JP2008303152A - New copper complex and organic electroluminescent device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new light-emitting metal complex useful as an organic electronics material, particularly a material for an organic EL (electroluminescent) device. <P>SOLUTION: The mononuclear monovalent copper complex represented by formula (1) (wherein, X and Y are each independently N or CR<SB>6</SB>; R<SB>1</SB>to R<SB>6</SB>are each independently hydrogen, a halogen, a 1-40C substituted or unsubstituted alkyl group, a 2-40C substituted or unsubstituted alkenyl group, a 6-40C substituted or unsubstituted aryl group, a 3-40C substituted or unsubstituted heteroaryl group, a 1-40C substituted or unsubstituted alkoxy group, a 6-40C substituted or unsubstituted aryloxy group or a 1-40C substituted or unsubstituted alkylthio group and the adjacent groups in R<SB>1</SB>to R<SB>6</SB>may be bound to form a ring; L<SB>1</SB>and L<SB>2</SB>are each independently a ligand containing an element selected from nitrogen, phosphorus and arsenic and L<SB>1</SB>and L<SB>2</SB>may mutually be bound to form a bidentate ligand) is used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel metal complex, in particular, a luminescent metal complex, and an organic electronic material using the same, in particular, a material for an organic electroluminescence element or a light emitting material, and an organic electroluminescence element. More specifically, the present invention relates to an organic electroluminescence element or a light emitting material that can obtain particularly efficient light emission by using a specific copper complex as a material for an organic electroluminescence element or a light emitting material.

An organic electroluminescence (EL) element is a carrier-injection-type light-emitting element that has recently attracted attention as a next-generation flat panel display next to a liquid crystal display or a plasma display, and is partially put into practical use. In an organic EL element, there are two types of excitons generated by carrier recombination, singlet and triplet. If the recombination of electrons and holes occurs randomly and follows simple spin statistics, the production ratio should be singlet: triplet = 1: 3, which is 3 compared to singlet excitons. That is, triplet excitons are generated. Here, light emitted from singlet excitons is called fluorescence, and light emitted from triplet excitons is called phosphorescence.
By the way, in conventional fluorescent dyes frequently used as materials for organic EL elements, the radiation deactivation process from triplet is very slow due to spin prohibition, and overcomes non-radiative transition (thermal deactivation) at room temperature. It is not possible to observe phosphorescence emission at room temperature. Accordingly, triplet excitons generated by carrier recombination in the organic EL element are thermally deactivated and do not contribute to light emission. For these reasons, it is said that the upper limit of the internal quantum yield of a fluorescent organic EL device that uses only singlets is 25%. If the light extraction efficiency is added to this and converted into light that can actually be extracted to the outside, the upper limit of the external quantum yield (exQE) is said to be about 5%.

Thus, in order to improve the luminous efficiency of organic EL devices, it has been proposed to use triplet excitons, and benzophenone derivatives and lanthanide complexes have been studied, but the internal quantum yield does not reach that of fluorescent dyes. there were. Later, a study using d-block transition metals was made, and a phosphorescent EL device (red light emission) using a platinum porphyrin complex (PtOEP) was announced, but it still has an internal quantum yield similar to that of fluorescent dyes. there were. However, ortho-metal type iridium complex (green light emission) was reported afterwards, and the phosphorescence type EL element that achieved 26cd / A, 19lm / W, exQE = 7.5% in green light emission and exceeded the internal quantum yield limit of fluorescent dyes. Was realized. These d-block transition metal complexes are characterized by the use of heavy metals from the fifth period onward as the central metal, which increases spin-orbit interaction (heavy atom effect) and should be essentially spin-forbidden. Thus, the triplet-singlet transition becomes a permissible transition, and high-efficiency phosphorescence emission can be observed at room temperature.
Many iridium complexes have been studied on this occasion, but iridium metal is one of the elements with extremely low abundance in the earth's crust, so it is very expensive and emits light using cheaper and more readily available metals. A metal complex has been awaited.
On the other hand, many studies on luminescent metal complexes using metals other than iridium have been made. For example, there are platinum, osmium, etc., all of which are very expensive because of the same transition metals as the iridium in the sixth period, and light emission with high efficiency could not be realized. Therefore, a transition metal having a fourth period, which is cheaper and easily available, particularly a copper complex, has attracted particular attention, and some light emission characteristics have been reported so far.

Generally copper take monovalent and divalent oxidation state, but a divalent to take open-shell structure of the d ⁹ when the ground state, will doublet both excited state, their optical transitions same multiplet It is fluorescent because it is between each other. Therefore, high-efficiency light emission cannot be expected even when used as a light-emitting material for phosphorescent organic EL elements. In addition, since the optical transition is often a non-luminescent dd transition, few luminescent divalent copper complexes are known. In contrast, in the case of a monovalent copper complex, it is known that it takes a closed shell structure of d ¹⁰ and there is no dd transition that causes thermal deactivation, so that it is easy to emit light with high efficiency. Regarding the origin of light emission, it is known that a copper monovalent complex exhibits light emission based on a metal-ligand transition ( ³ MLCT) similar to iridium. Therefore, although a large spin-orbit interaction and thus high-efficiency phosphorescence can be expected, the emission efficiency has not yet reached the practical range, and an inexpensive and easily available copper complex that emits light with high efficiency has been desired.

Regarding the luminescent copper complex, several documents have been disclosed so far, but no practical luminescent complex has been obtained. Furthermore, although the luminescent copper complex and the organic EL element using the same are disclosed in Patent Literatures 1 to 3 and Non-Patent Literatures 1 to 4 as described below, the luminous efficiency is not sufficient.

Japanese Patent Laid-Open No. 2003-332074 JP 2005-36020 A JP 2006-286749 Appl. Phys. Lett., 88, 213508 (2006) Adv. Mater., 16, 432 (2004) J. Amer. Chem. Soc., 124, 6 (2002) Inorg. Chem., 41, 3313 (2002)

The first object of the present invention is to provide a novel luminescent metal complex useful as an organic electronic material, particularly as a material for an organic electroluminescence device.
The second object of the present invention is to provide a material for an organic electroluminescence device containing such a metal complex, an organic layer of an organic electroluminescence device containing the material, for example, a hole injection layer, a hole transport layer, a light emitting layer. It is to provide an electron transport layer and an electron injection layer.
The third object of the present invention is to provide an organic electroluminescent element containing such a material for an organic electroluminescent element, and a device including the organic electroluminescent element, for example, in-vehicle use, portable equipment use, personal computer use, television use, etc. Is to provide a display.
A fourth object of the present invention is to provide a novel luminescent metal complex useful as a luminescent material.

（式中、ＸおよびＹはそれぞれ独立にNまたはCR₆であり、R₁〜R₆はそれぞれ独立に、水素、ハロゲン、C₁〜C₄₀の置換もしくは無置換のアルキル基、C₂〜C₄₀の置換もしくは無置換のアルケニル基、C₆〜C₄₀の置換もしくは無置換のアリール基、C₃〜C₄₀の置換もしくは無置換のヘテロアリール基、C₁〜C₄₀の置換もしくは無置換のアルコキシ基、C₆〜C₄₀の置換もしくは無置換のアリールオキシ基、C₁〜C₄₀の置換もしくは無置換のアルキルチオ基であり、R₁〜R₆のうち隣接する基は互いに結合して環を形成してもよく、L₁およびL₂はそれぞれ独立に、窒素、燐及び砒素から選ばれる元素を含む配位子であり、L₁とL₂が互いに結合して２座配位子を形成してもよい。）
２．ＸがCR₆であり、ＹがＮである上記１に記載の銅錯体に関する。
３．ＸがＮであり、ＹがCR₆である上記１に記載の銅錯体に関する。
４．L₁およびL₂がそれぞれ独立に窒素及び燐から選ばれる元素を含む配位子であり、互いに結合して２座配位子を形成している、上記１〜３の何れか１に記載の銅錯体に関する。 By using a mononuclear monovalent copper complex having a specific structure, the inventors of the present invention obtain an organic electroluminescence element or a light emitting material that has high luminous efficiency, has a long luminous lifetime, and is inexpensive and easily available. I found out that I can. Specifically, the present invention
1. The present invention relates to a mononuclear monovalent copper complex represented by the following formula (1).

Wherein X and Y are each independently N or CR ₆ , and R _{1 to} R ₆ are each independently hydrogen, halogen, a C ₁ -C ₄₀ substituted or unsubstituted alkyl group, C ₂ -C ₄₀ substituted or unsubstituted alkenyl groups, C _{6 to} C ₄₀ substituted or unsubstituted aryl groups, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl groups, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group C ₆ -C _40, a substituted or unsubstituted alkylthio group of C ₁ -C _40, adjacent groups of R ₁ to R ₆ are bonded to each other to form a ring L ₁ and L ₂ are each independently a ligand containing an element selected from nitrogen, phosphorus and arsenic, and L ₁ and L ₂ are bonded to each other to form a bidentate ligand. It may be formed.)
2. 2. The copper complex according to 1 above, wherein X is CR ₆ and Y is N.
3. 2. The copper complex according to 1 above, wherein X is N and Y is CR ₆ .
4). L ₁ and L ₂ are each independently a ligand containing an element selected from nitrogen and phosphorus, and are bonded to each other to form a bidentate ligand, It relates to a copper complex.

（式中、R₁₀〜R₁₃はそれぞれ独立に水素、ハロゲン、C₁〜C₄₀の置換もしくは無置換のアルキル基、C₂〜C₄₀の置換もしくは無置換のアルケニル基、C₆〜C₄₀の置換もしくは無置換のアリール基、C₃〜C₄₀の置換もしくは無置換のヘテロアリール基、C₁〜C₄₀の置換もしくは無置換のアルコキシ基、C₆〜C₄₀の置換もしくは無置換のアリールオキシ基、C₁〜C₄₀の置換もしくは無置換のアルキルチオ基であり、R₁₀とR₁₁及び/又はR₁₂とR₁₃は互いに結合して環を形成してもよく、QはC₁〜C₆の置換もしくは無置換のアルキリデン基、C₂〜C₆の置換もしくは無置換のアルケニリデン基、C₆〜C₄₀の置換もしくは無置換のアリーレン基、C₃〜C₄₀の置換もしくは無置換のヘテロアリーレン基である。）
６．Qが、ハロゲン、C₁〜C₄₀の置換もしくは無置換のアルキル基、C₆〜C₄₀の置換もしくは無置換のアリール基で置換されてもよい下記構造；

から選ばれる有機基である、上記５に記載の銅錯体に関する。
７．上記１〜６の何れか１に記載の銅錯体を含有する発光材料に関する。
８．上記１〜６の何れか１に記載の銅錯体を含有する有機エレクトロルミネッセンス素子用材料に関する。
９．陰極と、陽極と、該陰極と該陽極との間に挟持された１層または複数層からなる有機層とを含み、該有機層が少なくとも発光層を含み、及び、該有機層の少なくとも１層が、上記８に記載の有機エレクトロルミネッセンス素子用材料を含む有機エレクトロルミネッセンス素子に関する。
１０．上記９に記載の有機エレクトロルミネッセンス素子を有する装置に関する。 5. The copper according to any one of 1 to 4 above, wherein L ₁ and L ₂ are bidentate ligands bonded to each other, and the ligand forms a bidentate phosphine of the following formula (2): Concerning the complex.

(Wherein R _{10 to} R ₁₃ are each independently hydrogen, halogen, a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, a C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{6 to} C _40, Substituted or unsubstituted aryl group, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl group, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, C _{6 to} C ₄₀ substituted or unsubstituted aryl oxy group, a substituted or unsubstituted alkylthio group of C ₁ ~C _40, R ₁₀ and R ₁₁ and / or R ₁₂ and R ₁₃ may bond together to form a ring, Q is C ₁ ~ C ₆ substituted or unsubstituted alkylidene group, C _{2 to} C ₆ substituted or unsubstituted alkenylidene group, C _{6 to} C ₄₀ substituted or unsubstituted arylene group, C _{3 to} C ₄₀ substituted or unsubstituted Heteroarylene group.)
6). Q is halogen, C ₁ -C ₄₀ substituted or unsubstituted alkyl group, C ₆ -C ₄₀ substituted or unsubstituted good following structure be substituted with an aryl group of;

It is related with the copper complex of said 5 which is an organic group chosen from these.
7). It is related with the luminescent material containing the copper complex of any one of said 1-6.
8). It is related with the material for organic electroluminescent elements containing the copper complex of any one of said 1-6.
9. A cathode, an anode, and an organic layer composed of one or more layers sandwiched between the cathode and the anode, the organic layer including at least a light emitting layer, and at least one layer of the organic layer Is related to the organic electroluminescent element containing the organic electroluminescent element material of said 8 ..
10. The present invention relates to an apparatus having the organic electroluminescence element as described in 9 above.

