JP5452881B2 - Organic thin film solar cell material and organic thin film solar cell using the same - Google Patents

Description

  The present invention relates to an organic thin film solar cell material and an organic thin film solar cell using the same.

An organic thin film solar cell is a device that shows an electrical output with respect to an optical input, as represented by a photodiode or an imaging device that converts an optical signal into an electrical signal, or a solar cell that converts optical energy into electrical energy, It is a device that exhibits a response opposite to that of an electroluminescence (EL) element that exhibits an optical output with respect to an electrical input. In particular, solar cells have attracted a great deal of attention as a clean energy source in recent years against the background of fossil fuel depletion and global warming, and research and development have been actively conducted.
Conventionally, silicon solar cells represented by single crystal Si, polycrystal Si, amorphous Si, etc. have been put into practical use. However, as the cost and raw material Si shortage problems surface, The demand for next generation solar cells is increasing. Against this background, organic solar cells are attracting much attention as next-generation solar cells next to silicon-based solar cells because they are inexpensive, have low toxicity, and do not have a fear of shortage of raw materials.

An organic solar cell basically has an n layer that transports electrons and a p layer that transports holes, and is roughly classified into two types depending on the material constituting each layer.
A layer in which a sensitizing dye such as ruthenium dye is adsorbed on the surface of an inorganic semiconductor such as titania as the n layer and an electrolyte solution is used as the p layer is called a dye-sensitized solar cell (so-called Gretzell cell). Although it has been energetically studied since 1991 due to its high conversion efficiency, since it uses a solution, it has drawbacks such as liquid leakage when used for a long time.
In order to overcome such drawbacks, recently, studies have been made to find an all-solid-state dye-sensitized solar cell by solidifying an electrolyte solution. However, the technology for impregnating organic matter into the pores of porous titania has a high degree of difficulty, and a cell capable of expressing high conversion efficiency with high reproducibility has not been completed.
On the other hand, organic thin-film solar cells consisting of organic thin films in both the n-layer and p-layer are all solid, so they have no drawbacks such as liquid leakage, are easy to manufacture, and do not use ruthenium, which is a rare metal. Attracted attention and researched energetically.

  Organic thin-film solar cells have been researched with single-layer films using merocyanine dyes, etc., but it has been found that conversion efficiency can be improved by using p-layer / n-layer multilayer films. Multilayer films are becoming mainstream. The materials used at this time were copper phthalocyanine (CuPc) for the p layer and peryleneimides (PTCBI) for the n layer.

Subsequently, it has been found that the conversion efficiency is improved by inserting an i layer (a mixed layer of p material and n material) between the p layer and the n layer to increase the number of layers. However, the materials used at this time were still phthalocyanines and peryleneimides. Further Thereafter, further conversion efficiency stack cell configuration in the p / i / n layers be stacked several layers have been found to improve the material system at that time was phthalocyanines and C _60.

On the other hand, in an organic thin film solar cell using a polymer, a conductive polymer is used as a p material, a C ₆₀ derivative is used as an n material, and they are mixed and heat-treated to induce micro-layer separation to form a heterointerface. Research on so-called bulk heterostructures has been mainly conducted to increase the conversion efficiency and improve the conversion efficiency. Here material system that has been used is mostly soluble polythiophene derivative called P3HT as p material was soluble C ₆₀ derivatives referred to as PCBM as an n material.

As described above, in the organic thin film solar cell, the conversion efficiency has been improved by optimizing the cell configuration and morphology, but the material system used in the organic thin film solar cell has not made much progress since the early days, and phthalocyanines, peryleneimides still remain. Class C ₆₀ has been used. Therefore, development of a new material system to replace them has been eagerly desired.

  In general, the operation process of an organic solar cell consists of (1) light absorption and exciton generation, (2) exciton diffusion, (3) charge separation, (4) carrier movement, and (5) electromotive force generation. Yes. Since organic substances generally do not have many absorption characteristics that match the sunlight spectrum, high conversion efficiency cannot often be achieved. In this regard, for example, the development of organic EL elements has been energetically performed in recent years, and among them, amine compounds that are excellent hole transport materials and hole injection materials have been found. Since such amine compounds have excellent hole transport properties, they have the potential to be used as p materials for organic thin film solar cells. However, since it does not show light absorption in the visible light region, it has the disadvantage that the absorption characteristics with respect to the sunlight spectrum are insufficient and the photoelectric conversion efficiency is not sufficient.

By the way, it is generally known that in order for an organic compound to have absorption in the visible light region, the π-electron conjugated system may be enlarged to increase the absorption maximum wavelength. However, if the conjugated system is expanded too much and the molecular weight becomes too large, the difficulty of purification becomes difficult due to a decrease in solubility in a solvent, or the sublimation temperature becomes high due to an increase in sublimation temperature. Thus, polyacenes are known as examples of compounds in which the absorption wavelength is efficiently increased while suppressing the molecular weight to some extent.
For example, Patent Documents 1 and 2 disclose techniques for applying polyacenes to solar cell materials. However, in general, polyacenes are unstable with respect to light and oxygen when the number of condensed rings is increased in order to expand the visible absorption region, so that purification and handling become difficult, and high purity is difficult. Has drawbacks. Since the organic solar cell materials disclosed in Patent Documents 1 and 2 have a condensed ring number of 5, the materials become unstable with respect to light and oxygen, so that purification and handling become difficult, and high purity is also difficult. It is not a practical solar cell material.
JP 2007-335760 A JP 2008-034764 A

  An object of the present invention is to provide an organic thin film solar cell material that is stable to light and oxygen and exhibits high efficiency photoelectric conversion characteristics when used in an organic thin film solar cell.

（式中、Ｒ_１〜Ｒ_１２はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキルアミノ基である。）
２．下記式（２）で示される有機薄膜太陽電池用材料。

（式中、Ｒ_１〜Ｒ_１４はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキルアミノ基である。）
３．下記式（３）で示される有機薄膜太陽電池用材料。

（式中、Ｒ_１〜Ｒ_１４はそれぞれ、水素、ハロゲン、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルケニル基、Ｃ_２〜Ｃ_４０の置換もしくは無置換のアルキニル基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_３〜Ｃ_４０の置換もしくは無置換のヘテロアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルキルアミノ基である。）
４．Ｒ_１〜Ｒ_１２のうち少なくともひとつが、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基である１に記載の有機薄膜太陽電池用材料。
５．Ｒ_１〜Ｒ_１４のうち少なくともひとつが、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリール基、Ｃ_１〜Ｃ_４０の置換もしくは無置換のアルコキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールオキシ基、Ｃ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基である２又は３に記載の有機薄膜太陽電池用材料。
６．Ｒ_８がＣ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基であり、Ｒ_１〜Ｒ_７及びＲ_９〜Ｒ_１２がそれぞれ、水素、又はＣ_１〜Ｃ_４０の置換もしくは無置換のアルキル基である１に記載の有機薄膜太陽電池用材料。
７．Ｒ_３がＣ_６〜Ｃ_４０の置換もしくは無置換のアリールアミノ基であり、Ｒ_１、Ｒ_２及びＲ_４〜Ｒ_１４がそれぞれ、水素、又はＣ_１〜Ｃ_４０の置換もしくは無置換のアルキル基である２に記載の有機薄膜太陽電池用材料。
８．一対の電極の間に少なくともｐ層を有し、前記ｐ層が１〜７のいずれかに記載の材料を含有する有機薄膜太陽電池。
９．上記８に記載の有機薄膜太陽電池を具備する装置。 According to the present invention, the following organic thin film solar cell materials and the like are provided.
1. An organic thin film solar cell material represented by the following formula (1).

Wherein R _{1 to} R ₁₂ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} C ₆ -C ₄₀ substituted or unsubstituted aryloxy group, C ₆ -C ₄₀ substituted or unsubstituted arylamino group, C ₁ -C ₄₀ substituted or unsubstituted alkylamino group.)
2. An organic thin film solar cell material represented by the following formula (2).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} C ₆ -C ₄₀ substituted or unsubstituted aryloxy group, C ₆ -C ₄₀ substituted or unsubstituted arylamino group, C ₁ -C ₄₀ substituted or unsubstituted alkylamino group.)
3. An organic thin film solar cell material represented by the following formula (3).

Wherein R _{1 to} R ₁₄ are each hydrogen, halogen, C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{2 to} C ₄₀ substituted or unsubstituted alkynyl _group, a substituted or unsubstituted aryl group having _C 6 ~C _40, C 3 ~C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C 1 _{-C 40} C ₆ -C ₄₀ substituted or unsubstituted aryloxy group, C ₆ -C ₄₀ substituted or unsubstituted arylamino group, C ₁ -C ₄₀ substituted or unsubstituted alkylamino group.)
4). At least one of R _{1 to} R ₁₂ is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group, a C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, or a C _{6 to} C ₄₀ substituted or unsubstituted group. an aryloxy group, an organic thin film solar cell material according to 1, which is substituted or unsubstituted arylamino group C ₆ -C _40.
5. At least one of R _{1 to} R ₁₄ is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group, a C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, a C _{6 to} C ₄₀ substituted or unsubstituted group. an aryloxy group, an organic thin film solar cell material according to 2 or 3 is a substituted or unsubstituted arylamino group C ₆ -C _40.
6). R ₈ is a C _{6 to} C ₄₀ substituted or unsubstituted arylamino group, and R _{1 to} R ₇ and R _{9 to} R ₁₂ are each hydrogen or a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group. 2. The material for an organic thin-film solar cell according to 1.
7). R ₃ is a C ₆ -C ₄₀ substituted or unsubstituted arylamino group, and R ₁ , R ₂ and R ₄ -R ₁₄ are each hydrogen, or a C ₁ -C ₄₀ substituted or unsubstituted alkyl group 2. The organic thin film solar cell material according to 2, which is
8). The organic thin-film solar cell which has a p layer at least between a pair of electrodes, and the said p layer contains the material in any one of 1-7.
9. 9. An apparatus comprising the organic thin film solar cell according to 8 above.

  According to the present invention, an organic thin-film solar cell exhibiting highly efficient conversion characteristics can be obtained by using a compound having a specific benzofluoranthene skeleton, rubicene skeleton, or isorubicene skeleton.

The organic thin film solar cell material of the present invention is a compound represented by the following formulas (1) to (3).

Each group of R _{1 to} R _{12 in} the formula (1) and each group of R _{1 to} R _{14 in} the formulas (2) and (3) are hydrogen, halogen, or substituted or unsubstituted C _{1 to} C ₄₀ , respectively. Alkyl groups, C ₂ -C ₄₀ substituted or unsubstituted alkenyl groups, C ₂ -C ₄₀ substituted or unsubstituted alkynyl groups, C ₆ -C ₄₀ substituted or unsubstituted aryl groups, C ₃ -C ₄₀ substituted or unsubstituted heteroaryl _group, a substituted or unsubstituted C 1 _-C substituted or unsubstituted alkoxy group _40, a substituted or unsubstituted aryloxy group _{C 6 ~C 40, C 6 ~C} 40 arylamino group, or a substituted or unsubstituted alkylamino group C ₁ -C _40.
Cx to Cy means that the carbon number is x to y.

In the formula (1), at least one of R _{1 to} R ₁₂ is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group, a C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, and C ₆ to C _{40. 40} substituted or unsubstituted aryloxy group is preferably a substituted or unsubstituted arylamino group C ₆ -C _40.
In particular, R ₈ is a C _{6 to} C ₄₀ substituted or unsubstituted arylamino group, and R _{1 to} R ₇ and R _{9 to} R ₁₂ are each hydrogen or C _{1 to} C ₄₀ substituted or unsubstituted. An alkyl group is preferred.

