent electrode is improved.

 Examples of the method for adsorbing the sensitizing dye include a method in which the sensitizing dye is dissolved or dispersed in an appropriate solvent, and the electrode substrate on which the layer of the inorganic porous material is prepared is immersed in this solution or dispersion. Examples of the solvent for dissolving or dispersing the sensitizing dye include water, alcohol solvents, amine solvents, ketone solvents, hydrocarbon solvents, and the like, and ethanol is particularly preferable.

 [0081] The photoelectric conversion battery of the present invention is formed by combining the above-described photoelectric conversion electrode with a conductive counter electrode via an electrolyte layer.

 The electrolyte layer used in the photoelectric conversion battery is preferably composed of an electrolyte, a medium, and an additive. Regarding these components, examples of the electrolyte include a liquid electrolyte obtained by adding a redox pair to a solvent, a polymer gel electrolyte, and a solid electrolyte. Examples of the liquid electrolyte solvent include nitrile solvents, carbonate solvents, glycol solvents, water, and the like, and in particular, acetonitrile and methoxyacetonitrile are preferable. Examples of the redox pair include a halogen redox pair, and an iodine redox pair is particularly preferable. The redox couple of iodine can be obtained by a combination of iodine and iodide ions. Examples of the raw material for iodide ions include metal iodide salts and quaternary ammonium salts, and particularly lithium iodide. In the same manner, redox couples can also be obtained for other boron and logogen compounds such as bromine.

[0082] As the conductive counter electrode, a metal such as platinum, rhodium, ruthenium, or indium was deposited. Examples thereof include a metal electrode, a carbon electrode, a conductive polymer electrode, and a composite electrode thereof.

 [0083] The battery is assembled by arranging the transparent electrode and the counter electrode through a spacer or the like so as to sandwich the laminated photoelectric conversion material, and filling the electrolyte therebetween. In order to prevent leakage of the electrolyte, the periphery of the photoelectric conversion element may be sealed. Examples of the sealing material include polymer adhesives.

 [0084] A compound called "co-adsorbent" or the like can be used together with the sensitizing dye for photoelectric conversion of the present invention. The co-adsorbent increases the photoelectric conversion efficiency by adsorbing to the inorganic porous material together with the sensitizing dye.

 The sensitizing dye for photoelectric conversion of the present invention is connected to an inorganic porous material exhibiting semiconductor characteristics via a single anchor! /, But this “connection” is almost the same as the above “adsorption”. It is synonymous.

 [0085] Examples of the co-adsorbent include steroid compounds having a carboxyl group and a sulfonic acid group, particularly cholic acid derivatives (cholic acid, deoxycholic acid, chenodeoxycholic acid, tauro chenodeoxycholic acid, Noreic acid, ursodeoxycholic acid, dehydrocholic acid) and metal salts thereof, amines (pyridine, 4 t-butylpyridine, polybutylpyridine, etc.), quaternary ammonium salts (tetrabutylammonium chloride, Tetrahexyl ammonium monoxide, etc.). As the co-adsorbent, cholic acid derivatives are preferable. Deoxycholic acid is particularly preferable.

 [0086] Examples of how to use the co-adsorbent include addition after adsorbing (linking) the dye to the inorganic porous material, addition to the electrolyte layer, and the like. If it is adsorbed (linked) to the inorganic porous material, it is not limited to this. Although the amount used varies depending on the color, high photoelectric conversion efficiency can be expected by adding about 10 to 60 mM.

 Example

 Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to these examples. In the following, the compound represented by the formula (A) is referred to as a compound (A), and the compounds represented by other formulas are also described in the same manner.

Example 1 Synthesis of Compound (A) [Chemical 17]

 [0089] Synthesis of Compound (A-1)

 In a 500 mL flask with a condenser, thermometer and magnetic rotor, 7 g of p-fluo-bensaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) and di (n-butyl) amamine (Wako Pure Chemical Industries, Ltd.) 19g) and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 34g, and 150mL of anhydrous dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were added and stirred at 80 ° C for 10 hours under nitrogen flow. It was. After cooling, the solid was filtered off, and the solvent was distilled off and concentrated to obtain 9.3 g of product. ^ —NMR measurement confirmed that the product was compound (A-1) (formula below).

[Chemical 18]

 H—NMR (300MHz, CDC1; TMS) δ 0. 97 (t, 1 = 7.4Hz, — CH, 6H), 1

 3 3

 31-1. 43 (m, — CH—, 4H), 1. 54— 1. 64 (m, — CH—, 4H), 3. 34 (t, J = 7.8 Hz, N-CH—, 4H), 6. 68 (d, J = 9.0 Hz, benzene ring hydrogen, 2H), 7.69 (m, benzene ring hydrogen, 2H), 9. 68 (d, —C (= 0) —H , 1H)

[0090] Synthesis of Compound (A-2)

 In a 500 mL flask with a condenser, thermometer, and magnetic rotor, 53.81 g of 4-bromo-2-fluorobenzyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.), triethyl phosphite (Kanto Chemical) 36.77 g and Wacetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 200 mL were added, and the mixture was heated to reflux for 9 hours under a nitrogen stream. After cooling, the solvent and the like were distilled off to obtain 6.36 g of product. ^ —NMR measurement confirmed that the product was compound (A-2). In the following formulae, “Et” represents an ethyl group.