By using a mononuclear monovalent copper complex having a specific structure according to the present invention, an organic electroluminescence element or a light-emitting material that has high luminous efficiency, has a long luminous lifetime, and is inexpensive and easily available can be obtained.
Moreover, the organic electroluminescent element material or light emitting material containing a mononuclear monovalent copper complex used in the present invention exhibits good light emission not only in a crystal state but also in a solution state or a dispersed state.

（式中、ＸおよびＹはそれぞれ独立にNまたはCR₆(R₆は１価の置換基。-C(-R₆)=の様に結合している)であり、R₁〜R₆はそれぞれ独立に、水素、ハロゲン、C₁〜C₄₀の置換もしくは無置換のアルキル基、C₂〜C₄₀の置換もしくは無置換のアルケニル基、C₆〜C₄₀の置換もしくは無置換のアリール基、C₃〜C₄₀の置換もしくは無置換のヘテロアリール基、C₁〜C₄₀の置換もしくは無置換のアルコキシ基、C₆〜C₄₀の置換もしくは無置換のアリールオキシ基、C₁〜C₄₀の置換もしくは無置換のアルキルチオ基であり、R₁〜R₆のうち隣接する基は互いに結合して環を形成してもよく、L₁およびL₂はそれぞれ独立に、窒素、燐及び砒素から選ばれる元素を含む配位子であり、L₁とL₂が互いに結合して２座配位子を形成してもよい。） (1) Copper Complex The copper complex of the present invention is a mononuclear monovalent copper complex represented by the following formula (1).

(Wherein X and Y are each independently N or CR ₆ (R ₆ is a monovalent substituent, bonded as in —C (—R ₆ ) ═), and R _{1 to} R ₆ are each independently, hydrogen, halogen, C ₁ -C substituted or unsubstituted alkyl group of _40, C ₂ substituted or unsubstituted alkenyl group -C _40, a substituted or unsubstituted aryl group having C ₆ -C _40, substituted or unsubstituted heteroaryl group C ₃ -C _40, substituted or unsubstituted alkoxy group C ₁ -C _40, a substituted or unsubstituted aryloxy group C ₆ -C _40, of C ₁ -C ₄₀ A substituted or unsubstituted alkylthio group, and adjacent groups of R _{1 to} R ₆ may be bonded to each other to form a ring, and L ₁ and L ₂ are each independently selected from nitrogen, phosphorus and arsenic L ₁ and L ₂ may be bonded to each other to form a bidentate ligand.)

Here, X = CR _6, a pyrrole derivative those Y = CR ₆ (however, may be R ₆ of X in R ₆ and Y are either the same or different from each other), one of X = CR _6, Y = N Are called pyrazole derivatives, X = N, Y = CR ₆ are called imidazole derivatives, and X = N, Y = N are called triazole derivatives.

The substituted or unsubstituted alkyl group of C _{1 to} C ₄₀ of R _{1 to} R ₆ may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, 1- Propyl, 2-propyl, 1-butyl, 2-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, 3,7-dimethyloctyl, cyclopropyl, cyclopentyl, cyclohexyl, Examples thereof include 1-adamantyl, 2-adamantyl, norbornyl, trifluoromethyl, trichloromethyl, benzyl, α, α-dimethylbenzyl, 2-phenylethyl, 1-phenylethyl and the like. Preferably, a substituted or unsubstituted alkyl group of C ₁ -C _20, more preferably, a substituted or unsubstituted alkyl group of C ₁ -C _10, more preferably, substituted C ₁ -C ₆ Or, it is an unsubstituted alkyl group. Specifically, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl and the like are preferable.
The C ₂ -C ₄₀ substituted or unsubstituted alkenyl group of R _{1 to} R ₆ may be linear, branched or cyclic, and specific examples thereof include vinyl, propenyl, butenyl, and oleyl. Eicosapentaenyl, docosahexaenyl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl and the like. Preferably, a substituted or unsubstituted alkenyl group having C ₂ -C _20, more preferably, a substituted or unsubstituted alkenyl group having C ₂ -C _10, in particular, preferably, vinyl, 2 , 2-diphenylvinyl and the like.

Specific examples of the C ₆ -C ₄₀ substituted or unsubstituted aryl group of R _{1 to} R ₆ include phenyl, 2-tolyl, 4-tolyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-cyano 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-phenanthryl, 1-pyrenyl, chrycenyl, naphthacenyl, coronyl and the like. Preferably, it is a C ₆ -C ₂₀ substituted or unsubstituted aryl group, more preferably a C ₆ -C ₁₄ substituted or unsubstituted aryl group, specifically, preferably phenyl, 4 -Biphenylyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl and the like.
Specific examples of the substituted or unsubstituted heteroaryl group C ₃ -C ₄₀ for R ₁ to R ₆ include furan, thiophene, pyrrole, imidazole, benzimidazole, pyrazole, Benzupirazoru, triazole, oxadiazole, pyridine, Examples include pyrazine, triazine, quinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, and carbazole. Preferably has one or more S, O or N group, a substituted or unsubstituted heteroaryl group C ₃ -C _20, more preferably, substituted or unsubstituted heteroaryl C ₄ -C ₅ Specifically, preferred are furan, thiophene, pyridine and the like.

A substituted or unsubstituted alkoxy group C ₁ -C ₄₀ of R ₁ to R ₆ may be either straight chain, branched chain or cyclic, as their specific examples, 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. Can be mentioned. Preferably, a substituted or unsubstituted alkoxy group C ₁ -C _20, more preferably, a substituted or unsubstituted alkoxy group C ₁ -C _10, more preferably, substituted C ₁ -C ₄ Alternatively, it is an unsubstituted alkoxy group, and specifically, preferably methoxy, ethoxy, ter-butyloxy and the like.
Specific examples of the substituted or unsubstituted aryloxy group C ₆ -C ₄₀ of R ₁ to R _6, the aryl group substituted group bonded through an oxygen. Preferably, it is a C ₆ -C ₂₀ substituted or unsubstituted aryloxy group, more preferably a C ₆ -C ₁₄ substituted or unsubstituted aryloxy group, specifically, preferably phenoxy Naphthoxy, phenanthryloxy and the like.

A substituted or unsubstituted alkylthio group C ₁ -C ₄₀ of R ₁ to R ₆ may be either straight chain, branched chain or cyclic, as their specific examples, methylthio, ethylthio, 1-propylthio 2-propylthio, 1-butylthio, 2-butylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, 2-ethylhexylthio, 3,7-dimethyloctylthio, cyclopropylthio, cyclopentylthio Cyclohexylthio, 1-adamantylthio, 2-adamantylthio, norbornylthio, trifluoromethylthio, benzylthio, α, α-dimethylbenzylthio, 2-phenylethylthio, 1-phenyltylthio and the like. Preferably, a substituted or unsubstituted alkylthio group of C ₁ -C _20, more preferably, a substituted or unsubstituted alkylthio group of C ₁ -C _10, more preferably, substituted C ₁ -C ₄ Alternatively, it is an unsubstituted alkylthio group, and specifically, preferably methylthio, ethylthio, ter-butylthio and the like.
Examples of the substituent of each of the above-described groups constituting R _{1 to} R ₆ include the alkyl group, alkenyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, and heteroaryl group.

When R ₁ and Y are CR ₆ , R ₆ is preferably a substituent other than hydrogen. The monovalent copper complex as contained in the mononuclear monovalent copper complex used in the present invention has the property of being easily oxidized by oxygen in the air and easily becoming a divalent copper complex. However, it is known that a divalent copper complex has an open-shell d-orbital and generally does not emit light because non-luminous dd transition becomes dominant. When R ₁ and Y are CR ₆ , at least one of R ₆ is substituted with a substituent other than hydrogen, resulting in steric hindrance, from a tetrahedral monovalent copper complex to a planar quadrilateral divalent copper complex. A copper complex that inhibits the isomerization reaction and stably emits light can be obtained. More preferable examples of R ₆ when R ₁ and Y are CR ₆ include substitutions having moderate steric hindrance such as alkyl groups of about C _{1 to} C ₈ and halogens represented by chlorine, bromine and the like. The group can be mentioned. Thus, when R ₁ and Y are CR ₆ and the substituent of R ₆ has an appropriate size, steric repulsion due to the substituent can be suppressed, and the stability of the monovalent copper complex can be maintained.

The adjacent groups among R _{1 to} R ₆ may be bonded to each other to form a ring. For example, when Y adjacent to R ₅ is CR ₆ , R ₆ may be bonded to each other to form a ring. Further, when X adjacent to R ₄ is CR ₆ , R ₆ may be bonded to each other to form a ring. Examples of the ring include an aromatic ring which is a 3- to 8-membered ring, preferably a 5- to 6-membered ring, and which may have an unsaturated bond in a part thereof.

In the formula (1), the materials for L ₁ and L ₂ are preferably amines such as triethylamine, ethylenediamine, and ethanolamine, pyridine, bipyridine, phenanthroline, dimethylphenanthroline, diphenylphenanthroline, dimethyldiphenylphenanthroline, and the like. Examples thereof include azines, phosphines such as triphenylphosphine, tributylphosphine, and tricyclohexylphosphine. More preferably, L ₁ and L ₂ may each independently be a ligand containing phosphorus.
Specific examples of L ₁ and L ₂ that are phosphorus-containing ligands include bisdiphenylphosphinomethane, bisdicyclohexylphosphinomethane, 1,2-bis (diphenylphosphino) ethane, and 1,3-bis. (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphino) ethylene, 1,2-bis (diphenylphosphino) benzene, 2,2'-bis ( Diphenylphosphino) biphenyl, 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 1,1'-bis (diphenylphosphino) ferrocene, 2,2'-bis (diphenylphosphino) diphenyl ether And bidentate phosphine ligands such as 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene.

（式中、R₁₀〜R₁₃はそれぞれ独立に水素、ハロゲン、C₁〜C₄₀の置換もしくは無置換のアルキル基、C₂〜C₄₀の置換もしくは無置換のアルケニル基、C₆〜C₄₀の置換もしくは無置換のアリール基、C₃〜C₄₀の置換もしくは無置換のヘテロアリール基、C₁〜C₄₀の置換もしくは無置換のアルコキシ基、C₆〜C₄₀の置換もしくは無置換のアリールオキシ基、C₁〜C₄₀の置換もしくは無置換のアルキルチオ基であり、R₁₀とR₁₁及び/又はR₁₂とR₁₃は互いに結合して環を形成してもよく、QはC₁〜C₆の置換もしくは無置換のアルキリデン基、C₂〜C₆の置換もしくは無置換のアルケニリデン基、C₆〜C₄₀、好ましくは、C₆〜C₂₀、より好ましくは、C₆〜C₁₄の置換もしくは無置換のアリーレン基、C₃〜C₄₀、好ましくはC₃〜C₂₀、より好ましくは、C₄〜C₅の置換もしくは無置換のヘテロアリーレン基（好ましくは、１以上のＳ、Ｏ又はＮ基を有するヘテロアリーレン基）である。） L ₁ and L ₂ are each independently a ligand containing an element selected from nitrogen and phosphorus, and are preferably bonded to each other to form a bidentate ligand. In the ligands forming L ₁ and L ₂ , nitrogen or phosphorus is preferably coordinated to copper.
Further, L ₁ and L ₂ are bidentate ligands bonded to each other, and it is more preferable that the ligand forms a bidentate phosphine of the following formula (2).

(Wherein R _{10 to} R ₁₃ are each independently hydrogen, halogen, a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, a C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{6 to} C _40, Substituted or unsubstituted aryl group, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl group, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, C _{6 to} C ₄₀ substituted or unsubstituted aryl oxy group, a substituted or unsubstituted alkylthio group of C ₁ ~C _40, R ₁₀ and R ₁₁ and / or R ₁₂ and R ₁₃ may bond together to form a ring, Q is C ₁ ~ C ₆ substituted or unsubstituted alkylidene group, C _{2 to} C ₆ substituted or unsubstituted alkenylidene group, C _{6 to} C ₄₀ , preferably C _{6 to} C ₂₀ , more preferably C _{6 to} C ₁₄ . a substituted or unsubstituted arylene group, C ₃ -C _40, preferably C ₃ -C _20, more preferably, substituted C ₄ -C ₅ Or an unsubstituted heteroarylene group (preferably a heteroarylene group having one or more S, O, or N groups).