In Formula (2) or Formula (3), at least one of R _{1 to} R ₁₄ is a C _{6 to} C ₄₀ substituted or unsubstituted aryl group, or a C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group. C ₆ -C ₄₀ substituted or unsubstituted aryloxy group and C ₆ -C ₄₀ substituted or unsubstituted arylamino group are preferable.
In formula (2), in particular, R ₃ is a C ₆ -C ₄₀ substituted or unsubstituted arylamino group, and R ₁ , R ₂ and R ₄ -R ₁₄ are each hydrogen or C ₁ -C It is preferably ₄₀ substituted or unsubstituted alkyl groups.

In formulas (1) to (3), the substituted or unsubstituted alkyl group of C _{1 to} C ₄₀ of R _{1 to} R ₁₄ may be linear, branched or cyclic, and specific examples thereof As methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, 3,7-dimethyl Examples include octyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl, trifluoromethyl, trichloromethyl, benzyl, α, α-dimethylbenzyl, 2-phenylethyl, 1-phenylethyl and the like. Of these, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl and the like are preferable from the viewpoint of availability of raw materials.

The C ₂ -C ₄₀ substituted or unsubstituted alkenyl group of R _{1 to} R ₁₄ may be linear, branched or cyclic, and specific examples thereof include vinyl, propenyl, butenyl and oleyl. , Eicosapentaenyl, docosahexaenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl and the like. Of these, vinyl, styryl, 2,2-diphenylvinyl and the like are preferable from the viewpoint of availability of raw materials.

Substituted or unsubstituted alkynyl group _C 2 _{-C 40} of R ₁ to R ₁₄ may be either a straight chain, branched chain or cyclic, as their specific examples, ethenyl, propynyl, 2-phenyl And ethenyl. Of these, ethenyl, 2-phenylethenyl, and the like are preferable from the viewpoint of availability of raw materials.

The C ₆ -C ₄₀ substituted or unsubstituted aryl group of R _{1 to} R ₁₄ may be linear, branched or cyclic, and specific examples thereof include phenyl, 4-propylphenyl, 4-pentylphenyl, 2-tolyl, 4-tolyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-cyanophenyl, 4- (methylphenylamino) phenyl, 2-biphenylyl, 3- Biphenylyl, 4-biphenylyl, terphenylyl, 3,5-diphenylphenyl, 3,4-diphenylphenyl, pentaphenylphenyl, 4- (2,2-diphenylvinyl) phenyl, 4- (1,2,2-triphenylvinyl) ) Phenyl, fluorenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 2-anthryl, 9-fu Nantoriru, 1-pyrenyl, chrysenyl, naphthacenyl, coronyl, and the like. Among these, from the viewpoint of availability of raw materials, phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4-pentylphenyl, 4-ethoxyphenyl, 4- (Methylphenylamino) phenyl and the like are preferred.

The substituted or unsubstituted heteroaryl group of C _{3 to} C ₄₀ of R _{1 to} R ₁₄ may be linear, branched or cyclic, and the bonding position in the case of a nitrogen-containing azole heterocycle is Can be bonded with nitrogen as well as carbon. Specific examples thereof include furan, thiophene, pyrrole, imidazole, benzimidazole, pyrazole, benzpyrazole, triazole, oxadiazole, pyridine, pyrazine, triazine, quinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, carbazole and the like. Can be mentioned. Of these, furan, thiophene, pyridine, carbazole and the like are preferable from the viewpoint of availability of raw materials.

The substituted or unsubstituted alkoxy group of C _{1 to} C ₄₀ of R _{1 to} R ₁₄ may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, 1-propyl Oxy, 2-propyloxy, 1-butyloxy, 2-butyloxy, sec-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, 2-ethylhexyloxy, 3,7-dimethyloctyloxy, Cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, 1-adamantyloxy, 2-adamantyloxy, norbornyloxy, trifluoromethoxy, benzyloxy, α, α-dimethylbenzyloxy, 2-phenylethoxy, 1-phenylethoxy, etc. Cited The Of these, methoxy, ethoxy, ter-butyloxy and the like are preferable from the viewpoint of availability of raw materials.

The C ₆ -C ₄₀ substituted or unsubstituted aryloxy group of R _{1 to} R ₁₄ may be linear, branched or cyclic, and as specific examples thereof, the aryl group may be oxygenated. And a substituent bonded via each other. Of these, phenoxy, naphthoxy, phenanthryloxy and the like are preferable from the viewpoint of availability of raw materials.

The C ₆ -C ₄₀ substituted or unsubstituted arylamino group of R _{1 to} R ₁₄ may be any group as long as at least one of the substituents bonded to the amino group is an aryl group. Specifically, phenylamino, methyl Phenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenyl m-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, Bis (4-methoxyphenyl) amino, phenyl-4-carbazolylphenylamino and the like can be mentioned. Of these, diphenylamino, ditolylamino, bis (4-methoxyphenyl) amino and the like are preferable from the viewpoint of availability of raw materials.

The substituted or unsubstituted alkylamino group of C _{1 to} C ₄₀ of R _{1 to} R ₁₄ may be the same as or different from the alkyl group bonded to the amino group, and may be bonded to each other to form a ring. . Specific examples include methylamino, dimethylamino, methylethylamino, diethylamino, bis (2-hydroxyethyl) amino, bis (2-methoxyethyl) amino, piperidino, morpholino and the like. Of these, dimethylamino, diethylamino, piperidino and the like are preferable from the viewpoint of availability of raw materials.

  As a compound which can be used by this invention, the compound of the following structures can be mentioned, for example.

  There are various methods for synthesizing the material of the present invention. Among them, the synthesis route for ring closure of anthracene derivatives is easy to obtain raw materials, mild reaction conditions, and high yield yield of the desired product. Etc. are preferable. An example of the synthesis route is shown below.

  Here, X is a halogen such as iodine, bromine or chlorine, or a trifluoromethanesulfonyloxy (trifuryloxy) group, a nonafluorobutanesulfonyloxy (nonafuryloxy) group, a toluenesulfonyloxy (tosyloxy) group, a methanesulfonyloxy ( It represents a pseudohalogen group such as a (mesyloxy) group. Of these, halogens such as chlorine and bromine are preferred in view of availability of raw materials.

  A combination of various metals and ligands can be used as the catalyst used for the ring closure reaction. In terms of giving a high yield, nickel or palladium is preferable as the metal, and triphenylphosphine, tri-t-butylphosphine, 2- (dicyclohexylphosphino) biphenyl (JohnPhos), 2- (dicyclohexylphosphine) as the ligand. Fino) -2 ′-(N, N-dimethylamino) biphenyl (DavePhos), 2- (2-dicyclohexylphosphino) -2 ′, 6′-dimethoxybiphenyl (S-Phos), 2- (2-dicyclohexylphos) Fino) -2 ', 4', 6'-triisopropylbiphenyl (X-Phos) and other phosphines are preferred.

  In the reaction, it is preferable to add a base. Examples of the base that can be used in this reaction include carbonates such as potassium carbonate and cesium carbonate, alkoxides such as sodium t-butoxide, diazabicycloundecene, diaza Although organic bases, such as bicyclononene, are mentioned, Organic bases, such as diazabicycloundecene, are preferable in terms of giving a high yield.

  In addition, a phase transfer catalyst can be added to increase the reactivity of the base, and examples of the phase transfer catalyst that can be used in this case include tetrabutylammonium hydrogen sulfate and benzyltriethylammonium chloride.

The member of the organic thin film solar cell containing the material of the present invention may be formed of the material of the present invention alone or may be formed of a mixture of the material of the present invention and other components.
The organic thin film solar cell using the material of the present invention exhibits high efficiency conversion characteristics.

The cell structure of the organic thin-film solar battery of the present invention is not particularly limited as long as it is a structure containing the above compound between a pair of electrodes. Specifically, a structure having the following configuration on a stable insulating substrate can be given.
(1) Lower electrode / organic compound layer / upper electrode (2) Lower electrode / p layer / n layer / upper electrode (3) Lower electrode / p layer / i layer (or a mixed layer of p and n materials) / n Layer / upper electrode (4) Lower electrode / mixed layer of p material and n material / upper electrode and a structure in which the p layer and the n layer in the constitutions (2) and (3) are replaced.
Moreover, you may provide a buffer layer between an electrode and an organic layer as needed. For example, as a specific example, when a buffer layer is provided in the configuration (1), a structure having the following configuration can be given.
(5) Lower electrode / buffer layer / p layer / n layer / upper electrode (6) Lower electrode / p layer / n layer / buffer layer / upper electrode (7) Lower electrode / buffer layer / p layer / n layer / buffer Layer / Top electrode

  The organic thin film solar cell material of the present invention can be used for, for example, an organic compound layer, p layer, n layer, i layer, a mixed layer of p material and n material, and a buffer layer. In particular, it is preferably used as a material for the p layer.

  In the organic thin-film solar cell of the present invention, any material constituting the battery may contain the material of the present invention. Moreover, the member containing the material of this invention may contain the other component collectively. About the member and mixed material which do not contain the material of this invention, the well-known member and material used with an organic thin film solar cell can be used. Hereinafter, each component will be briefly described.

1. Lower electrode, upper electrode The material of the lower electrode and the upper electrode is not particularly limited, and a known conductive material can be used. For example, a metal such as tin-doped indium oxide (ITO), gold (Au), osmium (Os), palladium (Pd) can be used as the electrode connected to the p layer, and silver as the electrode connected to the n layer. Metals such as (Ag), aluminum (Al), indium (In), calcium (Ca), platinum (Pt) lithium (Li) and the like, and binary metal systems such as Mg: Ag, Mg: In and Al: Li, Can use the electrode exemplified material connected to the p layer.
In order to obtain highly efficient photoelectric conversion characteristics, it is desirable that at least one surface of the organic thin film solar cell be sufficiently transparent to the sunlight spectrum. The transparent electrode is formed using a known conductive material so as to ensure predetermined translucency by a method such as vapor deposition or sputtering. The light transmittance of the electrode on the light receiving surface is preferably 10% or more. In a preferred configuration of the pair of electrode configurations, one of the electrode portions includes a metal having a high work function, and the other includes a metal having a low work function.

2. Organic compound layer One of a p-layer, a mixed layer (i-layer) of p-material and n-material, or an n-layer. When the material of the present invention is used for the organic compound layer, specifically, the lower electrode / the single layer of the material of the present invention / the upper electrode, the lower electrode / the material of the present invention, and the n layer material or p layer described later. Examples include a mixed layer / top electrode material.

3. p layer, n layer, i layer When the material of the present invention is used for the p layer, the n layer is not particularly limited, but a compound having a function as an electron acceptor is preferable. For example, if the organic _compound, fullerene derivatives such as _{C 60,} carbon nanotube, perylene derivatives, polycyclic quinone, quinacridone, the polymeric CN- poly (phenylene - vinylene), MEH-CN-PPV, -CN group or CF ₃ group-containing polymers, their -CF ₃ substituted polymers, poly (fluorene) derivatives and the like can be mentioned. A material having high electron mobility is preferred. Further, a material having a small electron affinity is preferable. Thus, a sufficient open-circuit voltage can be realized by combining materials having a small electron affinity as the n layer.