H— NMR(300MHz, CDC1； TMS) δ 1. 29 (m, — CH , 6H) , 3. 14 (m, Ar[19]

H— NMR (300 MHz, CDC1; TMS) δ 1. 29 (m, — CH, 6H), 3. 14 (m, Ar

— CH— P, 2H), 4. 06 (m, O CH—, 4H), 7. 26 (m, benzene ring hydrogen, 3H)

Synthesis of compound (A-3)

 Into a 300 mL flask with a condenser, thermometer, magnetic rotor, and dropping funnel, 4.00 g of compound (A-1) and 5.85 g of compound (A-2) obtained in the above procedure were dehydrated. Drofuran (manufactured by Wako Pure Chemical Industries, Ltd.) in 120 mL, then tert-butoxy potassium (manufactured by Wako Pure Chemical Industries, Ltd.) 2. 90 g and 18 Crown-6 (manufactured by Kanto Chemical Co., Ltd.) 0. 63 g twice It was added in portions and allowed to stir at room temperature for 180 minutes.

 After completion of the reaction, 1N hydrochloric acid was added to stop the reaction, and the organic phase was washed with water. After separation and drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel chromatography to obtain 6.02 g of the product. ^ It was confirmed by NMR measurement that the product was compound (A-3).

[Chemical 20]

 H NMR (300 MHz, CDC1; TMS) δ 0.96 (t, J = 7.2 Hz, -CH, 6H), 1

30-1.42 (m, — CH—, 4H), 1. 53— 1. 63 (m, — CH—, 4H), 3. 29 (t, J = 7.5 Hz, N-CH—, 4H) , 6. 61 (d, J = 9.0Hz, benzene ring hydrogen, 2H), 6. 9 2 (d, J = 16.5Hz, olefin fin hydrogen, 1H), 7.07 (d, J = 16.5Hz, olefin fin hydrogen , 1H), 7. 18-7. 24 (m, benzene ring hydrogen, 2H), 7. 37 (d, J = 8.7Hz, benzene ring hydrogen, 2H), 7.43 (t, J = 8.3Hz, Benzene ring hydrogen, 1H)

Synthesis of compound (A-4)

To an lOOmL flask with a condenser, thermometer, and magnetic rotor, add 6.00g of the compound (A-3) obtained in the above procedure and 7mL of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) After cooling to 78 ° C under a nitrogen stream, 11.7 mL of n-butyllithium monohexane solution (manufactured by Kanto Chemical Co., Inc.) (1.52 mol / L) was added. Stir at 78 ° C for 15 minutes Thereafter, 1-formylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) 2. 35 g was added. After stirring for 1 hour, the temperature was raised to room temperature, and 1N hydrochloric acid was added to stop the reaction. The organic phase was separated and washed with water. After drying, the solvent was distilled off under reduced pressure and concentrated, followed by separation and purification by silica gel chromatography to obtain 2.62 g of product. ^ —NMR measurement confirmed that the product was compound (A-4).

[Chemical 21]

 H— NMR (300 MHz, CDC1; TMS) 0.97 (t, J = 7.4 Hz, — CH, 6H), 1.3

1-1. 43 (m, — CH—, 4H), 1. 54— 1. 64 (m, — CH —, 4H), 3. 31 (t, J = 7.7Hz, N-CH—, 4H ), 6. 63 (d, J = 9.0 Hz, benzene ring hydrogen, 2H), 7.03 (d, J = 16.2 Ηζ, olefin hydrogen, 1H), 7.25 (d, J = 16.5 Hz , Olefin hydrogen, 1H), 7. 42 (d, J = 9.0 Hz, benzene ring hydrogen, 2H), 7.51—7.75 (m, benzene ring hydrogen, 3H), 9. 91 (s, -CHO, 1H)

Synthesis of compound (A-5)

 Dean with a cooling tube 'Stark fractionator, thermometer, lOOmL tetralo flask equipped with a magnetic rotator and compound (A-4) 1 · OOg obtained in the above procedure and tert-butyl cyanoacetate (Tokyo Kasei) 1. 67 g, and Morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 78 g were placed in 60 mL of toluene and heated to reflux until the reaction was completed. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solvent and the low boiling point reactant were distilled off and concentrated under reduced pressure, followed by separation and purification by silica gel chromatography to obtain 1.31 g of product. It was confirmed by 'H-NMR measurement that the product was compound (A-5).

[Chemical 22]

 H—NMR (300 MHz, CDC1; TMS) 0.97 (t, J = 7.4 Hz, -CH, 6H), 1.3

1-1. 43 (m, — CH—, 4H), 1. 56— 1. 62 (m, — CH —, — C (CH), 13H) , 3.31 (t, J = 7.5Hz, N-CH-, 4H), 6.63 (d, J = 9.0Hz, benzene ring hydrogen, 2Η), 7.03 (d, J = 16.2Hz, olefin hydrogen, 1H), 7.25 (d, J = 16.2Hz, olefin hydrogen, 1H), 7.42 (d, J = 9.0Hz, benzene ring hydrogen, 2H), 7.64—7.72 (m, benzene ring hydrogen, 3Η), 8.08 (s, ( CN) C = CH, 1H)

[0094] Synthesis of Compound (A)

 Add 1.30 g of the compound (A-5) obtained in the above procedure and 50 mL of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) to an lOOmL 4-liter flask equipped with a condenser, thermometer, and magnetic rotor. 5.04 g of% hydrobromic acid was added and stirred at room temperature. After completion of the reaction, the reaction mixture was poured into 30 mL of ion-exchanged water and extracted twice with 600 mL of methyl tert-butyl ether (Gordo Solvent Co., Ltd.). The extract was washed once with aqueous ammonia and twice with water, and the solvent was distilled off under reduced pressure and concentrated to obtain 0.94 g of the product. Further, it was confirmed by NMR measurement that the product was a compound (A) containing an amino group at the terminal of the present invention.