から選ばれる有機基であってもよい。 The formula (2) R ₁₀ to R C ₁ are mentioned as ₁₃ -C ₄₀ substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group having C ₂ -C _40, of C ₆ -C ₄₀ a substituted or unsubstituted aryl group, C ₃ -C substituted or unsubstituted heteroaryl group _40, a substituted or unsubstituted alkoxy group C ₁ -C _40, a substituted or unsubstituted aryloxy of C ₆ -C ₄₀ As the group, a substituted or unsubstituted alkylthio group of C _{1 to} C ₄₀ , the same groups as R _{1 to} R ₆ described above can be selected.
R ₁₀ and R ₁₁ and / or R ₁₂ and R ₁₃ may be bonded to each other to form a ring. Examples of the ring include an aromatic ring which is a 3- to 8-membered ring, preferably a 5- to 6-membered ring, and which may have an unsaturated bond in a part thereof.
The Q furthermore, halogen, C ₁ -C _40, preferably, C ₁ -C _20, more preferably, C ₁ -C _10, more preferably a substituted or unsubstituted alkyl group of C ₁ -C ₆ , C ₆ -C ₄₀ , preferably C ₆ -C ₂₀ , more preferably the following structure optionally substituted with a C ₆ -C ₁₄ substituted or unsubstituted aryl group;

It may be an organic group selected from:

（式中、Ｘ、Ｙ、Ｑ、Ｒ₁〜Ｒ₅、Ｒ₁₀〜Ｒ₁₃の定義は上記と同様である。） Specifically, the mononuclear monovalent copper complex of the present invention containing a bidentate ligand in which L ₁ and L ₂ are bonded to each other as in the above formula (2) can be expressed as in the following formula (3). it can.

(In the formula, the definitions of X, Y, Q, R _{1 to} R ₅ , and R _{10 to} R ₁₃ are the same as above.)

Specific examples of the mononuclear monovalent copper complex that can be used in the present invention are shown below.

また第二の方法として、X=N（イミダゾールまたはトリアゾール）およびY=N（ピラゾール）の場合は、L₁およびL₂とともに先に錯体形成を行ない、カチオン性錯体を単離した後に塩基を反応させて、本発明化合物（中性錯体）に誘導することも可能である。 A general synthesis route of the mononuclear monovalent copper complex of the present invention will be described below.
In the first method, the NH proton of the azole derivative is extracted with a base in an inert gas atmosphere such as argon or nitrogen, and the second ligand (L ₁ ) and the third ligand (L ₂ ) are extracted. In addition, it can be synthesized by further adding a copper (I) source and stirring at room temperature (about 25 ° C.).

As a second method, when X = N (imidazole or triazole) and Y = N (pyrazole), the complex is formed first with L ₁ and L ₂ and the base is reacted after isolating the cationic complex It is also possible to derive the compound of the present invention (neutral complex).

The base used in these reactions is not particularly limited. For example, alkali (earth) metal hydrides such as lithium hydride, sodium hydride and calcium hydride, alkoxides such as sodium methoxide and potassium t-butoxide. And organic lithiums such as n-butyllithium and t-butyllithium. Among these bases, alkali metal hydrides represented by sodium hydride and the like are preferable. Since these bases have low nucleophilicity, side reactions (addition reactions of bases to C = N bonds) are preferred. It can be suppressed and the yield can be improved. Moreover, as a copper (I) source, tetrakis (acetonitrile) copper (I) hexafluorophosphate (Cu (MeCN) ₄ PF ₆ ), complexes represented by Cu (PPh ₃ ) ₃ Cl, CuI, CuBr, Halides such as CuCl can be used.

The mononuclear monovalent copper complex synthesized in this way is stable at room temperature and in the air, and can be purified by column chromatography, recrystallization, or the like, if necessary. Further confirmation of the structure, the central metal can be used various nuclear magnetic resonance ^{(1 H-NMR, 13 C} -NMR, 31 P-NMR) because it closed-shell structure of the d ^10, if necessary It can also be confirmed by elemental analysis, X-ray structural analysis, and the like.

(2) Luminescent Material and Organic Electroluminescent Element Material The copper complex of the present invention can be used as an organic electronics element material or a luminescent material.
Specific examples of materials for organic electronics elements include organic electroluminescence materials, organic semiconductor materials, organic transistor materials, organic photoelectric conversion materials, organic solar cell materials, etc. Among these, preferable application examples are And organic electroluminescent materials.
Specific examples of the light emitting material include phosphorescent dyes and wavelength conversion elements, and preferable application examples include wavelength conversion elements.
The organic electroluminescent device material or luminescent material of the present invention is a material other than the above mononuclear monovalent copper complex, and the luminescent material, hole injecting material described in the section of (3) organic electroluminescent device described later, A hole transport material, an electron injection material, an electron transport material, and the like may be included.
Furthermore, the organic electroluminescent element material or light emitting material of the present invention may contain the following resins and additives, which are other known mixtures. Hereinafter, the organic electroluminescent element material or the light emitting material of the present invention will be described in detail. However, the “organic electroluminescent element material or light emitting material” is abbreviated as “organic electroluminescent element material or the like”.

(2-1) Resin The material for an organic electroluminescence element of the present invention may contain an appropriate resin for improving film formability and preventing pinholes in the film. Examples of such resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinylcarbazole. And photoconductive resins such as polysilane, and conductive resins such as polythiophene and polypyrrole.
(2-2) Additive The material for an organic electroluminescent element of the present invention may contain an appropriate additive for improving film formability and preventing pinholes in the film. Examples of such additives include antioxidants, ultraviolet absorbers, and plasticizers.

(3) Organic electroluminescent device The organic electroluminescent device of the present invention includes a cathode, an anode, and an organic layer composed of one or more layers sandwiched between the cathode and the anode. Moreover, the element of this organic electroluminescent element may be provided on the board | substrate. A protective layer may be further provided on the surface of the organic electroluminescence element of the present invention.
More specifically, the element structure of the organic electroluminescence element in the present invention is a structure in which one or more organic layers are laminated between electrodes. Examples of the organic layer include a hole injection layer, a hole transport layer (electron barrier layer), a light emitting layer, an electron transport layer (hole barrier layer), and an electron injection layer.
Specific element structures of the organic electroluminescence element of the present invention include, for example, (anode / light emitting layer / cathode), (anode / hole injection layer or transport layer / light emitting layer / electron injection layer or transport layer / cathode), (Anode / hole injection layer or transport layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer or transport layer / cathode), or (anode / hole injection layer / hole transport layer / light emitting layer / Examples thereof include an electron transport layer / electron injection layer / cathode).

(3-1) Light emitting layer As the light emitting material constituting the light emitting layer, the above mononuclear monovalent copper complex can be used as it is. Further, the light emitting layer may be a mixture of a host material and a dopant using the mononuclear monovalent copper complex used in the present invention as a topant. In general, the mass ratio of the dopant and the host material contained in the various organic layers is 1:99 to 50:50, preferably 5:95 to 20:80. The host material for the light emitting material is not particularly limited as long as it is a compound having a triplet energy gap wider than that of the metal complex in order to prevent reverse energy transfer from the mononuclear monovalent copper complex used in the present invention to the host material. Not. Particularly preferred host materials include m-dicarbazolylbenzene, carbazole derivatives represented by 4,4′-dicarbazolylbiphenyl, silicon derivatives represented by 1,3-bis (trimethylsilyl) benzene, 1 , 3,5-tris (3,5-diphenylphenyl) benzene, oligoarylenes, polymer compounds typified by polyvinylcarbazole, and the like, but are not limited thereto. Furthermore, the light emitting layer may contain other materials such as a hole injection material, a hole transport material, an electron injection material, and an electron transport material described later. The other material that can be included in the light emitting layer is, for example, 1 to 50% by mass, preferably 1 to 20% by mass with respect to the mass of the entire light emitting layer.

(3-2) Hole injection layer and hole transport layer (electron barrier layer)
The hole injection material and the hole transport material (electron barrier material) included in the hole injection layer and the hole transport layer (electron barrier layer) are not particularly limited, and are known hole injection materials and hole transports. Although a material (electron barrier material) can be used, a compound having an excellent thin film forming ability is preferable. The hole injection layer has a hole injection effect from the anode and an excellent hole injection effect for the light emitting layer or the light emitting material. The hole transport layer has the ability to transport holes. The hole transport layer is also called an electron barrier layer, and has an ability to prevent excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material. These hole injection layer and hole transport layer (electron barrier layer) may be used as independent layers, or may be used as a single layer having the characteristics of each layer. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, metal phthalocyanines, metal porphyrins, oligoarylenes, oligothiophenes, benzidine type triphenylamines, styrylamine type triphenylamines, starburst type triphenylamines. Phenylamines, tetracyanotetraazatriphenylenes and their polymers, and polymers such as polyvinyl carbazole and polysilane, polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), polyaniline / camphor sulfonic acid (PANI / CSA) ) And the like, and polymer materials such as a conductive polymer, inorganic oxides typified by germanium oxide, molybdenum oxide, and the like, but are not limited thereto.

Among hole injection materials and hole transport materials (electron barrier materials) that can be used in the organic electroluminescence device of the present invention, more effective hole injection materials and hole transport materials (electron barrier materials) are aromatic. Tertiary amine derivatives or phthalocyanine derivatives. Specific examples of the aromatic tertiary amine derivative are triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 '-Diamine, N, N, N', N '-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N', N '-(4-methylphenyl) ) -1,1′-biphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-( Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, etc. Or these oligomers having an aromatic tertiary amine skeleton Properly is a polymer, but is not limited thereto. Specific examples of the phthalocyanine (Pc) derivative include H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, Although it is a phthalocyanine derivative and a naphthalocyanine derivative such as VOPc, TiOPc, MoOPc, and GaPc-O-GaPc, it is not limited thereto.
Among hole injection materials and hole transport materials (electron barrier materials) that can be used in the organic electroluminescence device of the present invention, CuPc, PEDOT: PSS, N, N′-diphenyl-N, N'-dinaphthyl-1,1'-biphenyl-4,4'-diamine may also be used.

(3-3) Electron injection layer and electron transport layer (hole barrier layer)
The electron injection material and the electron transport material (hole barrier material) contained in the electron injection layer and the electron transport layer (hole barrier layer) are not particularly limited, and known electron injection materials and electron transport materials (holes). Although a barrier material can be used, a compound having an excellent thin film forming ability is preferable. The electron injection layer has an electron injection effect from the cathode and an excellent electron injection effect for the light emitting layer or the light emitting material. The electron transport layer has the ability to transport electrons. The electron transport layer is also referred to as a hole barrier layer, and has an ability to prevent migration of excitons generated in the light emitting layer to the hole injection layer. These electron injection layer and electron transport layer (hole blocking layer) may be used as independent layers, or may be used as a single layer having the characteristics of each layer. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives However, it is not limited to these. Further, the charge injection property can be improved by adding an electron accepting material to the hole injecting material and an electron donating material to the electron injecting material.

    In the organic electroluminescence device of the present invention, more effective electron injection materials and electron transport materials (hole barrier materials) are metal complex compounds or nitrogen-containing heterocyclic derivatives. Specific examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris ( 8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis ( 10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8-quinolinato) ) (1-Naphtholate) aluminum, bis (2-methyl-8-) Norinato) (2-naphtholato) gallium and the like, but not limited thereto.

   The nitrogen-containing hetero derivatives are preferably azole derivatives such as oxazole, thiazole, oxadiazole and thiadiazole, phenanthroline derivatives such as phenanthroline, bathophenanthroline and bathocuproine, and pyridines such as bipyridine and aryl-substituted pyridine. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenylthiadi Zolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like are exemplified, but not limited thereto.

If the electron injection layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved. As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved.
Specifically, preferred alkali metal chalcogenides include, for example, Li ₂ O, LiO, Na ₂ S, Na ₂ Se and NaO, and preferred alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO. , BaS, and CaSe. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.

  Further, the electron injection layer may be a layer in which a reducing dopant is added to an electron transport material usually used as an electron transport layer to function as an electron injection layer. The reducing dopant may be a reducing dopant having a work function of 2.9 eV or less. Here, the reducing dopant is defined as a substance that can reduce the electron transporting material. Accordingly, various materials can be used as long as they have a certain reducibility, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals. At least selected from the group consisting of oxides, alkaline earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, rare earth metal organic complexes One substance can be preferably used.