Moreover, if it is an inorganic compound, the inorganic semiconductor compound of an n-type characteristic can be mentioned. Specifically, doped semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CdSe, InP, Nb ₂ O ₅ , WO ₃ , Fe ₂ O ₃ , titanium dioxide (TiO ₂ ), monoxide Examples include titanium oxide such as titanium (TiO) and dititanium trioxide (Ti ₂ O ₃ ), and conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO ₂ ). You may use combining more than a seed. Preference is given to using titanium oxide, particularly preferably titanium dioxide.

  When the material of the present invention is used for the n layer, the p layer is not particularly limited, but a compound having a function as a hole acceptor is preferable. For example, in the case of an organic compound, N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD), 4, Amine compounds represented by 4 ′, 4 ″ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA), etc., phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl phthalocyanine (TiOPc) ), Phthalocyanines such as octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP) and the like, and polymer compounds such as polyhexylthiophene (P3HT), Methoxyethylhexyloxyphe Vinylene (MEHPPV) main chain type conjugated polymers such as side chain type polymers such as represented by polyvinyl carbazole, and the like.

  When the material of the present invention is used for the i layer, the i layer may be formed by mixing with the p layer compound or the n layer compound, but the material of the present invention can also be used alone as the i layer. In this case, any of the above exemplary compounds can be used for the p layer or the n layer.

4). Buffer layer In general, organic thin film solar cells often have a thin total film thickness, and therefore, the upper electrode and the lower electrode are short-circuited, and the yield of cell fabrication often decreases. In such a case, it is preferable to prevent this by laminating a buffer layer.
As a preferable compound for the buffer layer, a compound having sufficiently high carrier mobility is preferable so that the short-circuit current does not decrease even when the film thickness is increased. For example, if it is a low molecular compound, the aromatic cyclic acid anhydride represented by NTCDA shown below etc. will be mentioned, and if it is a high molecular compound, poly (3,4-ethylenedioxy) thiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline: camphorsulfonic acid (PANI: CSA), and other known conductive polymers.

  In addition, the buffer layer may have a role of preventing excitons from diffusing to the electrodes and deactivating. Inserting a buffer layer as an exciton blocking layer in this way is effective for increasing efficiency. The exciton blocking layer can be inserted on either the anode side or the cathode side, or both can be inserted simultaneously. In this case, as a preferable material for the exciton blocking layer, for example, a well-known material for a hole barrier layer or a material for an electron barrier layer in organic EL applications can be used. A preferable material for the hole blocking layer is a compound having a sufficiently large ionization potential, and a preferable material for the electron blocking layer is a compound having a sufficiently small electron affinity. Specifically, bathocuproin (BCP), bathophenanthroline (BPhen), and the like, which are well-known materials for organic EL applications, can be used as the cathode-side hole barrier layer material.

Furthermore, you may use the inorganic semiconductor compound illustrated as said n layer material for a buffer layer. As the p-type inorganic semiconductor compound, CdTe, p-Si, SiC, GaAs, WO ₃ or the like can be used.

5. Substrate The substrate preferably has mechanical and thermal strength and transparency. For example, there are a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.

The formation of each layer of the organic thin film solar cell of the present invention is performed by a dry film formation method such as vacuum deposition, sputtering, plasma, ion plating, or wet film formation such as spin coating, dip coating, casting, roll coating, flow coating, and ink jet. The law can be applied.
The thickness of each layer is not particularly limited, but is set to an appropriate thickness. Since it is generally known that the exciton diffusion length of an organic thin film is short, if the film thickness is too thick, the exciton is deactivated before reaching the heterointerface, resulting in low photoelectric conversion efficiency. If the film thickness is too thin, pinholes and the like are generated, so that sufficient diode characteristics cannot be obtained, resulting in a decrease in conversion efficiency. The normal film thickness is suitably in the range of 1 nm to 10 μm, but more preferably in the range of 5 nm to 0.2 μm.

  In the case of the dry film forming method, a known resistance heating method is preferable, and for forming the mixed layer, for example, a film forming method by simultaneous vapor deposition from a plurality of evaporation sources is preferable. More preferably, the substrate temperature is controlled during film formation.

  In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a light-emitting organic solution to form a thin film, and any solvent can be used. For example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, methanol, Alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, tetralin, Examples include ester solvents such as ethyl acetate, butyl acetate, and amyl acetate. Of these, hydrocarbon solvents or ether solvents are preferable. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.

In the present invention, in any organic compound layer of the organic thin film solar cell, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film. Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

The apparatus of this invention should just be an apparatus using the organic thin-film solar cell of this invention mentioned above. For example, there are a clock, a mobile phone, a mobile personal computer, and the like.
Since the organic thin film solar cell of the present invention is lightweight and flexible, when used in these devices, the device can be easily designed, and the weight can be reduced.

[Organic thin film solar cell materials]
Synthesis example 1
Compound A was synthesized by the following reaction.

(1) Synthesis of 1-chloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10-dihydroanthracene 1-bromo-4-propylbenzene (12 g, 60 mmol, 3 eq) under nitrogen atmosphere .) Was dissolved in a mixed solvent of anhydrous THF (70 ml) and anhydrous toluene (70 ml), and cooled to −62 ° C. in a dry ice / methanol bath. To this was added dropwise n-butyllithium / hexane solution (1.6 mol / l, 38 ml, 61 mmol, 1 eq.), And the mixture was stirred at −68 ° C. for 1 hour. 1-Chloroanthraquinone (4.9 g, 20 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off. A brown oil was obtained. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (8.4 g, 91%).
The results of nuclear magnetic resonance measurement ( ¹ H-NMR) of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.89 (3H, t, J = 7 Hz), 0.90 (3H, t, J = 7 Hz), 1.57 (4H, sextet, J = 7 Hz), 2.49 (4 H, t, J = 7 Hz), 3.38 (1 H, s), 4.40 (1 H, s), 6.96 (2 H, d, J = 8 Hz), 7.13 (2H, d, J = 8 Hz), 7.16 (2H, d, J = 8 Hz), 7.22-7.29 (5H, m), 7.69-7.71 (1H, m), 7 .77 (1H, d, J = 7Hz)

(2) Synthesis of 1-chloro-9,10-bis (4-propylphenyl) anthracene 1-chloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10-dihydroanthracene (8 0.4 g, 18 mmol), potassium iodide (9.0 g, 54 mmol, 3 eq.), Sodium phosphinate monohydrate (2.9 g, 27 mmol, 0.5 eq. To KI) dissolved in acetic acid (80 ml) for 2 hours. Refluxed. The reaction mixture was diluted with water (100 ml), the solid was filtered off, washed with water and methanol to give a pale yellow solid (7.4 g, 96%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.03 (3H, t, J = 7 Hz), 1.06 (3H, t, J = 7 Hz), 1.80 (4H, sextet, J = 7 Hz), 2.75 (4 H, t, J = 7 Hz), 7.13 (1 H, dd, J = 8 Hz, 6 Hz), 7.30-7.33 (8 H, m), 7.39 (2 H, d, J = 8 Hz), 7.45 (1H, d, J = 7 Hz), 7.61-7.64 (1H, m), 7.67 (2H, d, J = 9 Hz)

(3) Synthesis of Compound A Under a nitrogen atmosphere, 1-chloro-9,10-bis (4-propylphenyl) anthracene (7.4 g, 17 mmol), palladium acetate (0.39 g, 1.7 mmol, 10% Pd) , Potassium carbonate (10 g, 72 mmol, 4.3 eq.) And tetrabutylammonium hydrogen sulfate (5.8 g, 17 mmol, 1 eq.) Were suspended in anhydrous DMF (50 ml) and stirred at 120 ° C. for 10 hours. Water (100 ml) was added to the reaction mixture, and the resulting solid was filtered off and washed with water and methanol to obtain a black solid. This was suspended in toluene, passed through a silica gel pad, and washed with toluene. The filtrates were combined and evaporated to give a dark yellow solid. This was purified three times by column chromatography (silica gel / hexane + 1% dichloromethane) to obtain an orange solid (0.7 g, 10%).

The results of nuclear magnetic resonance measurement ( ¹ H-NMR), electrolytic detachment mass spectrometry (FDMS), and liquid chromatography (HPLC) of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 1.04 (3H, t, J = 7Hz), 1.06 (3H, t, J = 7Hz), 1.76-1.83 (4H M), 2.76 (4H, t, J = 7 Hz), 7.30 (1H, dd, J = 8 Hz, 2 Hz), 7.38 (2H, d, J = 8 Hz), 7.41 (1H , S), 7.42 (2H, d, J = 8 Hz), 7.53 (1H, dd, J = 9 Hz, 6 Hz), 7.63 (1H, t, J = 8 Hz), 7.68 (1H , D, J = 9 Hz), 7.84 (1H, d, J = 1 Hz), 7.95 (1H, d, J = 9 Hz), 7.98 (1H, d, J = 6 Hz), 8.30 (1H, d, J = 8 Hz), 8.80 (1H, d, J = 9 Hz)
FDMS: calculated value C ₃₂ H ₂₈ = 412, actually measured value m / z = 412 (M ⁺ , 100)
HPLC: purity 99.1% (detection wavelength 254 nm: area%)

The obtained solid (0.6 g) was purified by sublimation at 240 ° C./5.5×10 ⁻⁴ Pa to obtain an orange solid (0.54 g).
HPLC: purity 98.6% (detection wavelength 254 nm: area%)
The physical properties are as follows.
Melting point (mp): 147 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 455 nm

Synthesis example 2
Compound B was synthesized by the following reaction.

(1) Synthesis of 1-chloro-9,10-bis (4-ethoxyphenyl) -9,10-dihydroxy 9,10-dihydroanthracene 4-Bromophenetole (12 g, 60 mmol, 3 eq.) Was added under a nitrogen atmosphere. It was dissolved in a mixed solvent of anhydrous THF (60 ml) and anhydrous toluene (60 ml), and cooled to −65 ° C. in a dry ice / methanol bath. To this, n-butyllithium / hexane solution (1.6 mol / l, 37 ml, 60 mmol, 1 eq.) Was added dropwise and stirred at -68 ° C. for 1 hour. 1-Chloroanthraquinone (4.9 g, 20 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off to give a yellow color. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (9.0 g, 92%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.35 (6H, t, J = 7 Hz), 3.22 (1H, s), 3.93 (4H, q, J = 7 Hz), 4 .39 (1H, s), 6.64 (2H, d, J = 9 Hz), 6.65 (2H, d, J = 9 Hz), 7.06 (2H, d, J = 9 Hz), 7.11 (2H, d, J = 9 Hz), 7.20-7.36 (4H, m), 7.37 (1H, d, J = 8 Hz), 7.77-7.80 (1H, m), 7 .83 (1H, d, J = 8Hz)

(2) Synthesis of 1-chloro-9,10-bis (4-ethoxyphenyl) anthracene 1-chloro-9,10-bis (4-ethoxyphenyl) -9,10-dihydroxy 9,10-dihydroanthracene (9 0.0 g, 18 mmol), potassium iodide (9.2 g, 55 mmol, 3 eq.), Sodium phosphinate monohydrate (2.9 g, 27 mmol, 0.5 eq. To KI) are dissolved in acetic acid (80 ml), 3 Reflux for hours. The reaction mixture was diluted with water (100 ml), the solid was filtered off, washed with water and methanol to give a pale yellow solid (8.0 g, 98%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.51 (3H, t, J = 7 Hz), 1.52 (3H, t, J = 7 Hz), 4.18 (2H, q, J = 7 Hz), 4.19 (2H, q, J = 7 Hz), 7.03 (2H, d, J = 9 Hz), 7.12 (2H, d, J = 9 Hz), 7.15 (1H, dd, J = 9 Hz, 1 Hz), 7.28-7.34 (7 H, m), 7.47 (1 H, dd, J = 7 Hz, 1 Hz), 7.64-7.68 (1 H, m), 7. 70 (1H, dd, J = 8Hz, 1Hz)

(3) Synthesis of Compound B In a nitrogen atmosphere, 1-chloro-9,10-bis (4-ethoxyphenyl) anthracene (8.0 g, 18 mmol), tris (dibenzylideneacetone) dipalladium (0.40 g, 0. 44 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (3.3 g, 22 mmol, 1.2 eq.) Was suspended in anhydrous DMF (70 ml) and tri-t-butyl. A phosphine / toluene solution (66%, 0.27 ml, 0.88 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 11 hours. The reaction mixture was diluted with toluene (200 ml), washed with water (100 ml), 1% hydrochloric acid (100 ml) and saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a red solid. This was purified twice by column chromatography (silica gel / hexane + 17% dichloromethane, followed by hexane + 50% dichloromethane, last dichloromethane only) to give an orange solid (6.5 g, 87%). The obtained solid (5.5 g) was recrystallized from toluene (40 ml) to obtain red needle crystals (5.1 g, 68%).