 'H-NMROOOMHz, DMSO-d) 0.92 (t, J = 7.2Hz, — CH, 6H), 1.27

-1.39 (m, — CH—, 4H), 1.47— 1.56 (m, — CH—, 4H), 3.08— 3.55 (m, N-CH—, 4H), 6.65 (d, J = 9.0 Hz, benzene ring Hydrogen, 2H), 7.01 (d, J = 16.5Hz, olefin hydrogen, 1H), 7.23 (d, J = 16.2Hz, olefin fin hydrogen, 1H), 7.46 (d, J = 9.0Hz, benzene ring hydrogen, 2H), 7.86-7.96 (m, benzene ring hydrogen, 3 H), 8.28 (s, (CN) C = CH, 1H)

Example 2 Synthesis of Compound (B)

[Chemical 23]

 [0096] Synthesis of Compound (B-1)

In a 500 mL flask with a condenser, thermometer, and magnetic rotor, 7 g of 3, 4-difluo-bensaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and di (n-butyl) amamine (Wako Pure Chemical Industries, Ltd.) 19g) and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 34g and 150mL of anhydrous dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were charged and stirred at 80 ° C for 10 hours under nitrogen flow. It was. After cooling, the solid matter is filtered off and the solvent is distilled off. Concentration gave 9.3 g of product. ¾ NMR measurement confirmed that the product was the compound (B-1) (formula below).

[Chemical 24]

 H—NMR (300MHz, CDC1; TMS) 0.92 (t, J = 7.2Hz, — CH, 6H), 1.2

5- 1. 45 (m, — CH—, 4H), 1. 50— 1.65 (m, — CH—, 4H), 4. 09 (t, J = 6.3 Hz, N-CH—, 4H ), 6. 77 (t, J = 8.7Hz, benzene ring hydrogen, 1H), 7. 40—7.55 (m, benzene ring hydrogen, 2H), 9. 71 (d, — C (= 〇) — H, J = 2.1 Hz, 1H) Synthesis of compound (B-2)

 In the procedure for synthesizing the compound (A-2) described above, the same procedure was followed except that 4-bromo-2 fluorobenzyl bromide was replaced with 2,3 difluorobenzyl bromide (manufactured by AMAX Co., Ltd.). 68g was obtained. By NMR measurement, it was confirmed that the product was the compound (B-2) (the following formula).

[Chemical 25]

 H— NMR (300 MHz, CDC1; TMS) 1. 28 (t, J = 7.2 Hz, -CH, 6H), 3.2

2 (dd, J = l. 2, 21. 6Hz, Ar— CH— P (= 0), 2H), 4. 06 (q, J = 7.2 Hz, — O -CH -CH, 2H), 4 09 (q, J = 7.2 Hz, —O— CH—CH, 2H), 7. 02— 7.

13 (m, benzene ring hydrogen, 3H)

Synthesis of compound (B)

 In the procedure for synthesizing the above compound (A-3) !, the compounds (A-1) and (A-2) were synthesized with the compounds (B-1) and (B-2) synthesized by the above procedure. A procedure similar to that of Example 1 was performed except that 0.53 g of the product was obtained. ¾ NMR measurement confirmed that the product was a compound (B).

 'H-NMROOOMHz, DMSO-d) 0. 88 (t, J = 7.4Hz, — CH, 6H), 1.22

-1. 34 (m, — CH—, 4H), 1. 42— 1. 52 (m, — CH—, 4H), 3. 22 (t, J = 7. 5Hz, N-CH-, 4H), 6.93 (t, J = 8.6Hz, benzene ring hydrogen, 1H), 7.16 (d, J = 16.2Hz, olefin fin, 1H), 7.33 (d, J = 8.4Hz, Benzene ring hydrogen, 2H), 7.48 (d, J = 16.2Hz, olefin ring hydrogen, 1H), 7.74—7.81 (m, benzene ring hydrogen, 1H), 7.97-8.04 (m, benzene ring hydrogen, 1H), 8.28 ( s, (CN) C = CH, 1H) (Example 3) Synthesis of Compound (C)

[Chemical 26]

[0100] Synthesis of Compound (C 1)

 In the procedure for synthesizing the above compound (A-2), the same procedure was carried out except that 4-bromo-2 fluorobenzyl bromide was replaced with 3,5-difluorobenzyl bromide (manufactured by AMAX Co.). To give 1.26 g of product. It was confirmed by ifi—NMR measurement that the product was compound (C 1) (the following formula).

[Chemical 27]

 H—NMR (300 MHz, CDC1; TMS) 1.28 (t, J = 6.9 Hz, — CH, 6H), 3.1

2 (d, J = 21.9Hz, Ar-CH—P (= 0), 2H), 4.05 (q, J = 7.2Hz, OCH—Me, 2H), 4.07 (q, J = 6.9Hz, O CH —Me, 2H), 6.70 (m, benzene ring hydrogen, 1H), 6.84 (m, benzene ring hydrogen, 2H)

[0101] Synthesis of compound (C 2)

Add 500 g of dipromohydantoin (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) to a 500 mL tetra-flask equipped with a condenser, thermometer, magnetic rotor, and dropping funnel. It was. To the dropping funnel, 20 g of 2-methylthiophene (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were slowly added. After the completion of the dropping, the force was further stirred for 1 hour, and then azo polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by heating under reflux for 3 hours. Float after cooling! The filtrate was washed with water. After drying, the solvent was distilled off to obtain 21 g of product.

 As a result, it was confirmed that the product was the compound (C 2) (the following formula).

[Chemical 28]

 H-NMR (CDC1; TMS) 4. 63 (s, — CH—Br, 2H), 6. 8— 7 · 0 (m, thiof

 3 2

 Yen, 2H)

[0102] Synthesis of compound (C 3)

 In a 500 mL flask with a condenser, thermometer, and magnetic rotor, 25.5 g of the compound (C 2) obtained by the above procedure, triethyl phosphite (manufactured by Kanto Chemical Co., Ltd.) 16.5 g, acetonitrile ( 200 mL) was added, and the mixture was heated to reflux for 3 hours under a nitrogen stream. After cooling, the solvent and the like were distilled off to obtain 29 g of product. By NMR measurement, it was confirmed that the product was the compound (C 3) (the following formula). In the following formulae, “Et” represents an ethyl group.