More specifically, preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1 .95 eV), at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV). Particularly preferred are those having a work function of 2.9 eV, including at least one alkaline earth metal selected from the group consisting of
Among these, a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb, and Cs, more preferably Rb or Cs, and most preferably Cs. . These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the electron injection region (electron injection layer or electron injection region in the light emitting layer), the luminance of the organic electroluminescent device is improved and the lifetime is increased. Is planned.
Further, as a reducing dopant having a work function of 2.9 eV or less, a combination of these two or more alkali metals is also preferable. Particularly, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, A combination of Cs, Na and K is preferred. By including Cs in combination, the reducing ability can be efficiently exhibited, and the addition to the electron injection region (electron injection layer or electron injection region in the light emitting layer) improves the light emission luminance in the organic electroluminescence device. And longer life.

In the organic electroluminescence device of the present invention, more effective electron transport materials include tris (8-hydroxyquinoline) aluminum, bathocuproine, bathophenanthroline and the like.
In addition, if the electron transport layer is made of a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved. As a semiconductor composing the electron transport layer, oxides, nitridings containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn One kind or a combination of two or more kinds of compounds or oxynitrides. In addition, the inorganic compound constituting the electron transport layer is preferably a microcrystalline or amorphous insulating film. If the electron transport layer is composed of these insulating films, when the insulating film is formed into a thin film, a more uniform thin film is formed, so that pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include the above-mentioned alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides.

(3-4) Anode and cathode As the conductive material used as the anode of the organic electroluminescence device of the present invention, those having a work function larger than 4 eV are suitable, and carbon, aluminum, vanadium, iron, cobalt, Nickel, tungsten, silver, gold, platinum, palladium and the like and alloys thereof, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used. .

  As the conductive material used as the cathode of the organic electroluminescence device of the present invention, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, Aluminum and the like and alloys thereof are used, but are not limited thereto. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.

(3-5) Substrate The substrate is not limited as long as it has mechanical and thermal strength, and preferably has transparency. As the substrate, a glass substrate and a transparent resin film are preferable.
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.

(3-6) Protective layer In order to improve the stability of the organic electroluminescent device obtained by the present invention against temperature, humidity, atmosphere, etc., a protective layer can be provided on the surface of the device. Examples of the material constituting the protective layer include silicon oil and resin.

(3-7) Additives In any organic layer, the above-mentioned resins and additives (see (2-1) and (2-2)) should be used to improve film formability and prevent pinholes in the film. May be used.

(3-8) Properties of each layer The thickness of the organic electroluminescent element of the present invention is not particularly limited, but it is necessary to set it to an appropriate thickness. The film thickness of the organic electroluminescent element of the present invention is, for example, 5 nm to 10 μm, preferably 10 nm to 0.2 μm. If it is 10 μm or less, the applied voltage for obtaining a constant light output does not become too large, and efficiency can be improved. If it is 5 nm or more, pinholes or the like are not generated, and sufficient luminance can be obtained by applying an electric field, which is preferable.
Although the film thickness of each organic layer of the organic electroluminescent element of the present invention is not particularly limited, for example, 1 nm to 5 μm, preferably 5 nm to 1 μm is appropriate. If it is 1 nm or more, defects such as pinholes do not occur, and if it is 5 μm or less, the required applied voltage can be kept low and efficiency can be improved.
In particular, the thickness of the light emitting layer which is one of the organic layers is more preferably in the range of 1 nm to 500 nm, and most preferably in the range of 10 nm to 100 nm.

The thickness of the hole injection layer that is one of the organic layers is more preferably in the range of 1 nm to 100 nm, and most preferably in the range of 10 nm to 50 nm.
In the organic electroluminescence element, in order to emit light efficiently, it is desirable that the substrate, the protective layer, and at least one of the electrodes be sufficiently transparent in the light emission wavelength region of the element. Here, the transparent electrode is set so that predetermined translucency is ensured by a method such as vapor deposition or sputtering using the conductive material. The electrode used in the present invention has a light transmittance of 10% or more, preferably 30 to 100%, more preferably 50 to 100%.

(3-9) Production of each layer The formation of each layer of the organic electroluminescence device according to the present invention is performed by dry deposition methods such as vacuum deposition, sputtering, plasma, ion plating, spin coating, dip coating, casting, roll coating, Any of wet film forming methods such as flow coating and ink jet can be applied.

    In the case of the wet film forming method, the material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare an organic solution, and the organic solution is applied on a substrate using a spin coat method or the like, and dried. Get a thin film. Here, any solvent may 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 preferred. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.

(3-10) Manufacture and Properties of Organic Electroluminescent Element The organic electroluminescent element of the present invention is manufactured by sandwiching the organic layer between a cathode and an anode. Among these, an organic layer is manufactured by laminating | stacking each layer preferably on a board | substrate sequentially by the above-mentioned dry-type film-forming method or wet-type film-forming method.
Specifically, for example, first, a substrate is prepared. As the substrate, the various substrates described above can be used. An electrode is provided on this substrate to obtain an electrode-substrate assembly. Instead of this operation, an electrode-substrate assembly in which electrodes are previously provided on one surface of the substrate may be obtained from the market. On this joined body, the material constituting the organic layer is sequentially laminated using the above-described spin coating method or the like. Subsequent to the lamination of the organic layer, an electrode that forms a counter electrode with the electrode on the substrate is laminated by a vacuum deposition method or the like.
In addition, after preparing a board | substrate, a cathode, an anode, and an organic layer by a separate process, these may be crimped | bonded and laminated | stacked.
The obtained organic electroluminescence device has an emission maximum wavelength of, for example, 500 nm or less, preferably 400 nm to 500 nm, more preferably 430 nm to 480 nm. If it is 500 nm or less, it is preferable because it emits blue light, and if it is 400 nm or more, it is preferable because visibility of human eyes is improved. Here, the emission maximum wavelength is generally determined from the emission spectrum obtained by measuring the emission spectrum with a device such as a spectral radiance meter.
The obtained organic electroluminescence element has an emission lifetime of, for example, 1 ms or less, preferably 100 μs or less.

(4) Device having an organic electroluminescence element The organic electroluminescence element of the present invention can be used as a device such as a display for a vehicle, a portable device, a personal computer, a television or the like.

Ar雰囲気下、水素化ナトリウム(60%, 2.06g, 51.5mmol)を無水ＴＨＦ(60ml)に懸濁し、これに室温で3,3-ジメチル-2-ブタノン(tBuCOMe、6.1ml, 49.3mmol, 1.3eq)を少量ずつ加えた。水素ガスの発生が収まるまで室温で20分撹拌し、反応混合物を60℃に加熱した。これに、6-メチル-2-ピリジンカルボン酸エチルエステル(6.48g, 38.1mmol)を少量ずつ滴下し、70℃で20分撹拌した。反応混合物を放冷後、氷浴で冷却し、希塩酸を少量ずつ加えてpH=8〜9に調整した。エーテルで抽出し、有機層を飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去して黄色オイルを得た。これをエタノール(100ml)に溶かし、ヒドラジン１水和物(3.95g, 77.3mmol)のエタノール溶液(20ml)をゆっくり加え、2時間還流した。反応混合物を放冷し、溶媒留去後、残渣をジクロロメタンに溶かし、飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去して黄色オイルを得た。これをカラムクロマトグラフィ（シリカゲル／ヘキサン＋50%ジクロロメタン、続いてジクロロメタン＋20%酢酸エチル）で精製して淡黄色固体として5-(6-メチル-2-ピリジル)-3-t-ブチルピラゾール(7.3g, 89%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.38 (9H, s), 2.57 (3H, s), 6.62 (1H, s), 7.04 (1H, d, J=8Hz), 7.53 (1H, bs), 7.59 (1H, t, J=8Hz). Example 1
Complex A was synthesized according to the following synthesis scheme.

Under an Ar atmosphere, sodium hydride (60%, 2.06 g, 51.5 mmol) was suspended in anhydrous THF (60 ml), and 3,3-dimethyl-2-butanone (tBuCOMe, 6.1 ml, 49.3 mmol, 1.3) was suspended at room temperature. eq) was added in small portions. The mixture was stirred at room temperature for 20 minutes until hydrogen gas evolution ceased, and the reaction mixture was heated to 60 ° C. To this, 6-methyl-2-pyridinecarboxylic acid ethyl ester (6.48 g, 38.1 mmol) was added dropwise little by little, and the mixture was stirred at 70 ° C. for 20 minutes. The reaction mixture was allowed to cool and then cooled in an ice bath, and diluted hydrochloric acid was added little by little to adjust the pH to 8-9. The mixture was extracted with ether, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was dissolved in ethanol (100 ml), an ethanol solution (20 ml) of hydrazine monohydrate (3.95 g, 77.3 mmol) was slowly added, and the mixture was refluxed for 2 hours. The reaction mixture was allowed to cool and the solvent was evaporated. The residue was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by dichloromethane + 20% ethyl acetate) to give 5- (6-methyl-2-pyridyl) -3-t-butylpyrazole (7.3 g, 89%).
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.38 (9H, s), 2.57 (3H, s), 6.62 (1H, s), 7.04 (1H, d, J = 8Hz), 7.53 (1H, bs ), 7.59 (1H, t, J = 8Hz).

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (Xantphos, 1.14 g, 1.97 mmol), sodium hydride (60%, 84 mg, 2.1 mmol, 1.1 eq) in anhydrous THF ( 35 ml), and a solution of 5- (6-methyl-2-pyridyl) -3-t-butylpyrazole (0.42 g, 1.95 mmol) in anhydrous THF (10 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.19 g, 1.92 mmol) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered off, and the filtrate was evaporated to give a pale yellow solid. This was recrystallized twice from a mixed solvent of dichloromethane + diethyl ether to obtain complex A (0.3 g, 18%) as greenish yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.26 (9H, s), 1.46 (3H, s), 1.61 (3H, s), 1.89 (3H, s), 6.24 (1H, s), 6.54- 6.57 (2H, m), 6.66 (1H, d, J = 9Hz), 6.78 (3H, bs), 6.99-7.15 (16H, m), 7.29 (1H, d, J = 8Hz), 7.45-7.49 (3H m), 7.72 (3H, bs).

Ar雰囲気下、1,2-ビス(ジフェニルホスフィノ)ベンゼン(dppbz、0.92g, 2.06mmol)、水素化ナトリウム(60%, 90mg, 2.3mmol, 1.1eq)を無水ＴＨＦ(35ml)に懸濁し、5-(6-メチル-2-ピリジル)-3-t-ブチルピラゾール(0.45g, 2.1mmol)の無水ＴＨＦ溶液(15ml)を室温で滴下した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.20g, 2.1mmol)を加え、室温で5時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して黄色アモルファス固体を得た。これをジクロロメタン＋ジエチルエーテルの混合溶媒から再結晶することにより黄色板状晶として錯体Ｂ(0.74g, 50%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.28 (3, s), 1.54 (9H, s), 6.54 (1H, s), 6.57 (1H, d, J=8Hz), 7.21-7.45 (21H, m), 7.62-7.66 (2H, m), 8.00 (3H, bs). (Example 2)
Complex B was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 1,2-bis (diphenylphosphino) benzene (dppbz, 0.92 g, 2.06 mmol), sodium hydride (60%, 90 mg, 2.3 mmol, 1.1 eq) was suspended in anhydrous THF (35 ml), An anhydrous THF solution (15 ml) of 5- (6-methyl-2-pyridyl) -3-t-butylpyrazole (0.45 g, 2.1 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.20 g, 2.1 mmol) was added, and the mixture was stirred at room temperature for 5 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow amorphous solid. This was recrystallized from a mixed solvent of dichloromethane + diethyl ether to obtain Complex B (0.74 g, 50%) as yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.28 (3, s), 1.54 (9H, s), 6.54 (1H, s), 6.57 (1H, d, J = 8Hz), 7.21-7.45 (21H , m), 7.62-7.66 (2H, m), 8.00 (3H, bs).