The results of ¹ H-NMR, FDMS, and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 1.50 (3H, t, J = 7Hz), 1.51 (3H, t, J = 7Hz), 4.17 (2H, q, J = 7Hz), 4.20 (2H, q, J = 7Hz), 7.00 (1H, dd, J = 8Hz, 2Hz), 7.10 (2H, d, J = 8Hz), 7.35-7 .40 (1H, m), 7.25 (2H, d, J = 8 Hz), 7.53 (1H, dd, J = 7 Hz, 6 Hz), 7.58-7.63 (2H, m), 7 .70 (1H, d, J = 8 Hz), 7.95 (2H, d, J = 7 Hz), 8.26 (1H, d, J = 8 Hz), 8.73 (1H, d, J = 9 Hz)
FDMS: Calculated value C ₃₀ H ₂₄ O ₂ = 416, measured value m / z = 416 (M ⁺ , 100)
HPLC: purity 99.7% (detection wavelength 254 nm: area%)

The obtained solid (3.4 g) was purified by sublimation at 280 ° C./1.0×10 ⁻³ Pa to obtain an orange solid (3.2 g).
HPLC: purity 99.6% (detection wavelength 254 nm: area%)
The physical properties are as follows.
mp: 210 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 471 nm

Synthesis example 3
Compound C was synthesized by the following reaction.

(1) Synthesis of 1-chloro-9,10-bis (4-bromophenyl) -9,10-dihydroxy 9,10-dihydroanthracene Under a nitrogen atmosphere, 4-bromoiodobenzene (10.5 g, 37 mmol, 3 eq. ) Was dissolved in a mixed solvent of anhydrous THF (40 ml) and anhydrous toluene (40 ml), and cooled to −66 ° C. in a dry ice / methanol bath. To this, n-butyllithium / hexane solution (1.6 mol / l, 23 ml, 37 mmol, 1 eq.) Was added dropwise and stirred at -68 ° C. for 1 hour. 1-Chloroanthraquinone (3.0 g, 12 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours, and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off to give a yellow color. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (6.7 g, 98%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.52 (1H, s), 4.36 (1H, s), 7.10 (2H, d, J = 8 Hz), 7.13 (2H , D, J = 8 Hz), 7.17-7.34 (8H, m), 7.49 (1H, dd, J = 6 Hz, 4 Hz), 7.64 (2H, d, J = 8 Hz)

(2) Synthesis of 1-chloro-9,10-bis (4-bromophenyl) anthracene 1-chloro-9,10-bis (4-bromophenyl) -9,10-dihydroxy 9,10-dihydroanthracene (6 0.7 g, 12 mmol), potassium iodide (6.0 g, 36 mmol, 3 eq.), Sodium phosphinate monohydrate (2.0 g, 19 mmol, 0.5 eq. To KI) were dissolved in acetic acid (50 ml) for 3 hours. Refluxed. The reaction mixture was diluted with water (100 ml), and the solid was filtered off and washed with water and methanol to give a pale yellow solid (5.9 g, 94%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.17 (1H, dd, J = 9 Hz, 7 Hz), 7.26-7.36 (6H, m), 7.48 (1H, dd, J = 7 Hz, 1 Hz), 7.54-7.62 (5 H, m), 7.72 (2 H, d, J = 8 Hz)

(3) Synthesis of 1-chloro-9,10-bis (4- (N-methylphenylamino) phenyl) anthracene In a nitrogen atmosphere, 1-chloro-9,10-bis (4-bromophenyl) anthracene (5. 9 g, 11 mmol), N-methylaniline (2.7 g, 25 mmol, 2.3 eq.), Tris (dibenzylideneacetone) dipalladium (0.2 g, 0.22 mmol, 2% Pd), sodium t-butoxide (3 0.0 g, 31 mmol, 1.4 eq.) Are suspended in anhydrous toluene (50 ml), and a tri-t-butylphosphine / toluene solution (66%, 0.11 ml, 0.36 mmol, 0.8 eq. To Pd) is added. And stirred at room temperature for 10 hours and left overnight. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to give a pale green solid (6.1 g, 96%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.45 (3H, s), 3.46 (3H, s), 7.00 (1H, t, J = 8 Hz), 7.07 (1H , T, J = 8 Hz), 7.13-7.40 (18H, m), 7.49 (2H, d, J = 7 Hz), 7.76-7.80 (3H, m)

(4) Synthesis of Compound C In a nitrogen atmosphere, 1-chloro-9,10-bis (4- (N-methylphenylamino) phenyl) anthracene (6.1 g, 11 mmol), tris (dibenzylideneacetone) dipalladium ( 0.24 g, 0.26 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (2.0 g, 13 mmol, 1.2 eq.) Suspended in anhydrous DMF (80 ml). The solution became cloudy, and a tri-t-butylphosphine / toluene solution (66%, 0.16 ml, 0.52 mmol, 1 eq to Pd) was added, followed by stirring at 140 ° C. for 11 hours. The reaction mixture was cooled in a water bath and diluted with water (100 ml). The solid was filtered off and washed with water and methanol to give a dark red solid (4.9 g). This was purified twice by column chromatography (silica gel / hexane + 17% dichloromethane, followed by hexane + 33% dichloromethane, finally hexane + 50% dichloromethane) to give a red solid (4.8 g, 81%). The obtained solid (4.8 g) was recrystallized from ethanol (30 ml) + toluene (70 ml) to obtain a red solid (3.8 g, 64%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS): δ3.46 (3H, s), 3.48 (3H, s), 7.00 (1H, t, J = 7Hz), 7.07 (1H , T, J = 7 Hz), 7.13-7.17 (5H, m), 7.25 (2H, d, J = 8 Hz), 7.33-7.40 (7H, m), 7.52. (1H, dd, J = 8 Hz, 6 Hz), 7.62 (1H, t, J = 8 Hz), 7.71 (1H, d, J = 2 Hz), 7.79 (1H, d, J = 8 Hz) , 7.91 (1H, d, J = 6 Hz), 8.05 (1H, d, J = 9 Hz), 8.28 (1H, d, J = 8 Hz), 8.75 (1H, d, J = 9Hz)
FDMS: calculated value C ₄₀ H ₃₀ N ₂ = 538, measured value m / z = 538 (M ⁺ , 100)
-HPLC: 97.0% (UV254 area%)

The solid (2.0 g) obtained above was purified by sublimation at 320 ° C./2.7×10 ⁻⁴ Pa to obtain a purple solid (1.9 g).
HPLC: 97.5% (UV254 area%)
The physical properties are as follows.
mp: 211 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 500 nm

Synthesis example 4
Compound D was synthesized by the following reaction.

(1) Synthesis of 9-iodoanthracene Under a nitrogen atmosphere, 9-bromoanthracene (7.0 g, 27 mmol) was dissolved in a mixed solvent of anhydrous THF (35 ml) and anhydrous toluene (70 ml), and -30 in a dry ice / methanol bath. Cooled to ° C. A butyllithium / hexane solution (1.6 mol / l, 19 ml, 30 mmol, 1.1 eq.) Was added dropwise thereto, and the mixture was stirred at −25 to 0 ° C. for 1 hour. The reaction mixture was cooled to −68 ° C., and an iodine / THF solution (8.3 g, 33 mmol, 1.2 eq./15 ml) was gradually added dropwise over 10 minutes, followed by stirring at −74 ° C. for 1 hour and at room temperature for 5 hours. did. The reaction mixture was quenched by adding 10% aqueous sodium sulfite solution (100 ml), and the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a yellow solid. This was washed with ethanol to obtain a yellow solid (6.9 g, 84%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.42 (2H, t, J = 7 Hz), 7.52 (2H, t, J = 7 Hz), 7.86 (2H, d, J = 8Hz), 8.33 (1H, s), 8.41 (2H, d, J = 8Hz)

(2) Synthesis of 9- (2-bromophenyl) anthracene Under a nitrogen atmosphere, 2-bromophenylboronic acid (4.5 g, 22 mmol, 1 eq.), 9-iodoanthracene (6.9 g, 23 mmol), tetrakis (tri Phenylphosphine) palladium (0) (0.52 g, 0.45 mmol, 2% Pd) was suspended in 1,2-dimethoxyethane (70 ml), and 2M aqueous sodium carbonate solution (7.0 g, 66 mmol, 3 eq./35 ml) was suspended. ) And refluxed for 10 hours. The reaction mixture was diluted with toluene (100 ml), the organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane, followed by hexane + 5% dichloromethane, and finally hexane + 20% dichloromethane) to give a white solid (6.0 g, 82%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.31-7.50 (9H, m), 7.83 (1H, dd, J = 8 Hz, 1 Hz), 8.04 (2H, d, J = 8Hz), 8.52 (1H, s)

(3) Synthesis of benzofluoranthene 9- (2-bromophenyl) anthracene (6.0 g, 18 mmol), dichlorobis (triphenylphosphine) palladium (II) (1.3 g, 1.9 mmol, 10) under nitrogen atmosphere % Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (3.3 g, 2 mmol, 1.2 eq.) Was suspended in anhydrous DMF (70 ml) and stirred at 140 ° C. for 10 hours. . The reaction mixture was cooled in a water bath, water (100 ml) was added and extracted with toluene (150 ml). The organic layer was washed with 1% hydrochloric acid (100 ml) and saturated brine (50 ml), dried over anhydrous magnesium sulfate, evaporated and washed with methanol to give an orange solid (3.9 g). This was purified by column chromatography (silica gel / hexane + 5% dichloromethane followed by hexane + 10% dichloromethane and finally hexane + 17% dichloromethane) to give yellow needles (3.0 g, 66%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.38 (1H, t, J = 8 Hz), 7.44-7.50 (2H, m), 7.60-7.67 (2H, m), 7.96-7.99 (3H, m), 8.10 (1H, d, J = 8 Hz), 8.35 (1H, d, J = 8 Hz), 8.42 (1H, s) , 8.72 (1H, d, J = 9 Hz)