 [Chemical 29]

 z-, person, Br

 d (C-3)

 'H-NMRCCDCl; TMS) 1. 13- 1. 37 (m, -CH, 6H), 3. 27 (d, J = 20. 7

 3 3

 Hz, Th-CH— P, 2H), 4. 04— 4. 14 (m, — CH—, 4H), 6. 8— 7.0 (m, Chi Fen, 2H)

[0103] Synthesis of Compound (C4)

 In the procedure for synthesizing the compound (A-3) described above, the synthesis was performed in the same manner as in Example 1 except that the compound (A-2) was changed to the compound (C1). Got. NMR measurement confirmed that the product was compound (C 4) (the following formula).

30]

H—NMR (300 MHz, CDC1; TMS) 0.97 (t, J = 7.4 Hz, -CH, 6H), 1.3 1-1.43 (m, — CH—, 4H), 1.50— 1.64 (m, — CH—, 4H), 3.31 (t, J = 7.7Hz, N-CH—, 4H), 6.62 (d, J = 8.7Hz, benzene ring hydrogen, 2H), 6.74 (d, J = 16.2Ηζ, olefin fin, 1H), 7.00 (d, J = 10.5Hz, benzene ring hydrogen, 2H), 7.15 (d, J = 16.2Hz , Olefin fin, 1H), 7.38 (d, J = 9. OHz, benzene ring hydrogen, 2H), 10.26 (s, -CHO, 1H)

[0104] Synthesis of Compound (C)

 In the procedure for synthesizing compound (A-3) above, compound (A-1) was changed to compound (C-4) and compound (A-2) was changed to compound (C-3). Except for the above, the same procedure as in Example 1 was performed to obtain 0.54 g of a product. — NMR measurement confirmed that the product was compound (C).

 'H-NMROOOMHz, DMSO-d) 0.92 (t, J = 7.4Hz, — CH, 6H), 1.29

-1.36 (m, — CH—, 4H), 1.49— 1.51 (m, — CH—, 4H), 3.00— 3.58 (m, N-CH—, 4H), 6.64 (d, J = 9. OHz, benzene Ring hydrogen, 2H), 6.90 (d, J = 16.2Hz, olefin hydrogen, 1H), 7.08 (d, J = 16.5Hz, olefin fin hydrogen, 1H), 7.33 (d, J = 18.6Hz, olefin fin hydrogen, 1H), 7.34 (d, J = 10.8Hz, benzene ring hydrogen, 2H), 7.39 (d, J = 8.7Hz, benzene ring hydrogen, 2H), 7.55 (d, J = 2.7Hz, thiophene ring hydrogen, 1H), 7.58 (d, J = 17.1Hz, olefin hydrogen, 1H), 7.95 (d, J = 3.9Hz, thiophene ring hydrogen, 1H), 8.47 (s, (CN) C = CH, 1H)

Example 4 Synthesis of Compound (D)

 [Chemical 31]

 Synthesis of compound (D-1)

In the procedure for synthesizing the compound (A-1) described above, the same procedure was followed except that 3,4-difluorobenzaldehyde was replaced with 3,4,5-trifluorobenzaldehyde (manufactured by Sigma Aldrich). The procedure was performed to give 3.80 g of product. ^ —NMR measurement confirmed that the product was compound (D-1) (formula below).

 H NMR (300MHz, CDC1; TMS) 0.88 (t, J = 7.2Hz, — CH, 6H), 1.2

 3 3

 0- 1. 35 (m, — CH—, 4H), 1. 40— 1. 55 (m, — CH—, 4H), 3. 26 (t, J = 7.5 Hz, N-CH—, 4H ), 7. 30— 7. 35 (m, benzene ring hydrogen, 2H), 9. 77 (s,-C (= ○) one H, 1H

Synthesis of compound (D-2)

 In the procedure for synthesizing the compound (A-2) described above, the same procedure was followed except that 4-bromo-2-fluorobenzilbutamide was replaced with 4 bromobenzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.). 18g was obtained. It was confirmed by ifi-NMR measurement that the product was compound (D-2) (the following formula).

[Chemical 33]

H— NMR (300 MHz, CDC1; TMS) 1. 25 (t, J = 7.1 Hz, -CH, 6H), 3.0

 3 3

 9 (d, J = 21. 6Hz, Ar-CH―, 2H),

 3. 97-4. 07 (m, O CH—, 4H), 7. 17 (d, benzene ring hydrogen, 2H), 7. 43 (d, benzene ring hydrogen, 2H)

Synthesis of compound (D-3)

 In the procedure for synthesizing the above compound (A-3), the compound (A-1) was changed to the compound (D-1) and the compound (A-2) was changed to the compound (D-2). The synthesis was performed in the same manner as in Example 1 except that 4.95 g of a product was obtained. It was confirmed by NMR measurement that the product was compound (D-3) (the following formula).