Ar雰囲気下、2,2'-ビス(ジフェニルホスフィノ)ジフェニルエーテル(DPEphos、1.05g, 1.91mmol)、水素化ナトリウム(60%, 80mg, 2.0mmol, 1.1eq)を無水ＴＨＦ(35ml)に懸濁し、5-(6-メチル-2-ピリジル)-3-t-ブチルピラゾール(0.41g, 1.9mmol)の無水ＴＨＦ溶液(15ml)を室温で滴下した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.18g, 1.8mmol)を加え、室温で5時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して茶色アモルファス固体を得た。これをヘキサンで洗浄し、ジクロロメタン＋エタノールの混合溶媒から再結晶することにより白色固体として錯体Ｃ(0.37g, 25%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.37 (9H, s), 1.91 (3H, s), 6.22 (1H, s), 6.63-6.68 (3H, m), 6.84 (2H, t, J=8Hz), 6.94 (2H, d, J=8Hz), 7.12-7.20 (2H, m), 7.43 (1H, t, J=8Hz), 7.84 (2H, bs).
元素分析、C₄₉H₄₄CuN₃OP₂としての計算値: C, 72.09; H, 5.43; N, 5.15
実測値: C, 72.4; H, 5.5; N, 5.0 (Example 3)
Complex C was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 2,2'-bis (diphenylphosphino) diphenyl ether (DPEphos, 1.05 g, 1.91 mmol) and sodium hydride (60%, 80 mg, 2.0 mmol, 1.1 eq) were suspended in anhydrous THF (35 ml). 5- (6-methyl-2-pyridyl) -3-t-butylpyrazole (0.41 g, 1.9 mmol) in anhydrous THF (15 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.18 g, 1.8 mmol) was added, and the mixture was stirred at room temperature for 5 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a brown amorphous solid. This was washed with hexane and recrystallized from a mixed solvent of dichloromethane + ethanol to obtain Complex C (0.37 g, 25%) as a white solid.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.37 (9H, s), 1.91 (3H, s), 6.22 (1H, s), 6.63-6.68 (3H, m), 6.84 (2H, t, J = 8Hz), 6.94 (2H, d, J = 8Hz), 7.12-7.20 (2H, m), 7.43 (1H, t, J = 8Hz), 7.84 (2H, bs).
Elemental analysis, calculated as C ₄₉ H ₄₄ CuN ₃ OP ₂ : C, 72.09; H, 5.43; N, 5.15
Found: C, 72.4; H, 5.5; N, 5.0

Ar雰囲気下、1,2-ビス(ジフェニルホスフィノ)エタン(dppe、1.24g, 2.96mmol)、水素化ナトリウム(60%, 0.12g, 3.0mmol, 1.1eq)を無水ＴＨＦ(50ml)に懸濁し、5-(6-メチル-2-ピリジル)-3-t-ブチルピラゾール(0.63g, 2.93mmol)の無水ＴＨＦ溶液(20ml)を室温で滴下した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.28g, 2.83mmol)を加え、室温で4時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して黄色アモルファス固体を得た。これを少量のジクロロメタンに溶かし、ヘキサンで再沈することにより白色固体を得た。更にトルエン＋ヘキサンの混合溶媒から再結晶することにより淡黄色板状晶として錯体Ｄ(0.72g, 38%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.56 (9H, s), 1.70 (3H, s), 2.40 (4H, bs), 6.59 (1H, s), 6.65 (1H, d, J=8Hz), 7.16-7.18 (1H, m), 7.23-7.29 (12H, m), 7.40 (1H, d, J=8Hz), 7.48 (1H, t, J=8Hz), 7.74 (7H, bs).
元素分析、C₃₉H₄₀CuN₃P₂+0.8PhMeとしての計算値: C, 71.44; H, 6.24; N, 5.60
実測値: C, 71.0; H, 6.6; N, 5.6 Example 4
Complex D was synthesized according to the following synthesis scheme.

Under an Ar atmosphere, 1,2-bis (diphenylphosphino) ethane (dppe, 1.24 g, 2.96 mmol) and sodium hydride (60%, 0.12 g, 3.0 mmol, 1.1 eq) were suspended in anhydrous THF (50 ml). 5- (6-Methyl-2-pyridyl) -3-t-butylpyrazole (0.63 g, 2.93 mmol) in anhydrous THF (20 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.28 g, 2.83 mmol) was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow amorphous solid. This was dissolved in a small amount of dichloromethane and reprecipitated with hexane to obtain a white solid. Further, recrystallization from a mixed solvent of toluene and hexane gave Complex D (0.72 g, 38%) as pale yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.56 (9H, s), 1.70 (3H, s), 2.40 (4H, bs), 6.59 (1H, s), 6.65 (1H, d, J = 8Hz ), 7.16-7.18 (1H, m), 7.23-7.29 (12H, m), 7.40 (1H, d, J = 8Hz), 7.48 (1H, t, J = 8Hz), 7.74 (7H, bs).
Elemental _{analysis, C 39 H 40 CuN 3 P} 2 + calculated for 0.8PhMe: C, 71.44; H, 6.24; N, 5.60
Found: C, 71.0; H, 6.6; N, 5.6

Ar雰囲気下、ナトリウムメトキシド／メタノール溶液(1mol/l, 4.4ml, 44mmol)を無水ＴＨＦ(50ml)に溶かし、これに室温でアセトフェノン(4.9ml, 42mmol, 1.4eq)を加えた。次に6-メチル-2-ピリジンカルボン酸エチルエステル(4.98g, 29.4mmol)を加えて4時間還流した。反応混合物を放冷後、溶媒留去して、残渣を水に溶かし、2M塩酸を加えて中性にした。水層をエーテルで抽出し、有機層を飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去した。残渣をエタノール(50ml)に溶かし、ヒドラジン１水和物(1.94g, 37.9mmol)のエタノール溶液(15ml)をゆっくり加え、2時間還流した。反応混合物を放冷し、溶媒留去後、残渣をジクロロメタンに溶かし、飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去して黄色オイルを得た。これをカラムクロマトグラフィ（シリカゲル／ヘキサン＋50%ジクロロメタン、続いてジクロロメタン＋20%酢酸エチル）で精製して白色固体として5-(6-メチル-2-ピリジル)-3-フェニルピラゾール(1.92g, 28%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 2.60 (3H, s), 7.01 (1H, s), 7.10 (1H, d, J=8Hz), 7.34 (1H, t, J=8Hz), 7.43 (2H, t, J=8Hz), 7.51 (1H, bs), 7.64 (1H, t, J=8Hz), 7.86 (2H, d, J=8Hz), 11.24 (1H, bs). (Example 5)
Complex E was synthesized according to the following synthesis scheme.

Under an Ar atmosphere, sodium methoxide / methanol solution (1 mol / l, 4.4 ml, 44 mmol) was dissolved in anhydrous THF (50 ml), and acetophenone (4.9 ml, 42 mmol, 1.4 eq) was added thereto at room temperature. Next, 6-methyl-2-pyridinecarboxylic acid ethyl ester (4.98 g, 29.4 mmol) was added and refluxed for 4 hours. The reaction mixture was allowed to cool, the solvent was evaporated, the residue was dissolved in water, and neutralized with 2M hydrochloric acid. The aqueous layer was extracted with ether, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was dissolved in ethanol (50 ml), a solution of hydrazine monohydrate (1.94 g, 37.9 mmol) in ethanol (15 ml) was slowly added, and the mixture was refluxed for 2 hours. The reaction mixture was allowed to cool and the solvent was evaporated. The residue was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by dichloromethane + 20% ethyl acetate) to give 5- (6-methyl-2-pyridyl) -3-phenylpyrazole (1.92 g, 28%) as a white solid Got.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 2.60 (3H, s), 7.01 (1H, s), 7.10 (1H, d, J = 8Hz), 7.34 (1H, t, J = 8Hz), 7.43 (2H, t, J = 8Hz), 7.51 (1H, bs), 7.64 (1H, t, J = 8Hz), 7.86 (2H, d, J = 8Hz), 11.24 (1H, bs).

Under Ar atmosphere, 1,2-bis (diphenylphosphino) benzene (dppbz, 0.91 g, 2.04 mmol), sodium hydride (60%, 92 mg, 2.3 mmol, 1.1 eq) was suspended in anhydrous THF (35 ml), An anhydrous THF solution (10 ml) of 5- (6-methyl-2-pyridyl) -3-phenylpyrazole (0.47 g, 2.0 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.20 g, 2.0 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow-green amorphous solid. A small amount of ether was added to this and it became a solid when sonicated, so it was filtered and recrystallized from a mixed solvent of toluene and hexane to obtain complex E (0.79 g, 53%) as yellow needles. It was.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.75 (3H, s), 6.67 (1H, d, J = 4Hz), 6.9-7.3 (18H, m), 7.4-75 (6H, m), 7.62 -7.63 (2H, m), 7.95 (2H, bs), 8.08 (2H, d, J = 8Hz).
Elemental analysis, calculated as C ₄₅ H ₃₆ CuN ₃ P ₂ + H ₂ O: C, 70.90; H, 5.02; N, 5.51
Found: C, 71.1; H, 5.0; N, 5.3

Ar雰囲気下、4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン(XantPhos、1.04g, 1.8mmol)、水素化ナトリウム(60%, 81mg, 2.0mmol, 1.1eq)を無水ＴＨＦ(35ml)に懸濁し、5-(6-メチル-2-ピリジル)-3-フェニルピラゾール(0.42g, 1.79mmol)の無水ＴＨＦ溶液(10ml)を室温で滴下した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.17g, 1.72mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して淡緑色アモルファス固体を得た。これに少量のエーテルを加え、超音波処理すると固体になったので、ろ別し、トルエン＋ヘキサンの混合溶媒から再結晶することにより白色固体として錯体Ｆ(0.48g, 32%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.48 (3H, s), 1.62 (3H, s), 1.91 (3H, s), 6.50-6.52 (2H, m), 6.74 (1H, d, J=7Hz), 6.82 (4H, bs), 6.90 (1H, s), 7.0-7.2 (15H, m), 7.30 (2H, t, J=8Hz), 7.5-7.6 (4H, m), 7.69 (4H, bs), 7.99 (2H, d, J=8Hz).
元素分析、C₅₄H₄₄CuN₃OP₂としての計算値: C, 74.00; H, 5.06; N, 4.79
実測値: C, 73.9; H, 5.1; N, 4.7 (Example 6)
Complex F was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos, 1.04 g, 1.8 mmol), sodium hydride (60%, 81 mg, 2.0 mmol, 1.1 eq) in anhydrous THF ( 35 ml), and a solution of 5- (6-methyl-2-pyridyl) -3-phenylpyrazole (0.42 g, 1.79 mmol) in anhydrous THF (10 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.17 g, 1.72 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a pale green amorphous solid. A small amount of ether was added to the solution, which became a solid when sonicated. Thus, it was filtered and recrystallized from a mixed solvent of toluene and hexane to obtain Complex F (0.48 g, 32%) as a white solid.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.48 (3H, s), 1.62 (3H, s), 1.91 (3H, s), 6.50-6.52 (2H, m), 6.74 (1H, d, J = 7Hz), 6.82 (4H, bs), 6.90 (1H, s), 7.0-7.2 (15H, m), 7.30 (2H, t, J = 8Hz), 7.5-7.6 (4H, m), 7.69 (4H , bs), 7.99 (2H, d, J = 8Hz).
Elemental analysis, calculated as C ₅₄ H ₄₄ CuN ₃ OP ₂ : C, 74.00; H, 5.06; N, 4.79
Actual value: C, 73.9; H, 5.1; N, 4.7

Ar雰囲気下、1,2-ビス(ジフェニルホスフィノ)ベンゼン(1.0g, 2.24mmol)、水素化ナトリウム(60%, 96mg, 2.4mmol, 1.1eq)を無水ＴＨＦ(30ml)に懸濁し、2-(2-ピリジル)ベンズイミダゾール(pybimH、0.44g, 2.25mmol)を室温で少量ずつ添加した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.22g, 2.22mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して黄色アモルファス固体を得た。これに少量のエーテルを加え、超音波処理すると固体になったので、ろ別し、ジクロロメタン＋ヘキサン＋エーテルの混合溶媒から３回再結晶することにより黄色板状晶として錯体Ｇ(0.51g, 33%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 6.93-6.94 (1H, m), 7.0-7.5 (23H, m), 7.5-7.6 (5H, m), 7.74 (1H, t, J=8Hz), 7.85 (1H, d, J=8Hz), 8.51 (1H, d, J=6Hz).
元素分析、C₄₂H₃₂CuN₃P₂+0.5H₂Oとしての計算値: C, 70.73; H, 4.66; N, 5.89
実測値: C, 70.7; H, 4.9; N, 5.8 (Example 7)
Complex G was synthesized according to the following synthesis scheme.