(4) Synthesis of 4-bromobenzofluoranthene Benzofluoranthene (3.0 g, 12 mmol) was suspended in anhydrous DMF (40 ml), and N-bromosuccinimide (2.3 g, 13 mmol, 1.1 eq.) Anhydrous DMF solution (5 ml) was added, and the mixture was stirred at room temperature for 3 hours and allowed to stand overnight. The reaction mixture was cooled in a water bath, water (100 ml) was added, the solid was filtered off and washed with methanol to give an orange solid (3.8 g, 96%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.40-7.46 (2H, m), 7.63-7.73 (3H, m), 7.95-7.98 (2H, m), 8.27 (1H, d, J = 9 Hz), 8.32 (1H, d, J = 7 Hz), 8.64 (1H, d, J = 8 Hz), 8.74 (1H, d, J = 9Hz)

(5) Synthesis of Compound D In a nitrogen atmosphere, 4-bromobenzofluoranthene (2.0 g, 6.0 mmol), diphenylamine (1.2 g, 7.1 mmol, 1.2 eq.), Tris (dibenzylideneacetone) Di-palladium (0) (0.08 g, 87 μmol, 3% Pd) and sodium t-butoxide (0.8 g, 8.3 mmol, 1.4 eq.) Were suspended in anhydrous toluene (30 ml) and tri-t-butylphosphine. / Toluene solution (66%, 0.04 ml, 0.13 mmol, 0.8 eq. To Pd) was added and refluxed for 11 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The orange solid (2.5 g) obtained by evaporating the solvent from the filtrate was purified by column chromatography (silica gel / hexane + 5% dichloromethane followed by hexane + 10% dichloromethane and finally hexane + 33% dichloromethane) to give a red solid ( 2.2 g, 88%). The obtained solid was recrystallized from ethanol (30 ml) + toluene (40 ml) to obtain red plate crystals (1.3 g, 52%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 6.89 (2H, t, J = 7 Hz), 7.09-7.18 (8H, m), 7.38-7.50 (4H M), 7.61 (1H, t, 7 Hz), 7.93 (2H, t, J = 8 Hz), 7.97 (1H, d, J = 8 Hz), 8.27 (1H, d, J = 9 Hz), 8.37 (1 H, d, J = 8 Hz), 8.79 (1 H, d, J = 9 Hz)
FDMS: Calculated value C ₃₂ H ₂₁ N = 419, measured value m / z = 419 (M ⁺ , 100)
HPLC: 99.1% (UV254 area%)

The solid (2.0 g) obtained above was purified by sublimation at 320 ° C./2.7×10 ⁻⁴ Pa to obtain a purple solid (1.9 g).
HPLC, 99.5% (UV254 area%)
The physical properties are as follows.
mp: 239 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 498 nm

Synthesis example 5
Compound E was synthesized by the following reaction.

  Under a nitrogen atmosphere, 4-bromobenzofluoranthene (1.8 g, 5.4 mmol), N- (4-carbazolylphenyl) phenylaniline (2.2 g, 6.6 mmol, 1.2 eq.), Tris ( Dibenzylideneacetone) dipalladium (0) (0.07 g, 76 μmol, 3% Pd) and sodium t-butoxide (0.7 g, 7.3 mmol, 1.4 eq.) Were suspended in anhydrous toluene (25 ml), A t-butylphosphine / toluene solution (66%, 0.04 ml, 0.13 mmol, 0.8 eq. to Pd) was added and refluxed for 11 hours. The reaction mixture was diluted with methanol (50 ml), the solid was filtered off and washed with methanol to give an orange solid (3.1 g). This was purified by column chromatography (silica gel / hexane + 10% dichloromethane followed by hexane + 33% dichloromethane and finally hexane + 66% dichloromethane) to give an orange solid (3.0 g, 90%). The obtained solid was recrystallized from toluene (50 ml) to obtain orange needle crystals (1.4 g).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 6.95-6.98 (1H, m), 7.22-7.45 (16H, m), 7.47-7.52 (1H M), 7.58 (1H, dd, J = 8 Hz, 6 Hz), 7.67 (1H, t, J = 8 Hz), 7.98 (1H, d, J = 7 Hz), 8.02 (1H , D, J = 8 Hz), 8.04 (1H, d, J = 9 Hz), 8.10 (2H, d, J = 8 Hz), 8.37 (1H, d, J = 9 Hz), 8.41 (1H, d, J = 7Hz), 8.85 (1H, d, J = 9Hz)
FDMS: calculated value C ₄₄ H ₂₈ N ₂ = 584, actually measured value m / z = 584 (M ⁺ , 100)
HPLC: 99.3% (UV254 area%)

The solid (1.4 g) obtained above was purified by sublimation at 340 ° C./9.9×10 ⁻⁵ Pa to obtain an orange solid (1.2 g).
HPLC: 99.5% (UV254 area%)
The physical properties are as follows.
mp: 318 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 496 nm.

Synthesis Example 6
Compound F was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10-dihydroanthracene 1-bromo-4-propylbenzene (8.6 g) under nitrogen atmosphere , 43 mmol, 3 eq.) Was dissolved in a mixed solvent of anhydrous THF (50 ml) and anhydrous toluene (50 ml), and cooled to −68 ° C. in a dry ice / methanol bath. To this, n-butyllithium / hexane solution (1.6 mol / l, 27 ml, 43 mmol, 1 eq.) Was added dropwise and stirred at -72 ° C. for 1 hour. 1,5-Dichloroanthraquinone (4.0 g, 14 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours, and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated to give a brown color. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (5.2 g, 72%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.91 (6H, t, J = 7 Hz), 1.60 (4H, sextet, J = 7 Hz), 2.53 (4H, t, J = 7 Hz), 4.46 (2 H, s), 7.03 (4 H, d, J = 8 Hz), 7.20-7.27 (8 H, m), 7.93 (2 H, d, J = 8 Hz)

(2) Synthesis of 1,5-dichloro-9,10-bis (4-propylphenyl) anthracene 1,5-dichloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10- Dihydroanthracene (5.2 g, 10 mmol), potassium iodide (5.0 g, 30 mmol, 3 eq.), Sodium phosphinate monohydrate (1.6 g, 15 mmol, 0.5 eq. To KI) in acetic acid (50 ml) And then refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), the solid was filtered off, washed with water and methanol to give a pale yellow solid (4.5 g, 93%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.03 (6H, t, J = 7 Hz), 1.79 (4H, sextet, J = 7 Hz), 2.75 (4H, t, J = 7 Hz), 7.10 (1H, dd, J = 9 Hz, 7 Hz), 7.27 (4H, d, J = 8 Hz), 7.30 (4H, d, J = 8 Hz), 7.47 (2H, dd, J = 7 Hz, 1 Hz), 7.66 (2H, dd, J = 9 Hz, 1 Hz)

(3) Synthesis of Compound F Under a nitrogen atmosphere, 1,5-dichloro-9,10-bis (4-propylphenyl) anthracene (4.0 g, 8.3 mmol), palladium acetate (0.37 g, 1.6 mmol, 10% Pd), potassium carbonate (9.8 g, 71 mmol, 4.3 eq.), And tetrabutylammonium hydrogen sulfate (5.6 g, 16 mmol, 1 eq.) Were suspended in anhydrous DMF (100 ml) and treated at 120 ° C. for 22 hours. Stir. The reaction mixture was cooled in a water bath, water (100 ml) was added, and the resulting solid was filtered off and washed with water and methanol to give a black solid (3.8 g). This was purified by column chromatography (silica gel / hexane + 5% dichloromethane followed by hexane + 17% dichloromethane and finally hexane + 50% dichloromethane) to give purple plate crystals (1.1 g, 32%). The obtained solid was recrystallized from ethanol (20 ml) + toluene (70 ml) to obtain purple plate crystals (0.9 g, 26%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 1.04 (6H, t, J = 7Hz), 1.78 (4H, sextet, J = 7Hz), 2.75 (4H, t, J = 7 Hz), 7.26 (2H, dd, J = 8 Hz, 2 Hz), 7.73 (2H, dd, J = 9 Hz, 7 Hz), 7.78 (2H, d, J = 1 Hz), 7.97. (2H, d, J = 7 Hz), 8.19 (2H, d, J = 8 Hz), 8.54 (2H, d, J = 8 Hz)
FDMS: calculated value C ₃₂ H ₂₆ = 410, measured value m / z = 410 (M ⁺ , 100)
HPLC: 98.9% (UV254 area%)

The solid (0.9 g) obtained above was purified by sublimation at 300 ° C./1.2×10 ⁻³ Pa to obtain an orange solid (0.78 g).
HPLC: 98.6% (UV254 area%)
The physical properties are as follows.
mp: 253 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 541 nm

Synthesis example 7
Compound G was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-9,10-bis (4-phenoxyphenyl) -9,10-dihydroxy 9,10-dihydroanthracene 4-bromodiphenyl ether (9.4 g, 38 mmol, 3 eq) under nitrogen atmosphere .) Was dissolved in a mixed solvent of anhydrous THF (45 ml) and anhydrous toluene (45 ml), and cooled to −62 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.6 mol / l, 24 ml, 38 mmol, 1 eq.) Was added dropwise thereto, and the mixture was stirred at −68 ° C. for 1 hour. 1,5-Dichloroanthraquinone (3.5 g, 13 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours, and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (6.7 g, 84%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 4.45 (2H, s), 6.84 (4H, d, J = 8 Hz), 6.96 (4H, d, J = 7 Hz), 7 .07 (2H, t, J = 7 Hz), 7.24-7.32 (12H, m), 7.91 (2H, dd, J = 8 Hz, 1 Hz)

(2) Synthesis of 1,5-dichloro-9,10-bis (4-phenoxyphenyl) anthracene 1,5-dichloro-9,10-bis (4-phenoxyphenyl) -9,10-dihydroxy 9,10- Dihydroanthracene (6.7 g, 11 mmol), potassium iodide (5.4 g, 33 mmol, 3 eq.), Sodium phosphinate monohydrate (1.7 g, 16 mmol, 0.5 eq. To KI) in acetic acid (50 ml) And then refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), the solid was filtered off and washed with water and methanol to give a pale yellow solid (5.8 g, 90%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.13-7.24 (12H, m), 7.32 (3H, d, J = 9 Hz), 7.40 (4H, dd, J = 9Hz, 7Hz), 7.51 (2H, dd, J = 7Hz, 1Hz), 7.70 (2H, dd, J = 9Hz, 1Hz)

(3) Synthesis of Compound G Under a nitrogen atmosphere, 1,5-dichloro-9,10-bis (4-ethophenoxyphenyl) anthracene (5.8 g, 9.9 mmol), tris (dibenzylideneacetone) dipalladium (0 .46 g, 0.50 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (4.2 g, 28 mmol, 1.4 eq.) Was suspended in anhydrous DMF (60 ml). Tri-butylphosphine / toluene solution (66%, 0.31 ml, 1.0 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 11 hours. The reaction mixture was diluted with methanol (60 ml), and the solid was filtered off and washed with methanol to obtain a reddish purple solid (4.6 g). This was recrystallized from toluene (400 ml) to obtain red plate crystals (3.2 g, 63%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.12-7.18 (8H, m), 7.38-7.42 (4H, m), 7.63 (2H, d, J = 2Hz), 7.77 (2H, t, J = 7Hz), 7.96 (2H, t, J = 7Hz), 8.26 (2H, d, J = 8Hz), 8.58 (2H, d) , J = 9Hz)
FDMS: calculated value C ₃₈ H ₂₂ O ₂ = 510, actually measured value m / z = 510 (M ⁺ , 100)
HPLC: 99.5% (UV254 area%)