H— NMR(300MHz, CDC1； TMS) 0.83— 0.93 (m, — CH , 6H) , 1.24—[Chemical 34]

H—NMR (300MHz, CDC1; TMS) 0.83— 0.93 (m, — CH, 6H), 1.24—

1.34 (m, — CH—, 4H), 1.36— 1.47 (m, — CH—, 4H), 3. 13 (t, J = 7.4 Hz, N-CH—, 4H), 7.01 (d, J = 10.5 Hz, benzene ring hydrogen, 2H), 7.01 (d, J = 15.9Hz, olefin hydrogen, 1H), 7.10 (d, J = 16.2Hz, olefin fin, 1H), 7.62 (d, J = 8.4Hz, benzene ring Hydrogen, 2H), 7.87 (d, J = 8.4Hz, benzene ring hydrogen, 2H), 9.99 (s, — CHO, 1H)

[0109] Synthesis of Compound (D)

 In the procedure for synthesizing the above compound (A-3)! /, The compound (A-1) was changed to the compound (D-3) and the compound (A-2) was changed to the compound (C-3). Except for the above, the same procedure as in Example 1 was performed to obtain 0.81 g of the product. ifi—NMR measurement confirmed that the product was compound (D).

 'H-NMROOOMHz, DMSO-d) 0.83 (t, J = 7.4Hz, — CH, 6H), 1.21

-1.36 (m, — CH—, 8H), 3.04— 3.09 (m, N-CH—, 4H), 7.15— 7.3 8 (m, benzene ring hydrogen, olefin fin hydrogen, 5H), 7.46 (d, J = 3.9 Hz, Thiophene ring hydrogen, 1H), 7.60 (d, J = 8.1Hz, Benzene ring hydrogen, 2H), 7.63 (d, J = 15.6Hz, Olefin hydrogen, 1H), 7.70 (d, J = 8.4Hz, Benzene Ring hydrogen, 2H), 7.96 (d, J = 3.9Hz, Thiophene ring hydrogen, 1H), 8.47 (s, (CN) C = CH, 1H)

[0110] Synthesis of Compound (E)

[Chemical 35]

 In the procedure for synthesizing the above compound (A-3)! / Example 1 except that the compound (A-2) was changed to the compound (B-2) while leaving the compound (A-1) as it was. The same procedure was carried out to obtain 0.77 g of the product. ¾—It was confirmed by NMR measurement that the product was compound (E) (formula).

 'H-NMROOOMHz, DMSO-d) 0.92 (t, J = 7.4Hz, — CH, 6H), 1.27—

1.39 (m, — CH—, 4H), 1.47— 1.52 (m, — CH—, 4H), 3.08— 3.55 (m, N-CH—, 4H), 6.67 (d, J = 9.0 Hz, benzene ring hydrogen , 2H), 7.01 (d, J = l 5.9Hz, olefin fin, 1H), 7.48 (d, J = 15.9Hz, olefin fin, 1H), 7.4 9 (d, J = 9.0Hz, benzene ring hydrogen, 2H), 7.78 (t, J = 7.8Hz, Benzene ring hydrogen, 1 H), 8.00 (t, J = 7.8Hz, benzene ring hydrogen, 1H), 8.27 (s, (CN) C = CH, 1H) Synthesis of Comparative Example 1

[Chemical 36]

 In the procedure for synthesizing the above compound (A-3)! / Example 1 except that the compound (A-2) was changed to the compound (D-2) while leaving the compound (A-1) as it was. The same procedure was carried out to obtain 0.13 g of product. ^ It was confirmed by NMR measurement that the product was the compound of Comparative Example 1 (formula above).

 'H-NMROOOMHz, CDC1; TMS) 0.96 (t, J = 7.2Hz, — CH, 6H), 1.31

-1.43 (m, — CH—, 4H), 1.54— 1.64 (m, — CH—, 4H), 3.32 (t, J = 7.7Hz, N-CH—, 4H), 6.69 (d, J = 8.1 Hz, benzene ring hydrogen, 2H), 6.89 (d, J = 16.2Hz, olefin fin, 1H), 7.29 (d, J = 16.2Hz, olefin fin, 1H), 7.42 (d, J = 8.7Hz, benzene ring Hydrogen, 2H), 7.59 (d, J = 9. OHz, benzene ring hydrogen, 2H), 7.99 (d, J = 8.4Hz, benzene ring hydrogen, 2H), 8.23 (s, (CN) C = CH, 1H)

Synthesis of Comparative Example 2

[Chemical 37]

 In the procedure for synthesizing the above compound (A-3), the synthesis was performed in the same manner as in Example 1 except that the compound (A-2) was changed to the compound (D-2). Got. NMR measurement confirmed that the product was the compound of Comparative Example 21 (the following formula).

[Chemical 38]

 H—NMR (300MHz, CDC1; TMS) 0.85— 0.96 (m, — CH, 6H), 1.26—

 3 3

 1.38 (m, — CH—, 4H), 1.45— 1.55 (m, — CH—, 4H), 2.49— 2.51 (m, N-CH—, 4H), 6.62 (d, J = 8.7Hz, benzene ring hydrogen , 2H), 6.88 (d, J = l 6.5Hz, olefin fin, 1H), 7.13 (d, J = 16.2Hz, olefin fin, 1H), 7.3 8 (d, J = 8.4Hz, benzene ring hydrogen, 2H ), 7.46 (d, J = 8.7Hz, benzene ring hydrogen, 2H), 7.50 (d, J = 8.7Hz, benzene ring hydrogen, 2H)

[0113] Further, in the procedure for synthesizing the compound (A-3), the compound (A-1) was compared with the comparative example.

 The same procedure as in Example 1 was performed except that the compound (A-2) was changed to the compound (C-3) in (2-1) to obtain 0.37 g of a product. — NMR measurement confirmed that the product was the compound of Comparative Example 2 (formula above).