Under an Ar atmosphere, 1,2-bis (diphenylphosphino) benzene (1.0 g, 2.24 mmol), sodium hydride (60%, 96 mg, 2.4 mmol, 1.1 eq) was suspended in anhydrous THF (30 ml), and 2- (2-Pyridyl) benzimidazole (pybimH, 0.44 g, 2.25 mmol) was added in small portions at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.22 g, 2.22 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow amorphous solid. A small amount of ether was added to this and it became a solid when sonicated. Filtered off and recrystallized three times from a mixed solvent of dichloromethane + hexane + ether to give complex G (0.51 g, 33) as yellow plate crystals. %).
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 6.93-6.94 (1H, m), 7.0-7.5 (23H, m), 7.5-7.6 (5H, m), 7.74 (1H, t, J = 8Hz) , 7.85 (1H, d, J = 8Hz), 8.51 (1H, d, J = 6Hz).
Elemental analysis, calculated as C ₄₂ H ₃₂ CuN ₃ P ₂ + 0.5H ₂ O: C, 70.73; H, 4.66; N, 5.89
Found: C, 70.7; H, 4.9; N, 5.8

Ar雰囲気下、4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン(1.00g, 1.73mmol)、水素化ナトリウム(60%, 80mg, 2.0mmol, 1.1eq)を無水ＴＨＦ(30ml)に懸濁し、2-(2-ピリジル)ベンズイミダゾール(pybimH、0.34g, 1.74mmol)を室温で少量ずつ添加した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.17g, 1.72mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して黄色固体を得た。これをジクロロメタン＋エーテルの混合溶媒から２回再結晶することにより黄色板状晶として錯体Ｈ(0.21g, 15%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.70 (3H, s), 1.88 (3H, s), 6.35 (1H, d, J=8Hz), 6.41-6.64 (2H, m), 6.63 (1H, t, J=7Hz), 6.91-7.20 (24H, m), 7.58 (2H, dd, J=8Hz, 2Hz), 7.69 (1H, t, J=8Hz), 7.75 (1H, d, J=8Hz), 8.01 (1H, d, J=5Hz), 8.52 (1H, d, J=8Hz).
元素分析、C₅₁H₄₀CuN₃OP₂としての計算値: C, 73.24; H, 4.82; N, 5.02、
実測値: C, 72.9; H, 5.1; N, 4.9 (Example 8)
Complex H was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (1.00 g, 1.73 mmol), sodium hydride (60%, 80 mg, 2.0 mmol, 1.1 eq) in anhydrous THF (30 ml) 2- (2-pyridyl) benzimidazole (pybimH, 0.34 g, 1.74 mmol) was added in small portions at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.17 g, 1.72 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow solid. This was recrystallized twice from a mixed solvent of dichloromethane + ether to obtain Complex H (0.21 g, 15%) as yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.70 (3H, s), 1.88 (3H, s), 6.35 (1H, d, J = 8Hz), 6.41-6.64 (2H, m), 6.63 (1H , t, J = 7Hz), 6.91-7.20 (24H, m), 7.58 (2H, dd, J = 8Hz, 2Hz), 7.69 (1H, t, J = 8Hz), 7.75 (1H, d, J = 8Hz ), 8.01 (1H, d, J = 5Hz), 8.52 (1H, d, J = 8Hz).
Elemental analysis, calculated as C ₅₁ H ₄₀ CuN ₃ OP ₂ : C, 73.24; H, 4.82; N, 5.02,
Found: C, 72.9; H, 5.1; N, 4.9

Ar雰囲気下、2,2'-ビス(ジフェニルホスフィノ)ジフェニルエーテル(1.39g, 2.53mmol)、水素化ナトリウム(60%, 0.11g, 2.75mmol, 1.1eq)を無水ＴＨＦ(30ml)に懸濁し、2-(2-ピリジル)ベンズイミダゾール(pybimH、0.49g, 2.51mmol)を室温で少量ずつ添加した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.25g, 2.53mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して緑色アモルファス固体を得た。これをジクロロメタン＋エーテル＋ヘキサンから再結晶し、続いてジクロロメタン＋トルエンの混合溶媒から再結晶することにより緑色板状晶として錯体I(1.68g, 84%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 6.74 6.76 (2H, m), 6.81 (1H, t, J=8Hz), 6.90 (2H,t, J=8Hz), 7.0-7.2 (22H, m), 7.33 (1H,d, J=8Hz), 7.64 (1H, t, J=8Hz), 7.77 (1H, d , J=8Hz), 7.94 (1H,d , J=5Hz), 8.45 (1H, d, J=8Hz).
元素分析、C₅₁H₄₀CuN₃OP₂+0.4PhMeとしての計算値: C, 73.24; H, 4.74; N, 5.04、
実測値: C, 73.0; H, 5.1; N, 4.8 Example 9
Complex I was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 2,2′-bis (diphenylphosphino) diphenyl ether (1.39 g, 2.53 mmol), sodium hydride (60%, 0.11 g, 2.75 mmol, 1.1 eq) was suspended in anhydrous THF (30 ml), 2- (2-Pyridyl) benzimidazole (pybimH, 0.49 g, 2.51 mmol) was added in small portions at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.25 g, 2.53 mmol) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered off and the filtrate was evaporated to give a green amorphous solid. This was recrystallized from dichloromethane + ether + hexane, and then recrystallized from a mixed solvent of dichloromethane + toluene to obtain Complex I (1.68 g, 84%) as green plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 6.74 6.76 (2H, m), 6.81 (1H, t, J = 8Hz), 6.90 (2H, t, J = 8Hz), 7.0-7.2 (22H, m ), 7.33 (1H, d, J = 8Hz), 7.64 (1H, t, J = 8Hz), 7.77 (1H, d, J = 8Hz), 7.94 (1H, d, J = 5Hz), 8.45 (1H, d, J = 8Hz).
Elemental analysis, calculated for C ₅₁ H ₄₀ CuN ₃ OP ₂ + 0.4PhMe: C, 73.24; H, 4.74; N, 5.04,
Actual value: C, 73.0; H, 5.1; N, 4.8

6-ブロモピコリン酸(5.0g, 24.2mmol)、炭酸カリウム(3.76g, 27.2mmol, 1.1eq.)をN,N-ジメチルホルムアミド(DMF、60ml)に懸濁し、沃化エチル(4ml, 48.8mmol, 2eq.)を加え、室温で1時間撹拌後、55℃で7時間加熱した。反応混合物を水(150ml)で希釈し、エーテルで抽出した。有機層を水(50ml x 3)で洗浄し、無水硫酸ナトリウムで乾燥、溶媒留去して無色オイルを得た。これをカラムクロマトグラフィ（シリカゲル／ヘキサン、続いてヘキサン＋50%ジクロロメタン、最後にジクロロメタンのみ）で精製して無色オイルとして6-ブロモピコリン酸エチル(5.4g, 95%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.43 (3H, t, J=8Hz), 4.47 (2H, q, J=8Hz), 7.66 (1H, dd, J=8Hz, 1Hz), 7.70 (1H, t, J=8Hz), 8.08 (1H, dd, J=7Hz, 1Hz). (Example 10)
Complex J was synthesized according to the following synthesis scheme.

6-Bromopicolinic acid (5.0 g, 24.2 mmol) and potassium carbonate (3.76 g, 27.2 mmol, 1.1 eq.) Were suspended in N, N-dimethylformamide (DMF, 60 ml) and ethyl iodide (4 ml, 48.8 mmol). , 2eq.) Was added, and the mixture was stirred at room temperature for 1 hour and then heated at 55 ° C for 7 hours. The reaction mixture was diluted with water (150 ml) and extracted with ether. The organic layer was washed with water (50 ml x 3), dried over anhydrous sodium sulfate, and evaporated to give a colorless oil. This was purified by column chromatography (silica gel / hexane, followed by hexane + 50% dichloromethane, finally dichloromethane only) to give ethyl 6-bromopicolinate (5.4 g, 95%) as a colorless oil.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.43 (3H, t, J = 8Hz), 4.47 (2H, q, J = 8Hz), 7.66 (1H, dd, J = 8Hz, 1Hz), 7.70 ( 1H, t, J = 8Hz), 8.08 (1H, dd, J = 7Hz, 1Hz).

Under Ar atmosphere, ethyl 6-bromopicolinate (3.85 g, 16.7 mmol), 1,1′-bis (diphenylphosphino) ferrocene palladium dichloride (PdCl ₂ (dppf), 0.27 g, 0.33 mmol, 2% Pd) A THF solution (0.5 mol / l, 50 ml, 25.0 mmol, 1.5 eq.) Of propyl zinc bromide (PrZnBr) was added, and the mixture was stirred at room temperature for 2 hours and then heated at 55 ° C. for 6 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a reddish brown oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by dichloromethane, finally hexane + 8% ethyl acetate) to give ethyl 6-propylpicolinate (1.18 g, 37%) as a yellow oil.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.78 (3H, t, J = 7Hz), 1.43 (3H, t, J = 7Hz), 1.78 (2H, sextet, J = 7Hz), 2.88 (2H, t, J = 7Hz), 4.47 (2H, q, J- = 7Hz), 7.32 (1H, d, J = 8Hz), 7.72 (1H, t, J = 8Hz), 7.93 (1H, d, J = 8Hz ).

Under an Ar atmosphere, sodium hydride (60%, 0.3 g, 7.5 mmol) was suspended in anhydrous THF (30 ml), and 3,3-dimethyl-2-butanone (MeCOtBu, 0.92 ml, 7.44 mmol, 1.3 mmol) was suspended at room temperature. eq) was added in small portions. The mixture was stirred at room temperature for 20 minutes until hydrogen gas evolution ceased, and the reaction mixture was heated to 60 ° C. To this was added dropwise an anhydrous THF solution (15 ml) of ethyl 6-propyl-2-pyridinecarboxylate (1.1 g, 5.69 mmol), and the mixture was stirred at 70 ° C. for 20 minutes. The reaction mixture was allowed to cool and then cooled in an ice bath, and diluted hydrochloric acid was added little by little to adjust the pH to 8-9. The mixture was extracted with ether, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was dissolved in ethanol (20 ml), an ethanol solution (15 ml) of hydrazine monohydrate (0.59 g, 11.8 mmol) was slowly added, and the mixture was refluxed for 2 hours. The reaction mixture was allowed to cool and the solvent was evaporated. The residue was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / dichloromethane, followed by dichloromethane + 8% ethyl acetate, finally dichloromethane + 1% methanol) to give 5- (6-propyl-2-pyridyl) -3-t-butylpyrazole as a pale yellow solid (1.13 g, 82%) was obtained.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 0.98 (3H, t, J = 7Hz), 1.40 (9H, s), 1.79 (2H, sextet, J = 7Hz), 2.78 (2H, t, J = 7Hz), 6.60 (1H, s), 7.04 (1H, d, J = 8Hz), 7.49 (1H, d, J = 8Hz), 7.60 (1H, t, J = 8Hz).