The solid (2.0 g) obtained above was purified by sublimation at 340 ° C./4.1×10 ⁻⁴ Pa to obtain a reddish brown solid (1.8 g).
HPLC: 98.8% (UV254 area%)
The physical properties are as follows.
mp: 275 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 551 nm

Synthesis example 8
Compound H was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-10- (4-methoxyphenyl) -10-hydroxyanthrone 1,5-dichloroanthraquinone (5.0 g, 18 mmol) was suspended in anhydrous THF (140 ml) under a nitrogen atmosphere. 4-methoxyphenylmagnesium bromide in THF (0.5 mol / l, 40 ml, 20 mmol, 1.1 eq.) Was gradually added dropwise at room temperature over 1 hour. The reaction mixture was stirred at room temperature for 9 hours and left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to give a green solid. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by hexane + 66% dichloromethane and finally hexane + 83% dichloromethane) to give a pale orange solid (4.2 g, 61%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.72 (3H, s), 4.56 (1H, s), 6.75 (2H, d, J = 9 Hz), 7.20 (2H , D, J = 9 Hz), 7.38 (1H, dd, J = 8 Hz, 2 Hz), 7.43 (1H, t, J = 8 Hz), 7.47 (1H, t, J = 8 Hz), 7 .57 (1H, dd, J = 8 Hz, 2 Hz), 7.79 (1H, dd, J = 8 Hz, 2 Hz), 8.27 (1H, dd, J = 8 Hz, 1 Hz)

(2) Synthesis of 1,5-dichloro-9-phenyl-10- (4-methoxyphenyl) -9,10-dihydroxy-9,10-dihydroanthracene Under a nitrogen atmosphere, phenylcyclohexane + ether solution (1. 1 mol / l, 41 ml, 44 mmol, 4 eq.) Was mixed with anhydrous THF (30 ml) and cooled to −58 ° C. in a dry ice / methanol bath. 1,5-Dichloro-10- (4-methoxyphenyl) -10-hydroxyanthrone (4.2 g, 11 mmol) was added thereto, and the mixture was stirred at room temperature for 9 hours and left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale orange amorphous solid (4.3 g, 84%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.75 (3H, s), 4.47 (1H, s), 4.48 (1H, s), 6.76 (2H, d, J = 9 Hz), 7.18-7.34 (9 H, m), 7.36 (2 H, d, J = 7 Hz), 7.90-7.93 (2 H, m)

(3) Synthesis of 1,5-dichloro-9-phenyl-10- (4-methoxyphenyl) -anthracene 1,5-dichloro-9-phenyl-10- (4-methoxyphenyl) -9,10-dihydroxy- 9,10-dihydroanthracene (4.3 g, 9.3 mmol), potassium iodide (4.6 g, 28 mmol, 3 eq.), Sodium phosphinate monohydrate (1.5 g, 14 mmol, 0.5 eq. To KI) ) Was dissolved in acetic acid (40 ml) and refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), and the solid was filtered off and washed with water and methanol to give a pale yellow solid (2.7 g, 68%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 3.94 (3H, s), 7.04 (2H, d, J = 9 Hz), 7.14 (1H, t, J = 7 Hz), 7 .16 (1H, t, J = 7 Hz), 7.28 (2H, d, J = 9 Hz), 7.37-7.39 (2H, m), 7.59 (1H, dd, J = 9 Hz) 1 Hz), 7.68 (1 H, dd, J = 9 Hz, 1 Hz)

(4) Synthesis of Compound H Under a nitrogen atmosphere, 1,5-dichloro-9-phenyl-10- (4-methoxyphenyl) -anthracene (2.7 g, 6.3 mmol), tris (dibenzylideneacetone) dipalladium ( 0.29 g, 0.32 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (2.7 g, 18 mmol, 1.4 eq.) In anhydrous DMF (35 ml). The solution became cloudy, and a tri-t-butylphosphine / toluene solution (66%, 0.19 ml, 0.62 mmol, 1 eq to Pd) was added, followed by stirring at 140 ° C. for 11 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to obtain a reddish purple solid (1.8 g). This was recrystallized from toluene (250 ml) to obtain reddish purple plate crystals (1.0 g, 46%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 3.98 (3H, s), 6.99 (1H, dd, J = 8Hz, 2Hz), 7.38 (1H, t, J = 7Hz ), 7.46 (1H, t, J = 7 Hz), 7.53 (1H, d, J = 2 Hz), 7.74-7.79 (2H, m), 7.97 (1H, d, J = 7 Hz), 7.99 (1 H, d, J = 7 Hz), 8.03 (1 H, d, J = 6 Hz), 8.21 (1 H, d, J = 8 Hz), 8.32 (1 H, d) , J = 8 Hz), 8.54 (1H, d, J = 8 Hz), 8.60 (1H, d, J = 9 Hz)
FDMS: calculated value C ₂₇ H ₁₆ O = 356, actually measured value m / z = 356 (M ⁺ , 100)
HPLC: 99.2% (UV254 area%)

The solid (1.0 g) obtained above was purified by sublimation at 280 ° C./1.4×10 ⁻⁴ Pa to obtain a reddish brown solid (0.8 g).
HPLC: 99.0% (UV254 area%)
The physical properties are as follows.
mp: 281 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 556 nm

Synthesis Example 9
Compound I was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-10-phenyl-10-hydroxyanthrone 1,5-dichloroanthraquinone (10 g, 36 mmol) was suspended in anhydrous THF (140 ml) under a nitrogen atmosphere, and a solution of phenylmagnesium bromide in THF (1.1 mol / l, 37 ml, 40 mmol, 1.1 eq.) Was gradually added dropwise at room temperature over 1 hour. The reaction mixture was stirred at room temperature for 10 hours and left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was diluted with toluene (100 ml), and insoluble materials were filtered off. The organic layer was separated from the filtrate, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to give a pale green solid. This was purified twice by column chromatography (silica gel / hexane + 50% dichloromethane followed by hexane + 66% dichloromethane and finally hexane + 83% dichloromethane) to give a white solid (5.1 g, 40%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 4.58 (1H, s), 7.17 (1H, t, J = 8 Hz), 7.24 (2H, t, J = 8 Hz), 7 .31 (2H, d, J = 8 Hz), 7.40 (1H, dd, J = 8 Hz, 2 Hz), 7.43 (1H, t, J = 8 Hz), 7.58 (1H, dd, J = 8Hz, 1Hz), 7.79 (1H, dd, J = 7Hz, 2Hz), 8.31 (1H, dd, J = 8Hz, 2Hz)

(2) Synthesis of 1,5-dichloro-9-phenyl-10- (4-bromophenyl) -9,10-dihydroxy-9,10-dihydroanthracene In a nitrogen atmosphere, 4-bromoiodobenzene (12.2 g, 43 mmol, 3 eq.) Was dissolved in a mixed solvent of anhydrous THF (40 ml) and anhydrous toluene (40 ml), and cooled to −64 ° C. in a dry ice / methanol bath. To this was added an n-butyllithium / hexane solution (1.6 mol / l, 27 ml, 43 mmol, 1 eq.), And the mixture was stirred at -68 ° C for 1 hour. To this, 1,5-dichloro-10-phenyl-10-hydroxyanthrone (5.1 g, 14 mmol) was added, stirred at room temperature for 9 hours and allowed to stand overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a white solid (7.1 g, 97%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 4.36 (1H, s), 4.47 (1H, s), 7.22-7.39 (13H, m), 7.86 (1H , Dd, J = 8 Hz, 2 Hz), 7.95 (1H, dd, J = 8 Hz, 2 Hz)

(3) Synthesis of 1,5-dichloro-9-phenyl-10- (4-bromophenyl) -anthracene 1,5-dichloro-9-phenyl-10- (4-bromophenyl) -9,10-dihydroxy- 9,10-dihydroanthracene (7.1 g, 14 mmol), potassium iodide (6.9 g, 42 mmol, 3 eq.), Sodium phosphinate monohydrate (2.2 g, 21 mmol, 0.5 eq. To KI). Dissolved in acetic acid (70 ml) and refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), and the solid was filtered off and washed with water and methanol to give a pale yellow solid (6.2 g, 93%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.16 (1H, t, J = 6 Hz), 7.18 (1H, t, J = 6 Hz), 7.27 (2H, d, J = 8 Hz), 7.36-7.39 (12 H, m), 7.48-7.51 (5 H, m), 7.56 (1 H, dd, J = 9 Hz, 1 Hz), 7.61 (1 H, dd, J = 9 Hz, 1 Hz), 7.64 (2H, d, J = 8 Hz)

(4) Synthesis of 1,5-dichloro-9-phenyl-10- (4- (N-methyl-N-phenylamino) phenyl) -anthracene 1,5-dichloro-9-phenyl-10- under nitrogen atmosphere (4-Bromophenyl) -anthracene (3.0 g, 6.3 mmol), N-methylaniline (0.8 g, 7.5 mmol, 1.2 eq.), Tris (dibenzylideneacetone) dipalladium (0.06 g, 66 μmol, 2% Pd) and sodium t-butoxide (0.9 g, 9.4 mmol, 1.5 eq.) Were suspended in anhydrous toluene (20 ml), and a tri-t-butylphosphine / toluene solution (66%, 0.8%) was suspended. 03 ml, 98 μmol, 0.8 eq. To Pd) was added, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (300 ml). The dark yellow solid (3.3 g) obtained by evaporating the solvent from the filtrate was purified by column chromatography (silica gel / hexane + 17% dichloromethane, followed by hexane + 33% dichloromethane) to give a yellow solid (2.5 g, 79% )
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.03 (1H, t, J = 8 Hz), 7.11-7.25 (8H, m), 7.34-7.40 (4H, m), 7.48-7.50 (5H, m), 7.59 (1H, dd, J = 9 Hz, 1 Hz), 7.80 (1H, dd, J = 9 Hz, 1 Hz)

(5) Synthesis of Compound I Under a nitrogen atmosphere, 1,5-dichloro-9-phenyl-10- (4- (N-methyl-N-phenylamino) phenyl) -anthracene (2.5 g, 5.0 mmol), Tris (dibenzylideneacetone) dipalladium (0.23 g, 0.25 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (2.1 g, 14 mmol, 1.4 eq. ) Was suspended in anhydrous DMF (30 ml), tri-t-butylphosphine / toluene solution (66%, 0.15 ml, 0.49 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 11 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to obtain a reddish purple solid (1.9 g). This was purified by column chromatography (silica gel / hexane + 17% dichloromethane, followed by hexane + 33% dichloromethane, finally dichloromethane) to give dark purple plate crystals (1.7 g, 79%). The obtained solid was recrystallized from toluene (100 ml) to obtain dark purple plate crystals (1.3 g).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 3.49 (3H, s), 7.05-7.07 (2H, m), 7.19 (2H, d, J = 8Hz), 7.34-7.38 (3H, m), 7.44 (1H, t, J = 7 Hz), 7.60 (1H, d, J = 2 Hz), 7.68-7.74 (2H, m) ), 7.88 (1H, d, J = 6 Hz), 7.96 (1H, d, J = 7 Hz), 7.99 (1H, d, J = 6 Hz), 8.16 (1H, d, J = 8 Hz), 8.28 (1 H, d, J = 8 Hz), 8.50 (1 H, d, J = 9 Hz), 8.54 (1 H, d, J = 9 Hz)
FDMS: Calculated value C ₃₃ H ₂₁ N = 431, measured value m / z = 431 (M ⁺ , 100)
HPLC: 95.8% (UV254 area%)

The solid (1.2 g) obtained above was purified by sublimation at 320 ° C./3.5×10 ⁻⁴ Pa to obtain a black purple solid (1.1 g).
HPLC: 95.2% (UV254 area%)
The physical properties are as follows.
mp: 236 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 570 nm.