 'H-NMROOOMHz, DMSO-d) 0.92 (t, J = 7.4Hz, — CH, 6H), 1.26

 6 3

 -1.36 (m, — CH—, 4H), 1.46— 1.56 (m, — CH—, 4H), 3.08— 3.55 (m, N-CH—, 4H), 6.63 (d, J = 9.0 Hz, benzene ring Hydrogen, 2H), 6.93 (d, J = 16.2Hz, olefin hydrogen, 1H), 7.18 (d, J = 16.5Hz, olefin fin, 1H), 7.26 (d, J = 15.9Hz, olefin hydrogen, 1H ), 7.40 (d, J = 8.7Hz, benzene ring hydrogen, 2Η), 7.44 (d, J = 4.2Hz, thiophene ring hydrogen, 1H), 7.53 (d, J = 8.1Hz, benzene ring hydrogen, 2H) , 7.57 (d, J = 15. OHz, olefin hydrogen, 1H), 7.63 (d, J = 8 • 4Hz, benzene ring hydrogen, 2H), 7.94 (d, J = 4.2Hz, thiophene ring hydrogen, 1H), 8. 46 (s, (CN) C = CH, 1H)

[0114] (UV-visible absorption spectrum)

Compounds (A) to (E) which are aromatic compounds containing an amino group at the terminal of the present invention synthesized in Examples, Reference Example Dye (Ru Dye (Ruthenium535 bis TBA manufactured by Solaronix)), and Comparative Example 1 A solution prepared by using acetononitrile as a solvent for compound ~ 2 in quartz cell (path length lcm), and UV-visible with a spectrophotometer (JASCO Corporation UV-Vis near-infrared spectrophotometer V-570) The absorption spectrum was measured. These results are [Table 10]

[0115] In the compound represented by the formula (1) of the present invention, the compound which is a divalent aromatic hydrocarbon group substituted with at least one of X and Y with one or more fluorine atoms is visible in the ultraviolet. It was found to be effective for the absorption spectrum. From this, it is considered that the maximum absorption wavelength and the molar extinction coefficient can be optimized by introducing an appropriate number of fluorine groups at appropriate positions as in the present invention.

[0116] (Measurement of CV)

The compounds (A) to (D), which are aromatic compounds containing amino groups at the ends of the present invention synthesized in Examples, and Comparative Examples;! To 2 are each added to a supporting electrolyte (0.1 mol / L of tetra A measurement solution was prepared by adding 0.001 mol / L to (n-butynole) ammonium tetraphoroborate-acetonitrile solution). As the working electrode, the counter electrode, and the reference electrode, dull carbon, platinum wire, and Ag / Ag + (0. Olmol / L silver nitrate + 0 · lmol / L tetrabutylammonium perchlorate-acetonitrile solution) were used, respectively. Sample 10 mL as the measurement solution, perform nitrogen publishing for 10 minutes, and then use an electrochemical measurement device (PGSTAT12 manufactured by ECO CHE MIE) to adjust the potential range of 2.00 V force, 1.80 V to 0. lV / s. of CV measurement was performed at the pulling speed. We compared the data obtained by making corrections to NHE (Standard Hydrogen Electrode) using Huekousen as the reference material. The results are shown in the table below.

 [Table 11]

[0117] The compound represented by the formula (1) of the present invention has a component that the one-electron oxidation potential of the dye is greatly shifted to the oxidation side as compared with the compound of the comparative example having no fluorine atom. I got it. This result suggests that the potential can be tuned to the optimal position by introducing an appropriate number of fluorine groups at the appropriate position of the dye.

 [0118] (Photoelectric conversion test)

 In the photoelectric conversion test, a photoelectric conversion cell was prepared using the compound which is an aromatic compound containing an amino group at the end of the present invention synthesized in the example and the dye of the reference example as a sensitizing dye, and the photoelectric conversion efficiency was measured. did. Specifically, the photoelectric conversion test was performed according to the following procedure.

 [0119] <Photoelectric conversion test: Part 1>

 Photoelectric conversion cell

 Figure 1 is a schematic diagram of a test sample of the photoelectric conversion cell used in this test.

[0120] Dawn electrode 1. A 1 mm thick fluorine-doped tin oxide layer (transparent electrode layer) 2 with glass substrate 1 (manufactured by Solaronix) was used.

[0121] Titanium oxide paste

 A commercially available Titanium nanoxide HTSP (manufactured by Solaronix) was used.

[0122] Titanium oxide porous iron electrode

 Using a 120-mesh polyester sheet (Tetron network), apply a titanium oxide paste to the conductive surface of the transparent electrode (surface of the transparent electrode layer 2) by screen printing, and after drying at 50 ° C for 20 minutes, 450 Bake for 30 minutes in an oven at ° C. After firing, the temperature of the oven was dropped to 80 ° C. to maintain the temperature.

 [0123] m ^ m

Aromatic compounds containing a terminal amino group of the present invention as a sensitizing dye (A), (E) and reference examples of the dye, the Comparative Example 1 as the solution concentration of 4. 0 X 10_ ³ mol / L Dissolved in ethanol. In the dye solution (room temperature), a porous titanium oxide electrode maintained at 80 ° C. after firing was placed and immersed for 24 hours. Thereafter, an excess of the titanium oxide porous layer was scraped off so as to have an effective area of 0.25 cm ² to obtain a titanium oxide porous electrode having a desired titanium oxide porous layer 4.

[0124] Thunder Dissolution

 A commercially available redox electrolyte Iodolyte PN 50 (manufactured by Solaronix) was used.

[0125] Forming a conductive counter electrode (platinum electrode layer 3) by stacking a platinum layer by sputtering on the conductive layer (transparent electrode layer 2) of glass substrate 1 with fluorine-doped tin oxide layer (transparent electrode layer) 2 did. The spacer between the titanium oxide porous electrode (titanium oxide porous layer 4) and the conductive counter electrode (platinum electrode layer 3) is a spacer 6 made of resin film (SX-1170-60 thermoplast heat). Dissolved sealing sheet (Solaronix thickness 60 μm)) was used. After the cell was prepared, the electrolyte solution 5 was injected and then sealed to complete a photoelectric conversion cell test sample. Conductive lead wire 7 is bonded to the end of the conductive counter electrode (platinum electrode layer 3) of the test sample and the end of the transparent electrode conductive layer (transparent electrode layer 2) on the side where the titanium porous electrode is provided. did.