Under Ar atmosphere, 1,2-bis (diphenylphosphino) benzene (dppbz, 1.01 g, 2.17 mmol), sodium hydride (60%, 97 mg, 2.43 mmol, 1.1 eq) was suspended in anhydrous THF (35 ml), An anhydrous THF solution (15 ml) of 5- (6-propyl-2-pyridyl) -3-t-butylpyrazole (0.54 g, 2.22 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.22 g, 2.22 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow-green amorphous solid. A small amount of ether was added to this and it became a solid when sonicated, so it was filtered and recrystallized from a mixed solvent of ether and hexane to obtain complex J (0.79 g, 53%) as pale yellow crystals. .
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ -0.07 (3H, t, J = 7Hz), 0.89 (2H, sextet, J = 7Hz), 1.55 (9H, s), 1.68 (2H, t, J = 7Hz), 6.55 (1H, s), 6.61 (1H, d, J = 8Hz), 7.3-7.5 (24H, m), 7.63 (2H, m).
Elemental analysis, C ₄₅ H ₄₄ CuN ₃ calculated for _{P 2: C, 71.84; H} , 5.89; N, 5.59,
Found: C, 71.7; H, 6.3; N, 5.5

Ar雰囲気下、4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン(XantPhos、1.07g, 1.85mmol)、水素化ナトリウム(60%, 85mg, 2.1mmol, 1.1eq)を無水ＴＨＦ(30ml)に懸濁し、5-(6-プロピル-2-ピリジル)-3-t-ブチルピラゾール(0.45g, 1.85mmol)の無水ＴＨＦ溶液(10ml)を室温で滴下した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.18g, 1.82mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して淡褐色固体を得た。これをヘキサン＋ジエチルエーテルの混合溶媒から１回、ヘキサン＋エタノールから１回再結晶することにより淡緑色板状晶として錯体Ｋ(0.31g, 19%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ -0.15 (3H, t, J=7Hz), 0.96 (2H, sextet, J=7Hz), 1.26 (9H, s), 1.45 (3H, s), 1.89 (3H, s), 2.12 (2H, t, J=7Hz), 6.24 (1H, s), 6.54-6.56 (2H, m), 6.7-6.8 (5H, m), 6.9-7.1 (14H, m), 7.32 (1H, d, J=8Hz), 7.48 (2H, d, J=8Hz), 7.54 (1H, t, J=8Hz), 7.77 (4H, bs).
元素分析、C₅₄H₅₂CuN₃OP₂+EtOHとしての計算値: C, 73.33; H, 5.93; N, 4.75、
実測値: C, 72.1; H, 6.2; N, 4.5 (Example 11)
Complex K was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos, 1.07 g, 1.85 mmol), sodium hydride (60%, 85 mg, 2.1 mmol, 1.1 eq) in anhydrous THF ( 30 ml), and a solution of 5- (6-propyl-2-pyridyl) -3-t-butylpyrazole (0.45 g, 1.85 mmol) in anhydrous THF (10 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.18 g, 1.82 mmol) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered off, and the filtrate was evaporated to give a light brown solid. This was recrystallized once from a mixed solvent of hexane + diethyl ether and once from hexane + ethanol to obtain Complex K (0.31 g, 19%) as pale green plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ -0.15 (3H, t, J = 7Hz), 0.96 (2H, sextet, J = 7Hz), 1.26 (9H, s), 1.45 (3H, s), 1.89 (3H, s), 2.12 (2H, t, J = 7Hz), 6.24 (1H, s), 6.54-6.56 (2H, m), 6.7-6.8 (5H, m), 6.9-7.1 (14H, m ), 7.32 (1H, d, J = 8Hz), 7.48 (2H, d, J = 8Hz), 7.54 (1H, t, J = 8Hz), 7.77 (4H, bs).
Elemental analysis, calculated for C ₅₄ H ₅₂ CuN ₃ OP ₂ + EtOH: C, 73.33; H, 5.93; N, 4.75,
Actual value: C, 72.1; H, 6.2; N, 4.5

6-メチルピリジン-2-カルボキサルデヒド(2.05g, 16.9mmol)、o-フェニレンジアミン(1.82g, 16.0mmol)を水(130ml)に懸濁し、炭酸カリウム(3.42g, 24.7mmol)を加えて室温で20分撹拌した。これに、沃化カリウム(0.69g, 4.16mmol)と沃素(0.98g, 3.86mmol)の水溶液を加え、続いて沃素(3.21g, 12.6mmol)を少量ずつ加えた。反応混合物を90℃で50分撹拌し、室温まで放冷した後、5%チオ硫酸ナトリウム水溶液を加えて未反応の沃素を失活させた。反応混合物を酢酸エチルで抽出し、有機層を無水硫酸ナトリウムで乾燥、溶媒留去後、カラムクロマグラフィ（シリカゲル／ヘキサン＋50%ジクロロメタン、続いてヘキサン＋5%酢酸エチル）で精製して淡褐色固体として2-(6-メチル-2-ピリジル)ベンズイミダゾール(1.23g, 37%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 2.62 (3H, s), 7.22 (1H, d, J=8Hz), 7.28-7.30 (2H, m), 7.47-7.49 (1H, m), 7.74 (1H, t, J=8Hz), 7.83-7.85 (1H, m), 8.23 (1H, d, J=8Hz). (Example 12)
Complex L was synthesized according to the following synthesis scheme.

6-methylpyridine-2-carboxaldehyde (2.05 g, 16.9 mmol) and o-phenylenediamine (1.82 g, 16.0 mmol) are suspended in water (130 ml), and potassium carbonate (3.42 g, 24.7 mmol) is added. Stir at room temperature for 20 minutes. To this was added an aqueous solution of potassium iodide (0.69 g, 4.16 mmol) and iodine (0.98 g, 3.86 mmol), and then iodine (3.21 g, 12.6 mmol) was added in small portions. The reaction mixture was stirred at 90 ° C. for 50 minutes and allowed to cool to room temperature, and 5% aqueous sodium thiosulfate solution was added to deactivate unreacted iodine. The reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and purified by column chromatography (silica gel / hexane + 50% dichloromethane, then hexane + 5% ethyl acetate) to obtain a light brown solid. 2- (6-Methyl-2-pyridyl) benzimidazole (1.23 g, 37%) was obtained.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 2.62 (3H, s), 7.22 (1H, d, J = 8Hz), 7.28-7.30 (2H, m), 7.47-7.49 (1H, m), 7.74 (1H, t, J = 8Hz), 7.83-7.85 (1H, m), 8.23 (1H, d, J = 8Hz).

Under an Ar atmosphere, 1,2-bis (diphenylphosphino) benzene (dppbz, 1.24 g, 2.78 mmol) and sodium hydride (60%, 0.12 g, 3.0 mmol, 1.1 eq) were suspended in anhydrous THF (45 ml). 2- (6-Methyl-2-pyridyl) benzimidazole (0.58 g, 2.77 mmol) was added in small portions at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.27 g, 2.73 mmol) was added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow amorphous solid. When a small amount of ether was added to this, it became a solid, which was separated by filtration and recrystallized once from a mixed solvent of toluene + hexane and twice from a mixed solvent of dichloromethane + ether to form complex L as yellowish green plate crystals. (0.48 g, 24%) was obtained.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.68 (3H, s), 6.92 (1H, d, J = 8Hz), 6.98 (1H, t, J = 7Hz), 7.09-7.26 (18H, m) , 7.49 (4H, bs), 7.54-7.57 (2H, m), 7.64-7.69 (3H, m), 7.86 (1H, d, J = 8Hz), 8.42 (1H, d, J = 8Hz).
Elemental _{analysis, C 43 H 34 CuN 3 P} 2 + calculated for 0.3PhMe: C, 71.91; H, 4.77; N, 5.85,
Found: C, 72.4; H, 5.2; N, 5.6

Ar雰囲気下、4,5-ビス(ジフェニルホスフィノ)-9,9-ジメチルキサンテン(XantPhos、1.20g, 2.07mmol)、水素化ナトリウム(60%, 91mg, 2.28mmol, 1.1eq)を無水ＴＨＦ(35ml)に懸濁し、2-(6-メチル-2-ピリジル)ベンズイミダゾール(0.44g, 2.1mmol)を室温で少量ずつ添加した。反応混合物を室温で1時間撹拌後、塩化第一銅(0.20g, 2.02mmol)を加え、室温で3時間撹拌した。反応混合物をろ別し、ろ液を溶媒留去して黄色固体を得た。これをジクロロメタン＋エーテルの混合溶媒から再結晶することにより黄色板状晶として錯体M(1.25g, 73%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.67 (3H, s), 1.69 (3H, s), 1.85 (3H, s), 6.5-6.53 (2H, m), 6.85 (1H, d, J=7Hz), 6.87 (1H, t, J=8Hz), 6.93-7.08 (16H, m), 7.14-7.25 (8H, m), 7.54 (2H, d, J=8Hz), 7.67 (1H, t, J=8Hz), 7.75 (1H, d, J=8Hz), 8.44 (1H, d, J=8Hz).
元素分析、C₅₂H₄₂CuN₃OP₂としての計算値: C, 73.44; H, 4.98; N, 4.94、
実測値: C, 73.2; H, 5.2; N, 4.7 (Example 13)
Complex M was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos, 1.20 g, 2.07 mmol), sodium hydride (60%, 91 mg, 2.28 mmol, 1.1 eq) in anhydrous THF ( 35 ml) and 2- (6-methyl-2-pyridyl) benzimidazole (0.44 g, 2.1 mmol) was added in small portions at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.20 g, 2.02 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off and the filtrate was evaporated to give a yellow solid. This was recrystallized from a mixed solvent of dichloromethane + ether to obtain Complex M (1.25 g, 73%) as yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.67 (3H, s), 1.69 (3H, s), 1.85 (3H, s), 6.5-6.53 (2H, m), 6.85 (1H, d, J = 7Hz), 6.87 (1H, t, J = 8Hz), 6.93-7.08 (16H, m), 7.14-7.25 (8H, m), 7.54 (2H, d, J = 8Hz), 7.67 (1H, t, J = 8Hz), 7.75 (1H, d, J = 8Hz), 8.44 (1H, d, J = 8Hz).
Elemental analysis, calculated for C ₅₂ H ₄₂ CuN ₃ OP ₂ : C, 73.44; H, 4.98; N, 4.94,
Actual value: C, 73.2; H, 5.2; N, 4.7

Ar雰囲気下、6-ブロモピコリン酸エチル(3.0g, 13.0mmol)、フェニルボロン酸(1.98g, 16.2mmol)、テトラキス(トリフェニルホスフィン)パラジウム(0)(0.3g, 0.26mmol, 2%Pd)を1,2-ジメトキシエタン(50ml)に溶かし、2M炭酸ナトリウム水溶液(4.19g, 39.5mmol, 3eq./20ml)を加えて8時間還流した。反応混合物をジクロロメタンで抽出し、有機層を分取、飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥、溶媒留去して黄色オイルを得た。これをカラムクロマトグラフィ（シリカゲル／ヘキサン＋30%ジクロロメタン）で精製して淡黄色固体としてフェニルピコリン酸エチル(1.55g, 53%)を得た。
¹H-NMR (400MHz, CDCl₃, TMS) δ 1.47 (3H, t, J=7Hz), 4.49 (2H, q, J=7Hz), 7.42-7.51 (3H, m), 7.89-7.92 (2H, m), 8.04-8.09 (3H, m). (Example 14)
Complex N was synthesized according to the following synthesis scheme.

Under Ar atmosphere, ethyl 6-bromopicolinate (3.0 g, 13.0 mmol), phenylboronic acid (1.98 g, 16.2 mmol), tetrakis (triphenylphosphine) palladium (0) (0.3 g, 0.26 mmol, 2% Pd) Was dissolved in 1,2-dimethoxyethane (50 ml), 2M aqueous sodium carbonate solution (4.19 g, 39.5 mmol, 3 eq./20 ml) was added, and the mixture was refluxed for 8 hours. The reaction mixture was extracted with dichloromethane, the organic layer was separated, washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 30% dichloromethane) to obtain ethyl phenylpicolinate (1.55 g, 53%) as a pale yellow solid.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.47 (3H, t, J = 7Hz), 4.49 (2H, q, J = 7Hz), 7.42-7.51 (3H, m), 7.89-7.92 (2H, m), 8.04-8.09 (3H, m).

Under an Ar atmosphere, sodium hydride (60%, 0.34 g, 8.5 mmol) was suspended in anhydrous THF (40 ml), and 3,3-dimethyl-2-butanone (MeCOtBu, 1.1 ml, 8.9 mmol, 1.3) was suspended at room temperature. eq) was added in small portions. The mixture was stirred at room temperature for 20 minutes until hydrogen gas evolution ceased, and the reaction mixture was heated to 60 ° C. To this was added dropwise an anhydrous THF solution (20 ml) of ethyl 6-phenyl-2-pyridinecarboxylate (1.5 g, 6.6 mmol), and the mixture was stirred at 70 ° C. for 20 minutes. The reaction mixture was allowed to cool and then cooled in an ice bath, and diluted hydrochloric acid was added little by little to adjust the pH to 8-9. The mixture was extracted with ether, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was dissolved in ethanol (30 ml), an ethanol solution (10 ml) of hydrazine monohydrate (0.67 g, 13.4 mmol) was slowly added, and the mixture was refluxed for 2 hours. The reaction mixture was allowed to cool and the solvent was evaporated. The residue was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / dichloromethane, followed by dichloromethane + 1% methanol) to give 5- (6-phenyl-2-pyridyl) -3-t-butylpyrazole (1.42 g, 76%) as a white solid. It was.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.40 (9H, s), 6.72 (1H, s), 7.43-7.51 (3H, m), 7.65 (2H, t, J = 7Hz), 7.79 (1H , t, J = 8Hz), 8.06 (2H, d, J = 8Hz).