Synthesis Example 10
Compound J was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-9-phenyl-10- (4′-pentyl-4-biphenylyl) -9,10-dihydroxy-9,10-dihydroanthracene 4-bromo-4 ′ under nitrogen atmosphere -Pentylbiphenyl (7.7 g, 25 mmol, 3 eq.) Was dissolved in a mixed solvent of anhydrous THF (30 ml) and anhydrous toluene (30 ml), and cooled to -30 ° C in a dry ice / methanol bath. To this was added an n-butyllithium / hexane solution (1.6 mol / l, 16 ml, 26 mmol, 1 eq.), And the mixture was stirred at −50 ° C. for 1 hour. To this, 1,5-dichloro-10-phenyl-10-hydroxyanthrone (3.0 g, 8.5 mmol) was added and stirred at room temperature for 10 hours and allowed to stand overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a pale yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a white amorphous solid (3.7 g, 75%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.89 (3H, t, J = 7 Hz), 1.31-1.35 (4H, m), 1.63 (2H, quintet, J = 7 Hz), 2.62 (2 H, t, J = 7 Hz), 4.46 (1 H, s), 4.49 (1 H, s), 7.20-7.30 (9 H, m), 7.39. -7.42 (4H, m), 7.47 (4H, d, J = 8Hz), 7.95 (1H, dd, J = 8Hz, 2Hz)

(2) Synthesis of 1,5-dichloro-9-phenyl-10- (4′-pentyl-4-biphenylyl) -anthracene 1,5-dichloro-9-phenyl-10- (4′-pentyl-4-biphenylyl) ) -9,10-dihydroxy-9,10-dihydroanthracene (3.7 g, 6.4 mmol), potassium iodide (3.2 g, 19 mmol, 3 eq.), Sodium phosphinate monohydrate (1.0 g, 9.4 mmol, 0.5 eq. To KI) was dissolved in acetic acid (30 ml) and refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), the solid was filtered off, washed with water and methanol to give a pale yellow solid (3.4 g, 97%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.92 (3H, t, J = 7 Hz), 1.35 to 1.39 (4H, m), 1.69 (2H, quintet, J = 7 Hz), 2.68 (2H, t, J = 7 Hz), 7.14-7.19 (2H, m), 7.31 (2H, d, J = 8 Hz), 7.38-7.41 ( 2H, m), 7.43 (2H, d, J = 8 Hz), 7.48-7.51 (5H, m), 7.61 (1H, dd, J = 8 Hz, 1 Hz), 7.68- 7.75 (5H, m)

(3) Synthesis of Compound J Under a nitrogen atmosphere, 1,5-dichloro-9-phenyl-10- (4′-pentyl-4-biphenylyl) -anthracene (3.4 g, 6.2 mmol), tris (dibenzylideneacetone) ) Dipalladium (0.29 g, 0.32 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (2.6 g, 17 mmol, 1.4 eq.) In anhydrous DMF ( 40 ml), tri-t-butylphosphine / toluene solution (66%, 0.19 ml, 0.62 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 11 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to give a reddish brown solid (2.9 g). This was purified twice by column chromatography (silica gel / hexane + 17% dichloromethane followed by hexane + 50% dichloromethane and finally dichloromethane) to give a reddish brown solid (2.5 g, 85%). The obtained solid was recrystallized from toluene (100 ml) to obtain reddish brown plate crystals (2.1 g).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.94 (3H, t, J = 7 Hz), 1.37-1.41 (4H, m), 1.69-1.73 (2H M), 2.70 (2H, t, J = 7 Hz), 7.34 (2H, d, J = 8 Hz), 7.38 (1H, t, J = 7 Hz), 7.45 (1H, t , J = 7 Hz), 7.65-7.75 (5H, m), 7.93-8.60 (3H, m), 8.14 (1H, s), 8.28 (2H, d, J = 8 Hz), 8.52 (2H, dd, J = 9 Hz, 3 Hz)
FDMS: calculated value C ₃₇ H ₂₈ = 472, measured value m / z = 236 (M ²⁺ , 3), 472 (M ⁺ , 100)
HPLC: 99.9% (UV254 area%)

The solid (1.9 g) obtained above was purified by sublimation at 320 ° C./2.2×10 ⁻⁴ Pa to obtain a black purple solid (1.8 g).
HPLC: 99.5% (UV254 area%)
The physical properties are as follows.
mp: 237 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 546 nm.

Synthesis Example 11
Compound K was synthesized by the following reaction.

(1) Synthesis of 1,5-dichloro-9-phenyl-10- (4- (diphenylamino) phenyl) -anthracene 1,5-dichloro-9-phenyl-10- (4-bromophenyl) under nitrogen atmosphere Anthracene (3.2 g, 6.7 mmol), diphenylamine (1.4 g, 8.3 mmol, 1.2 eq.), Tris (dibenzylideneacetone) dipalladium (0.09 g, 98 μmol, 3% Pd), 2, 2′-bis (diphenylphosphino) -1,1′-binaphthyl (0.18 g, 0.29 mmol, 1.5 eq. To Pd), sodium t-butoxide (1.0 g, 10 mmol, 1.5 eq.). It was suspended in anhydrous toluene (20 ml) and refluxed for 11 hours. The reaction mixture was filtered off through a silica gel pad and washed with toluene (200 ml). The dark red oil obtained by evaporating the solvent from the filtrate was purified by column chromatography (silica gel / hexane + 10% dichloromethane followed by hexane + 17% dichloromethane and finally hexane + 33% dichloromethane) to give an orange solid (2.7 g, 71%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.06 (2H, t, J = 7 Hz), 7.16 (1H, dd, J = 9 Hz, 7 Hz), 7.20-7.25 ( 9H, m), 7.32 (4H, t, J = 7 Hz), 7.38-7.40 (2H, m), 7.46-7.52 (5H, m), 7.60 (1H, dd, J = 9 Hz, 1 Hz), 7.84 (1H, dd, J = 9 Hz, 1 Hz)

(2) Synthesis of Compound K Under a nitrogen atmosphere, 1,5-dichloro-9-phenyl-10- (4- (diphenylamino) phenyl) -anthracene (3.8 g, 6.7 mmol), tris (dibenzylideneacetone) Di-palladium (0.31 g, 0.34 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (2.9 g, 19 mmol, 1.4 eq.) In anhydrous DMF (40 ml) ), A tri-t-butylphosphine / toluene solution (66%, 0.21 ml, 0.69 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 11 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to give a black solid (2.7 g). This was recrystallized from toluene (100 ml) to obtain black purple plate crystals (2.1 g, 66%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 7.08 (2H, t, J = 8Hz), 7.16 (1H, dd, J = 8Hz, 2Hz), 7.27 (4H, d , J = 8 Hz), 7.31 (4H, t, J = 8 Hz), 7.38 (1H, t, J = 8 Hz), 7.46 (1H, t, J = 8 Hz), 7.70-7. .76 (3H, m), 7.87 (1H, d, J = 7 Hz), 7.98 (1H, d, J = 8 Hz), 8.02 (1H, d, J = 7 Hz), 8.17 (1H, d, J = 8 Hz), 8.32 (1H, d, J = 7 Hz), 8.53 (1H, d, J = 9 Hz), 8.59 (1H, d, J = 9 Hz)
FDMS: Calculated value C ₃₈ H ₂₃ N = 493, measured value m / z = 493 (M ⁺ , 100)
HPLC: 99.2% (UV254 area%)

The solid (1.9 g) obtained above was purified by sublimation at 320 ° C./6.2×10 ⁻³ Pa to obtain a black purple solid (1.8 g).
The physical properties are as follows.
mp: 297 ° C
HPLC: 99.1% (UV254 area%)

Synthesis Example 12
Compound L was synthesized by the following reaction.

(1) Synthesis of 1,4-dichloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10-dihydroanthracene 1-bromo-4-propylbenzene (10.8 g) under nitrogen atmosphere , 54 mmol, 3 eq.) Was dissolved in a mixed solvent of anhydrous THF (60 ml) and anhydrous toluene (60 ml), and cooled to −66 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.6 mol / l, 34 ml, 54 mmol, 1 eq.) Was added dropwise thereto, and the mixture was stirred at −68 ° C. for 1 hour. 1,4-Dichloroanthraquinone (5.0 g, 18 mmol) was added to the reaction mixture, the cooling bath was removed, and the mixture was stirred at room temperature for 10 hours and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off to give a yellow color. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (8.6 g, 92%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 0.90 (6H, t, J = 7 Hz), 1.60 (4H, sextet, J = 7 Hz), 2.54 (4H, t, J = 7Hz), 4.11 (2H, s), 7.09-7.11 (5H, m), 7.26 (2H, s), 7.42-7.46 (5H, m)

(2) Synthesis of 1,4-dichloro-9,10-bis (4-propylphenyl) anthracene 1,4-dichloro-9,10-bis (4-propylphenyl) -9,10-dihydroxy 9,10- Dihydroanthracene (8.6 g, 17 mmol), potassium iodide (8.3 g, 50 mmol, 3 eq.), Sodium phosphinate monohydrate (2.7 g, 25 mmol, 0.5 eq. To KI) and acetic acid (70 ml) And then refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), the solid was filtered off, washed with water and methanol to give a pale yellow solid (8.0 g, 98%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 1.03 (6H, t, J = 7 Hz), 1.78 (4H, sextet, J = 7 Hz), 2.75 (4H, t, J = 7Hz), 7.29 (10H, s), 7.35 (2H, dd, J = 7Hz, 4Hz), 7.68 (2H, dd, J = 7Hz, 4Hz)

(3) Synthesis of Compound L Under a nitrogen atmosphere, 1,4-dichloro-9,10-bis (4-propylphenyl) anthracene (8.0 g, 17 mmol), tris (dibenzylideneacetone) dipalladium (0.76 g, 0.83 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (7.1 g, 47 mmol, 1.4 eq.) Was suspended in anhydrous DMF (80 ml) and tri-t -A butylphosphine / toluene solution (66%, 0.51 ml, 1.7 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to give a brown solid (7.0 g). The obtained solid was recrystallized from toluene (100 ml) to obtain dark brown needle crystals (4.9 g, 72%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
_{^{· 1 H-NMR (400MHz,}} CDCl 3, TMS) δ: 1.01 (6H, t, J = 8Hz), 1.72 (4H, sextet, J = 8Hz), 2.60 (4H, t, J = 8 Hz), 6.98 (2H, dd, J = 8 Hz, 1 Hz), 7.37 (2H, d, J = 2 Hz), 7.44 (2H, s), 7.44-7.47 (2H) M), 7.74 (2H, d, J = 8 Hz), 8.33 (2H, dd, J = 7 Hz, 3 Hz)
FDMS: calculated value C ₃₂ H ₂₆ = 410, measured value m / z = 410 (M ⁺ , 100)
HPLC: 99.1% (UV254 area%)

The solid (2.5 g) obtained above was purified by sublimation at 300 ° C./1.9×10 ⁻³ Pa to obtain a brown solid (2.4 g).
HPLC: 99.2% (UV254 area%)
The physical properties are as follows.
mp: 222 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 482 nm.

Synthesis Example 13
Compound M was synthesized by the following reaction.