[0126] Measurement of conversion efficiency

A solar simulator (OTENTO-SUN III manufactured by Spectrometer Co., Ltd.) is used as the measurement light source. A combination of an air mass filter and a light meter adjusted to a light intensity of 100 mW / cm ² was used. Potentiostats HAUTOLAB PGSTAT12) was used to measure the IV curve characteristics. Conversion efficiency 7] was calculated by the following equation using Vo c (open circuit voltage value), Jsc (short circuit current value), and ff (fill factor) obtained from IV curve characteristics measurement.

Country n (%) = V o c (V) X J s c _ (mA) x f f x l o 0

1 0 0 (mW / c rn ² ) x 0.25 (cm ² ) Photoelectric conversion efficiency measurement results are shown in [Table 12].

<Photoelectric conversion test: Part 2>

 A photoelectric conversion cell was prepared and measured in the same manner except that the production conditions for the photoelectric conversion cell were changed as follows: titanium oxide paste, titanium oxide porous electrode preparation, electrolyte solution, and sensitizing dye adsorption. Went.

Titanium oxide paste

 A titanium oxide paste manufactured by Catalytic Chemical Industry was used.

Production of titanium oxide I, lightning pole

 Using a 90 mesh polyethylene sheet, apply titanium oxide paste to the conductive surface of the transparent electrode (the surface of the transparent electrode layer 2) by screen printing (the thickness of the titanium oxide film is about 4-5 m). Bake for 30 minutes in an oven at 450 ° C. After firing, the temperature of the oven was lowered to 80 ° C. and the temperature was maintained.

 ^ m

 As a sensitizing dye, an aromatic compound containing an amino group at the terminal synthesized by the above procedure (B)

~ (D), using the compound of dye and Comparative Examples 1 and 2 of Reference Example, the solution concentration is 3. 0 X 10 - ⁴ was dissolved in ethanol such that the mol / L. In the dye solution (40 ° C.), a porous titanium oxide electrode maintained at 80 ° C. after firing was placed and immersed for 6 hours. Thereafter, an excess of the titanium oxide porous layer was scraped off so as to have an effective area of 0.25 cm ² to obtain a titanium oxide porous electrode having a desired titanium oxide porous layer 4.

Preparation of Thunder Horn g Liquid 5 Electrolyte 5 was obtained with the following formulation.

 Solvent is methoxyacetonitrile, lithium iodide is 0.1 mol / L, iodine is 0.05 mol / L, 4-tert butylpyridine is 0.5 mol / L, 1 propyl-2,3 dimethylimidazolium iodide Was adjusted to 0.6 mol / L.

 Spacer

 As the spacer, Spacer 6 made of resin film (Himiran 1702 (Mitsui. DuPont Poly Chemical Co., thickness 50 m)) was used! /.

As a measurement light source, a solar simulator (K 0206 manufactured by Spectrometer Co., Ltd., light source SX—150C xenon lamp 150W) is combined with an air mass filter, and the light intensity is adjusted to 100 m W / cm ^{2 with} a light meter. A light source was used. While the test sample was irradiated with light, the IV curve characteristics were measured using a potentiostat (solatronl 287).

 The measurement results of photoelectric conversion efficiency are shown in [Table 13].

[0128] <Photoelectric conversion test: Part 3>

 Addition of deoxycholic acid

 For the photoelectric conversion cell preparation conditions in <Photoelectric conversion test: Part 2> above!

Compound (A), using the reference examples and comparative examples 1 compound, the solution concentration is 3. 0 X 10- ⁴ mol

A photoelectric conversion cell was prepared and measured in the same manner as in the above <Photoelectric conversion test: Part 2>, except that the dye solution was dissolved in ethanol so that the concentration of L / L was increased and 20 mM deoxycholate was added. It was.

 Table 14 shows the measurement results of photoelectric conversion efficiency in the case of this test with addition of deoxycholic acid.

[0129] [Table 12] Photoelectric conversion efficiency (short circuit current (mA / cm ² ) open circuit voltage (V) ff) Compound (A) 6.0 0.64 0.64 2.46 Compound (E) 6.7 0.65 0.60 2.62

 Reference example 7.9 0.67 0.56 2.98 Comparative example 1 4.8 0.59 0.66 1.85

[Table 13]

[Table 14] Deoxycholic acid 2 OmM added

[表 12]より化合物 (A)および化合物（E)と比較例 1を比較するとフッ素含有色素（ 化合物 (A)および化合物（E) )の方が良好な結果であり、参考例に近!/、値が得られ た。また、 [表 13]より化合物（B)と比較例 1、化合物（C)および化合物（D)と比較例 2とをそれぞれ比較すると、実施例で合成した本発明の末端にアミノ基を含有する芳 香族化合物は、フッ素原子を有しない比較例の化合物と比較して、高い光電変換効 率を有することが分かった。また、光電変換効率に関わるファクターである短絡電 sc、開放電圧 Voc、フィルファクター ffが同等または向上した値を示した。以上述べ たように、色素骨格の適切な位置に適切な数のフッ素基を導入することは、光電変換 効率に関わるファクターを向上させる効果があると考えられ、結果的に光電変換効率 の向上につながるのではないかと考えられる。

From Table 12, the compound (A) and the compound (E) are compared with Comparative Example 1 to find a fluorine-containing dye ( Compound (A) and compound (E)) showed better results, and values were close to those of the reference examples. Further, when comparing Compound (B) with Comparative Example 1, Compound (C), and Compound (D) with Comparative Example 2 from [Table 13], each of them contains an amino group at the terminal of the present invention synthesized in the Examples. It was found that the aromatic compound has a higher photoelectric conversion efficiency than the compound of the comparative example having no fluorine atom. In addition, short-circuit electric sc, open-circuit voltage Voc, and fill factor ff, which are factors related to photoelectric conversion efficiency, showed the same or improved values. As described above, introduction of an appropriate number of fluorine groups at appropriate positions in the dye skeleton is thought to have an effect of improving factors related to photoelectric conversion efficiency, and as a result, the photoelectric conversion efficiency is improved. It may be connected.