Under Ar atmosphere, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene (XantPhos, 1.01 g, 1.75 mmol), sodium hydride (60%, 80 mg, 2.0 mmol, 1.1 eq) in anhydrous THF ( 40 ml), and a solution of 5- (6-phenyl-2-pyridyl) -3-t-butylpyrazole (0.48 g, 1.73 mmol) in anhydrous THF (10 ml) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hr, cuprous chloride (0.17 g, 1.72 mmol) was added, and the mixture was stirred at room temperature for 3 hr. The reaction mixture was filtered off, and the filtrate was evaporated to give a light brown solid. This was recrystallized from a mixed solvent of dichloromethane + diethyl ether to obtain Complex N (1.24 g, 78%) as pale yellow plate crystals.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.27 (9H, s), 1.39 (3H, bs), 1.96 (3H, bs), 6.08 (2H, t, J = 7Hz), 6.34-6.44 (4H , m), 6.82 (2H, bs), 7.00-7.49 (29H, m), 7.67-7.71 (4H, m).
Elemental analysis, calculated as C ₅₇ H ₅₀ CuN ₃ OP ₂ : C, 74.53; H, 5.49; N, 4.57,
Actual value: C, 74.1; H, 5.8; N, 4.5

Ar雰囲気下、2,3-ジブロモピリジン(8.73g, 36.9mmol)、ジフェニル(トリメチルシリル)ホスフィン(Me₃SiPPh₂、10g, 38.7mmol, 1.1eq)、ジクロロビス(アセトニトリル)パラジウム(II)(0.24g, 0.93mmol, 2.5%Pd)を無水トルエン(70ml)に溶かし、16時間還流した。反応混合物を飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥、溶媒留去して褐色オイルを得た。これをカラムクロマトグラフィ（シリカゲル／ヘキサン＋50%ジクロロメタン、続いてヘキサン＋1%酢酸エチル）で精製して白色固体(8.0g, 63%)を得た。このものは2-(ジフェニルホスフィノ)-3-ブロモピリジンと2-ブロモ-3-(ジフェニルホスフィノ)ピリジンの混合物であることが¹H-NMRから示唆されたが、このまま次の反応に用いた。
¹H-NMR (400MHz, CDCl₃, TMS) δ 7.08 (1H, dd, J=9Hz, 6Hz), 7.16 (1H, dd, J=7Hz, 4Hz), 7.33 (10H, s), 7.79-7.82 (1H, m), 7.91 (1H, dd, J=8Hz, 2Hz), 8.33 (1H, dd, J=5Hz, 2Hz), 8.56 (1H, d, J=4Hz).
FDMS, C₁₇H₁₃NBrPとしての計算値341、実測値m/z=341 (M₊, 100), 682 (2M⁺, 14). (Example 15)
Complex O was synthesized according to the following synthesis scheme.

Under Ar atmosphere, 2,3-dibromopyridine (8.73 g, 36.9 mmol), diphenyl (trimethylsilyl) phosphine (Me ₃ SiPPh ₂ , 10 g, 38.7 mmol, 1.1 eq), dichlorobis (acetonitrile) palladium (II) (0.24 g, 0.93 mmol, 2.5% Pd) was dissolved in anhydrous toluene (70 ml) and refluxed for 16 hours. The reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and the organic layer was dried over anhydrous sodium sulfate and evaporated to give a brown oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, followed by hexane + 1% ethyl acetate) to give a white solid (8.0 g, 63%). ¹ H-NMR suggested that this was a mixture of 2- (diphenylphosphino) -3-bromopyridine and 2-bromo-3- (diphenylphosphino) pyridine. It was.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 7.08 (1H, dd, J = 9Hz, 6Hz), 7.16 (1H, dd, J = 7Hz, 4Hz), 7.33 (10H, s), 7.79-7.82 ( 1H, m), 7.91 (1H, dd, J = 8Hz, 2Hz), 8.33 (1H, dd, J = 5Hz, 2Hz), 8.56 (1H, d, J = 4Hz).
FDMS, calculated as C ₁₇ H ₁₃ NBrP 341, measured m / z = 341 (M ₊ , 100), 682 (2M ⁺ , 14).

Under an Ar atmosphere, 2- (diphenylphosphino) -3-bromopyridine (4.12 g, 12 mmol) was dissolved in a mixed solvent of anhydrous ether (60 ml) + anhydrous THF (10 ml), and the temperature was adjusted to −60 ° C. in a dry ice / methanol bath. Cooled down. To this was added dropwise n-butyllithium / hexane solution (9 ml, 14.4 mmol, 1.2 eq), and the mixture was stirred at −40 ° C. for 30 minutes. The reaction mixture was cooled to −60 ° C., an ether solution (10 ml) of chlorodiphenylphosphine (2.7 ml, 14.7 mmol) was added dropwise, the cooling bath was removed, and the mixture was left at room temperature overnight. The reaction mixture was quenched with degassed ion-exchanged water, extracted with dichloromethane, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a brown oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane followed by hexane + 5% ethyl acetate) to give 2,3-bis (diphenylphosphino) pyridine (1.5 g, 28%) as a pale yellow solid.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 7.09-7.35 (22H, m), 8.64 (1H, d, J = 5Hz).

Under an Ar atmosphere, 2,3-bis (diphenylphosphino) pyridine (0.75 g, 1.87 mmol), sodium hydride (60%, 75 mg, 1.88 mmol, 1.1 eq) was suspended in anhydrous THF (45 ml), and 5- An anhydrous THF solution (10 ml) of (6-methyl-2-pyridyl) -3-t-butylpyrazole (pypz, 0.36 g, 1.67 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour, cuprous chloride (0.16 g, 1.62 mmol) was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered off, and the filtrate was evaporated to give a pale yellow amorphous solid. This was washed with hexane to obtain Complex O (0.83 g, 71%) as a pale yellow solid.
¹ H-NMR (400MHz, CDCl ₃ , TMS) δ 1.40 (3H, s), 1.55 (9H, s), 6.58 (1H, s), 6.59 (1H, d, J = 6Hz), 7.09-7.32 (18H , m), 7.37 (1H, d, J = 8Hz), 7.44 (1H, t, J = 8Hz), 7.88-8.28 (4H, m), 8.85-8.86 (1H, m).
Elemental analysis, calculated as C ₄₂ H ₃₉ CuN ₄ P ₂ : C, 69.55; H, 5.42; N, 7.72,
Found: C, 70.0; H, 5.8; N, 7.5

(Comparative Example 1)
The following complex R exemplified in JP-A-2006-286749 was synthesized according to Z. Naturforsch. B, 58, 950 (2003) and used as a comparative example.

<Evaluation>
The light emission quantum yield, the light emission maximum wavelength, and the light emission lifetime in the powder state of the complexes AH, JO, and R obtained in Examples 1 to 8, 10 to 15, and Comparative Example 1 were measured. The apparatus used for each measurement is shown below.
Emission maximum wavelength and emission quantum yield:
Organic EL quantum yield measuring device (C9920-01) manufactured by Hamamatsu Photonics
Luminous life:
Picosecond fluorescence lifetime measuring device (C4780) manufactured by Hamamatsu Photonics

The measurement results of the emission quantum yield, emission maximum wavelength and emission lifetime of the complexes A to H, J to O and R are shown in Table 1 below. Moreover, the emission spectrum in the powder state of complex AH and JO is shown in FIGS.

Table 1

  Thus, while the comparative complex R did not emit light, the complexes A to H and J to O emitted light in a high yield. It can be seen that the light emission lifetimes of the complexes A to H and J to N are in the range of 10 ms or less, and show a sufficiently fast response.

<Preparation of organic electroluminescence element>
(Example 16)
Using the complex A, an organic electroluminescence device comprising a substrate / anode / hole injection layer / light emitting layer / hole barrier layer / electron transport layer / electron injection layer / cathode was produced. A glass substrate with a transparent electrode of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, then UV ozone cleaning for 30 minutes, and electrode-glass substrate bonding Prepared the body. On this joined body, polyethylenedioxythiophene: polystyrene sulfonic acid (PEDOT: PSS) used for the hole injection layer by spin coating was formed with a film thickness of 40 nm to obtain a hole injection layer. Next, the light emitting layer is formed on the PEDOT: PSS hole injection layer using a 1% by mass chlorobenzene solution of a mixture of complex A and polyvinyl carbazole used in the light emitting layer (mass ratio of complex A and polyvinyl carbazole is 5:95). A film was formed by spin coating to obtain a light emitting layer. The thickness of this light emitting layer was 70 nm. Subsequently, the substrate thus formed is mounted on a substrate holder of a vacuum deposition apparatus, and 20-nm-thick bathocuproine (BCP) and then 20-nm-thick tris (8-hydroxyquinoline) aluminum (Alq) are vacuum-deposited. Was formed. This BCP film functions as a hole barrier layer, and the Alq film functions as an electron transport layer. Further, a 1 nm-thick lithium fluoride film was formed by a vacuum evaporation method to form an electron injection layer. Finally, an aluminum cathode was formed by a vacuum vapor deposition method to produce an organic electroluminescence element.

<Evaluation>
When the organic electroluminescence element obtained in Example 16 was used and a DC voltage of 15 V was applied with the Al electrode minus and the ITO electrode plus, 32 cd / m ² of green light emission was observed.

The emission spectrum of the complex A is shown. The emission spectrum of Complex B is shown. The emission spectrum of Complex C is shown. The emission spectrum of Complex D is shown. The emission spectrum of the complex E is shown. The emission spectrum of the complex F is shown. The emission spectrum of the complex G is shown. The emission spectrum of the complex H is shown. The emission spectrum of Complex J is shown. The emission spectrum of the complex K is shown. The emission spectrum of the complex L is shown. The emission spectrum of the complex M is shown. The emission spectrum of the complex N is shown. The emission spectrum of the complex O is shown.

Claims (10)

A mononuclear monovalent copper complex represented by the following formula (1).

Wherein X and Y are each independently N or CR ₆ , and R _{1 to} R ₆ are each independently hydrogen, halogen, a C ₁ -C ₄₀ substituted or unsubstituted alkyl group, C ₂ -C ₄₀ substituted or unsubstituted alkenyl groups, C _{6 to} C ₄₀ substituted or unsubstituted aryl groups, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl groups, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group C ₆ -C _40, a substituted or unsubstituted alkylthio group of C ₁ -C _40, adjacent groups of R ₁ to R ₆ are bonded to each other to form a ring L ₁ and L ₂ are each independently a ligand containing an element selected from nitrogen, phosphorus and arsenic, and L ₁ and L ₂ are bonded to each other to form a bidentate ligand. It may be formed.) The copper complex according to claim 1, wherein X is CR ₆ and Y is N. X is N, copper complex according to claim 1 Y is CR _6. L ₁ and L ₂ are each independently a ligand containing an element selected from nitrogen and phosphorus, and are bonded to each other to form a bidentate ligand. The described copper complex. The L ₁ and L ₂ are bidentate ligands bonded to each other, and the ligand forms a bidentate phosphine represented by the following formula (2). Copper complex.

(Wherein R _{10 to} R ₁₃ are each independently hydrogen, halogen, a C _{1 to} C ₄₀ substituted or unsubstituted alkyl group, a C _{2 to} C ₄₀ substituted or unsubstituted alkenyl group, C _{6 to} C _40, Substituted or unsubstituted aryl group, C _{3 to} C ₄₀ substituted or unsubstituted heteroaryl group, C _{1 to} C ₄₀ substituted or unsubstituted alkoxy group, C _{6 to} C ₄₀ substituted or unsubstituted aryl oxy group, a substituted or unsubstituted alkylthio group of C ₁ ~C _40, R ₁₀ and R ₁₁ and / or R ₁₂ and R ₁₃ may bond together to form a ring, Q is C ₁ ~ C ₆ substituted or unsubstituted alkylidene group, C _{2 to} C ₆ substituted or unsubstituted alkenylidene group, C _{6 to} C ₄₀ substituted or unsubstituted arylene group, C _{3 to} C ₄₀ substituted or unsubstituted Heteroarylene group.) Q is halogen, C ₁ -C ₄₀ substituted or unsubstituted alkyl group, C ₆ -C ₄₀ substituted or unsubstituted good following structure be substituted with an aryl group of;

The copper complex according to claim 5, which is an organic group selected from:   The luminescent material containing the copper complex of any one of Claims 1-6.   The material for organic electroluminescent elements containing the copper complex of any one of Claims 1-6.   A cathode, an anode, and an organic layer composed of one or more layers sandwiched between the cathode and the anode, the organic layer including at least a light emitting layer, and at least one layer of the organic layer The organic electroluminescent element containing the organic electroluminescent element material of Claim 8.   The apparatus which has an organic electroluminescent element of Claim 9.

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