(1) Synthesis of 1,4-dichloro-9,10-bis (4-phenoxyphenyl) -9,10-dihydroxy 9,10-dihydroanthracene In a nitrogen atmosphere, 4-bromo-diphenyl ether (6.7 g, 27 mmol, 3 eq.) Was dissolved in a mixed solvent of anhydrous THF (30 ml) and anhydrous toluene (30 ml), and cooled to −64 ° C. in a dry ice / methanol bath. To this, n-butyllithium / hexane solution (1.6 mol / l, 17 ml, 27 mmol, 1 eq.) Was added dropwise and stirred at -68 ° C. for 1 hour. 1,4-Dichloroanthraquinone (2.5 g, 9.0 mmol) was added to the reaction mixture, the cooling bath was removed, the mixture was stirred at room temperature for 10 hours, and then left overnight. The reaction mixture was cooled in a water bath, quenched with a saturated aqueous ammonium chloride solution (50 ml), the organic layer was separated, the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off to give a yellow color. I got oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by dichloromethane, finally dichloromethane + 3% methanol) to give a pale yellow amorphous solid (5.0 g, 90%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 4.07 (2H, s), 6.91 (4H, d, J = 9 Hz), 6.96 (4H, d, J = 8 Hz), 7 .07 (2H, t, J = 7 Hz), 7.17 (2H, dd, J = 6 Hz, 3 Hz), 7.27-7.31 (6H, m), 7.44-7.47 (6H, m)

(2) Synthesis of 1,4-dichloro-9,10-bis (4-phenoxyphenyl) anthracene 1,4-dichloro-9,10-bis (4-phenoxyphenyl) -9,10-dihydroxy 9,10- Dihydroanthracene (5.0 g, 8.1 mmol), potassium iodide (4.0 g, 24 mmol, 3 eq.), Sodium phosphinate monohydrate (1.3 g, 12 mmol, 0.5 eq. To KI) with acetic acid ( 35 ml) and refluxed for 2 hours. The reaction mixture was diluted with water (100 ml), and the solid was filtered off and washed with water and methanol to give a pale yellow solid (4.4 g, 93%).
The result of ¹ H-NMR of this solid is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 7.08-7.13 (10H, m), 7.27-7.30 (6H, m), 7.31-7.38 (6H, m), 7.68 (2H, dd, J = 7 Hz, 3 Hz)

(3) Synthesis of Compound M Under a nitrogen atmosphere, 1,4-dichloro-9,10-bis (4-phenoxyphenyl) anthracene (4.4 g, 7.5 mmol), tris (dibenzylideneacetone) dipalladium (0. 35 g, 0.38 mmol, 5% Pd), 1,8-diazabicyclo [5.4.0] undec-7-ene (3.2 g, 21 mmol, 1.4 eq.) Suspended in anhydrous DMF (35 ml), A tri-t-butylphosphine / toluene solution (66%, 0.23 ml, 0.75 mmol, 1 eq to Pd) was added, and the mixture was stirred at 140 ° C. for 10 hours. The reaction mixture was diluted with methanol (100 ml), the solid was filtered off and washed with methanol to give a dark brown solid (3.6 g). The obtained solid was recrystallized from toluene (40 ml) to obtain dark brown needles (2.5 g, 65%).

The results of ¹ H-NMR, FDMS and HPLC of this solid are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS) δ: 6.83 (2H, dd, J = 8 Hz, 3 Hz), 7.11-7.16 (6H, m), 7.21 (2H, d , J = 2 Hz), 7.36-7.40 (6H, m), 7.46 (2H, dd, J = 6 Hz, 3 Hz), 7.76 (2H, d, J = 8 Hz), 8.28. (2H, dd, J = 6 Hz, 3 Hz).
FDMS: calculated value C ₃₈ H ₂₂ O ₂ = 510, actually measured value m / z = 510 (M ⁺ , 100)
HPLC: 99.1% (UV254 area%)

The solid (1.9 g) obtained above was purified by sublimation at 320 ° C./9.1×10 ⁻³ Pa to obtain a black brown solid (1.7 g).
HPLC: 97.3% (UV254 area%)
The physical properties are as follows.
mp: 172 ° C
Absorption maximum wavelength (CH ₂ Cl ₂ ): 477 nm

[Organic thin film solar cells]
・ Configuration (ITO / P layer / C60 / Ag)
Example 1
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and the compound A synthesized in Synthesis Example 1 is resistance-heated on the surface on which the transparent electrode line as the lower electrode is formed. A film having a thickness of 30 nm was obtained by vapor deposition so as to cover the transparent electrode at 1 Å / s.
Subsequently, C60 shown below having a film thickness of 60 nm was formed on this Compound A film at 1 Å / s by resistance heating vapor deposition. Further, metal Ag was continuously deposited as a counter electrode with a film thickness of 80 nm to form an organic thin film solar cell. The area was 0.5 cm ² .

The IV characteristic was measured for the produced organic thin film solar cell under AM1.5 conditions (light intensity (Pin) 100 mW / cm ² ). As a result, open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF), and conversion efficiency (η) are shown in Table 1. The photoelectric conversion efficiency was derived from the following formula.

同じＰｉｎに対して、Ｖｏｃ、Ｊｓｃ及びＦＦがいずれも大きな化合物ほど優れた変換効率を示す。

For the same Pin, compounds with larger Voc, Jsc, and FF show better conversion efficiency.

Example 2
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that Compound A was changed to Compound B. The results are shown in Table 1.

Example 3
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that Compound A was changed to Compound F. The results are shown in Table 1.

Comparative Example 1
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that Compound A was changed to mTPD shown below. The results are shown in Table 1.

・ Configuration (ITO / P layer / PTCBI / Ag)
Example 4
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 2 except that C60 was changed to PTCBI shown below. The results are shown in Table 2.

Example 5
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 4 except that Compound B was changed to Compound D. The results are shown in Table 2.

Comparative Example 2
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 4 except that Compound B was changed to mTPD. The results are shown in Table 2.

・ Configuration (ITO / P layer / C60 / BCP / Al)
Example 6
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that Compound A was changed to Compound C and the cathode was changed from Ag to BCP / Al (10 nm / 80 nm) shown below. The results are shown in Table 3.

Example 7
An organic thin film solar cell was produced and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound D. The results are shown in Table 3.

Example 8
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound E. The results are shown in Table 3.

Example 9
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound G. The results are shown in Table 3.

Example 10
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound J. The results are shown in Table 3.

Example 11
An organic thin film solar cell was prepared, produced and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound K. The results are shown in Table 3.

Example 12
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 6 except that Compound C was changed to Compound M. The results are shown in Table 3.

Comparative Example 3
An organic thin-film solar cell was produced and evaluated in the same manner as in Example 6 except that Compound C was changed to mTPD. The results are shown in Table 3.

・ Configuration (ITO / P layer / PTCBI / BCP / Al)
Example 13
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 4 except that Compound B was changed to Compound C and the cathode was changed from Ag (80 nm) to BCP / Al (10 nm / 80 nm). The results are shown in Table 4.

Example 14
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 13 except that Compound C was changed to Compound D. The results are shown in Table 4.

Example 15
An organic thin film solar cell was produced and evaluated in the same manner as in Example 13 except that Compound C was changed to Compound E. The results are shown in Table 4.

Example 16
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 13 except that Compound C was changed to Compound G. The results are shown in Table 4.

Example 17
An organic thin-film solar cell was prepared and evaluated in the same manner as in Example 13 except that Compound C was changed to Compound H. The results are shown in Table 4.

Example 18
An organic thin film solar cell was produced and evaluated in the same manner as in Example 13 except that Compound C was changed to Compound I. The results are shown in Table 4.

Comparative Example 4
An organic thin film solar cell was prepared and evaluated in the same manner as in Example 13 except that Compound C was changed to mTPD. The results are shown in Table 4.

  As can be seen from Tables 1 to 4, in the battery using the organic thin film solar cell material of the present invention, it was revealed that the conversion efficiency was improved as compared with the comparative compound, and excellent solar cell characteristics were exhibited. .

  The organic thin film solar cell of the present invention can be used for watches, mobile phones, mobile personal computers and the like.

Claims (9)

An organic thin film solar cell material represented by the following formula (1).

(Wherein R _{1 to} R ₁₂ are each hydrogen, an unsubstituted alkyl group of C _{1 to} C ₄₀ , phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4 -Pentylphenyl, 4-ethoxyphenyl, 4- (methylphenylamino) phenyl, methoxy, ethoxy, ter-butyloxy, phenoxy, naphthoxy, phenanthryloxy, phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, Dim-tolylamino, phenyl m-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl -4-carbazolylpheny Ruamino. ) An organic thin film solar cell material represented by the following formula (2).

(Wherein R _{1 to} R ₁₄ are each hydrogen, an unsubstituted alkyl group of C _{1 to} C ₄₀ , phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4 -Pentylphenyl, 4-ethoxyphenyl, 4- (methylphenylamino) phenyl, methoxy, ethoxy, ter-butyloxy, phenoxy, naphthoxy, phenanthryloxy, phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, Dim-tolylamino, phenyl m-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl -4-carbazolylpheny Ruamino .
However, not all of R _{1 to} R ₁₄ are hydrogen. ) An organic thin film solar cell material represented by the following formula (3).

(Wherein R _{1 to} R ₁₄ are each hydrogen, an unsubstituted alkyl group of C _{1 to} C ₄₀ , phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4 -Pentylphenyl, 4-ethoxyphenyl, 4- (methylphenylamino) phenyl, methoxy, ethoxy, ter-butyloxy, phenoxy, naphthoxy, phenanthryloxy, phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, Dim-tolylamino, phenyl m-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl -4-carbazolylpheny Ruamino. ) At least one of R _{1 to} R ₁₂ is phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4-pentylphenyl, 4-ethoxyphenyl, 4- (methylphenylamino) ) Phenyl, methoxy, ethoxy, ter-butyloxy, phenoxy, naphthoxy, phenanthryloxy, phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenylm-tolylamino, phenyl-1-naphthyl 2. The amino acid according to claim 1, which is amino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl-4-carbazolylphenylamino. Organic thin Solar cell material. At least one of R _{1 to} R ₁₄ is phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-propylphenyl, 4-pentylphenyl, 4-ethoxyphenyl, 4- (methylphenylamino) ) Phenyl, methoxy, ethoxy, ter-butyloxy, phenoxy, naphthoxy, phenanthryloxy, phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenylm-tolylamino, phenyl-1-naphthyl 4. Amino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl-4-carbazolylphenylamino Described in Machine for thin film solar cells material. R ₈ is phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenylm-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) Amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl-4-carbazolylphenylamino , wherein R _{1 to} R ₇ and R _{9 to} R ₁₂ are each hydrogen or C ₁ to The organic thin-film solar cell material according to claim 1, which is a C ₄₀ unsubstituted alkyl group. R ₃ is phenylamino, methylphenylamino, diphenylamino, di-p-tolylamino, dim-tolylamino, phenylm-tolylamino, phenyl-1-naphthylamino, phenyl-2-naphthylamino, phenyl (sec-butylphenyl) Amino, phenyl t-butylamino, bis (4-methoxyphenyl) amino, or phenyl-4-carbazolylphenylamino , wherein R ₁ , R _2, and R _{4 to} R ₁₄ are each hydrogen or C ₁ to The organic thin-film solar cell material according to claim 2, which is a C ₄₀ unsubstituted alkyl group. Having at least a p-layer between a pair of electrodes;
The organic thin-film solar cell in which the said p layer contains the material in any one of Claims 1-7.   The apparatus which comprises the organic thin-film solar cell of Claim 8.