 Furthermore, the higher photoelectric conversion efficiency than the reference example was obtained by adding an appropriate amount of co-adsorbent deoxycholic acid from [Table 14]. It was suggested that the improvement of can be expected.

[0131] From these results, as in the aromatic compound (1) containing an amino group at the end of the present invention, the aromatic hydrocarbon group is substituted with a fluorine atom, so that the amount of the compound is higher than that of the unsubstituted compound. It was found that the photoelectric conversion efficiency was exhibited. Furthermore, it was also possible to obtain comparable conversion efficiency even when the compound of the present invention was used in place of the Ru dye, which is suitable as a sensitizing dye for photoelectric conversion cells. Moreover, since the oxidation-reduction potential can be adjusted by substituting fluorine atoms, it is considered possible to obtain desired performance in accordance with the conditions of the cell actually used.

 Industrial applicability

[0132] The aromatic compound containing an amino group at the end of the present invention represented by the above formula (1) has a wide absorption band in the visible region, and thus is particularly suitable for a photoelectric film used in a dye-sensitized photoelectric conversion battery. Suitable as a sensitizing dye for conversion. In addition, it can be applied to a wide range of applications such as nonlinear optical materials that are not limited to the applications listed here, as long as they do not interfere with the operation.

Claims

An aromatic compound containing an amino group at the terminal, represented by the following formula (1). (In the above formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic residue which may have a substituent. , R ¹ and R ² may form a ring together, and R ¹ and / or R ² may form a ring together with X. R ³ exhibits semiconducting properties An anchor group that can be linked to an inorganic porous material. X is a divalent aromatic hydrocarbon group or a combination of two or more divalent aromatic hydrocarbons. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed.  Y is a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent, and two or more rings may be condensed.  Z is a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, a divalent unsaturated hydrocarbon group, or a combination thereof. A divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, and a divalent unsaturated hydrocarbon group may have a substituent, and the divalent aromatic heterocyclic group and divalent aromatic group may be substituted. The aromatic hydrocarbon ring group may be condensed with two or more rings. However, it is a structure that forms a π-conjugated system from X to the anchor group. Also, at least one of X and Υ is a divalent aromatic hydrocarbon group substituted with one or more fluorine atoms. m is an integer from! n is an integer of 0 or 1. The double bond in the above formula (1) may generate any of cis-trans isomers. ) X in the formula (1) may be substituted with a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a biphenylene group or a terfenylene group. Yes, Y force each may have a substituent, a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and R ³ is either a carboxyl group, a phosphate group, or a sulfonate group. RR ² , R ⁴ , and R ⁵ are a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group, or a halogen atom, a cyano group, 2. An isocyanano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxyl group, a mercapto group, an amino group, an amide group, or a group represented by the following formula (2): An aromatic compound containing an amino group at the terminal described.  [Chemical 2] —ABA ¾-R ⁶  , No. (2) (In the above formula (2), A ¹ and A ² are each independently O, NH or S. B is a carbonyl group, a thiocarbonyl group, a sulfier group or a sulfonyl group. O and p are Each independently is 0 or 1. R ⁶ is a hydrogen atom, a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group, each optionally having a substituent, or A halogen atom, a cyano group, an isocyano group, a thiocyanate group, an isothiocyanate group, a nitro group, a hydroxy group, a mercapto group, an amino group, or an amide group.) [3] the above formula (1) in R ⁴ is an aromatic compound containing an amino group at the terminal of claim 1 or 2, characterized in that the electron-withdrawing group.  [4] The aromatic compound containing an amino group at the terminal according to [3], which is an electron-withdrawing basic force, which is a cyano group, an ester group, an amide group or a perfluoroalkyl group. 5. The aromatic compound containing an amino group at the terminal according to any one of claims 1 to 4, wherein R ³ in the formula (1) is a carboxyl group.  6. The terminal according to any one of claims 1 to 5, wherein Y in the formula (1) is a 1,4-phenylene group which may have a substituent. An aromatic compound containing an amino group.  [7] The terminal according to any one of [1] to [6], wherein X in the formula (1) is a 1,4-phenylene group which may have a substituent. An aromatic compound containing an amino group. [8] From the aromatic compound containing an amino group at the terminal according to any one of claims 1 to 7 A sensitizing dye for photoelectric conversion, characterized in that [9] A photoelectric conversion material obtained by linking the sensitizing dye for photoelectric conversion according to claim 8 and an inorganic porous material exhibiting semiconductor characteristics. 10. The photoelectric conversion material according to claim 9, wherein a coadsorbent is used together with the sensitizing dye for photoelectric conversion. [11] The inorganic porous material exhibiting semiconductor characteristics is composed of an inorganic oxide. The photoelectric conversion material according to 0. [12] A photoelectric conversion electrode obtained by laminating the photoelectric conversion material according to any one of claims 9 to 11 on a transparent electrode.  [13] A photoelectric conversion battery comprising the photoelectric conversion electrode according to claim 12, an electrolyte layer, and a conductive counter electrode.