JP2009143894A - Polynuclear complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive metal complex useful as a light-emitting material. <P>SOLUTION: Disclosed is a polynuclear complex represented by formula (I) (in the formula (I), M is a group 11 metal atom or metal ion; (a) is a number of ≥2; Ar is a tetravalent organic group; b is a number of ≥1; R is a hydrocarbon group; Q is a ligand having a coordinating atom selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom; c is a number of ≥0; X is a counter ion; and d is a number of ≥0). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polynuclear complex.

  As a light-emitting material used for an organic EL element or the like, a phosphorescent material considered to have higher light emission efficiency than a fluorescent material has attracted attention, and among them, an iridium complex is considered promising. However, since this complex uses iridium, which is a rare metal, its use is limited in terms of price, amount of resources, and the like. For this reason, various studies have been made on inexpensive metal complexes (see Non-Patent Document 1).

Coord. Chem. Rev. 250, 2093-2126 (2006)

However, known inexpensive metal complexes do not always have sufficient performance and are not necessarily useful as light emitting materials.
Therefore, the present invention provides an inexpensive metal complex useful as a light-emitting material.

（式（Ｉ）中、Ｍは１１族の金属原子又は金属イオンを表し、ａは２以上の数を表す。複数個のＭはそれぞれ同一であっても異なっていてもよい。Ａｒは芳香環を含む４価の有機基を表し、ｂは１以上の数を表す。Ａｒが複数存在する場合、それぞれ同一であっても異なっていてもよい。Ｒは置換されてもよい炭化水素基を表す。複数のＲは、それぞれ同一であっても異なっていてもよい。Ｑは窒素原子、リン原子、酸素原子及び硫黄原子からなる群から選ばれる配位原子を持つ配位子を表し、ｃは０以上の数である。Ｑが複数存在する場合、それらは、同一であっても異なっていてもよい。Ｘはカウンターイオンを表し、ｄは０以上の数である。Ｘが複数存在する場合、それぞれ同一であっても異なっていてもよい。） That is, the present invention provides a polynuclear complex represented by the following formula (I).

(In formula (I), M represents a group 11 metal atom or metal ion, a represents a number of 2 or more, and a plurality of M may be the same or different. Ar represents an aromatic ring. And b represents a number of 1 or more, and when a plurality of Ars are present, they may be the same or different, and R represents a hydrocarbon group that may be substituted. A plurality of R may be the same or different, Q represents a ligand having a coordination atom selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom, and c is It is a number greater than or equal to 0. When there are a plurality of Qs, they may be the same or different, X represents a counter ion, and d is a number greater than or equal to 0. When there are a plurality of Xs Each may be the same or different.)

  The polynuclear complex of the present invention is an inexpensive metal complex and is useful as a light emitting material.

  In the above formula (I), M represents a Group 11 metal atom or metal ion, and a plurality of M may be the same or different. The metal atom or metal ion is preferably copper or silver, and more preferably copper.

  From the viewpoint of the valence, the metal atom and metal ion can be appropriately selected from those normally present in nature. For example, in the case of copper, one having a mixed valence in which monovalent or divalent copper or both are mixed can be used. Especially, it is preferable that a metal ion is a copper (I) ion.

  a represents a number of 2 or more, and is represented as an average value when the polynuclear complex represented by the formula (I) is a mixture. a is preferably a number of 2 to 100, more preferably a number of 2 to 20, still more preferably a number of 2 to 10, and particularly preferably a number of 2 to 6.

  In the above formula (I), Ar represents a tetravalent organic group containing an aromatic ring, and when a plurality of Ar are present, they may be the same or different. The tetravalent organic group containing an aromatic ring is a group having four hydrogen atoms from a compound containing an aromatic ring.

  Here, as a compound containing an aromatic ring, a compound in which two or more selected from a monocyclic aromatic compound and a condensed aromatic compound are bonded directly or via a divalent group, a monocyclic aromatic compound , Condensed ring aromatic compounds and the like. Here, as the divalent group, a divalent group containing two or more atoms selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a carbon atom which may have a substituent, Examples thereof include an oxygen atom, a sulfur atom, a nitrogen atom which may have a substituent, and a phosphorus atom which may have a substituent.

  Specific examples of the compound containing an aromatic ring include benzene, naphthalene, ethanoanthracene, anthracene, dihydroanthracene, anthraquinone, biphenylene, pyrene, perylene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl disulfide, diphenylacetylene, stilbene, diphenylamine, diphenylphosphine. Benzophenone, p-terphenyl, binaphthyl, phenazine, thianthrene, bipyridine, bithiophene, bipyrrole and the like.

  Specific examples of Ar include benzene-1,2,4,5-tetrayl group, benzene-1,2,3,4-tetrayl group, naphthalene-1,2,5,6-tetrayl group, naphthalene-2 , 3,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, naphthalene-1,4,5,8-tetrayl group, anthracene-1,2,5,6-tetrayl group, anthracene -2,3,6,7-tetrayl group, anthracene-2,3,5,6-tetrayl group, anthracene-1,5,9,10-tetrayl group, anthracene-1,4,5,10-tetrayl group 9,10-dihydroanthracene-1,2,5,6-tetrayl group, 9,10-dihydroanthracene-2,3,6,7-tetrayl group, 9,10-dihydroanthracene-2,3,5, 6 Tetrayl group, ethanoanthracene-1,2,5,6-tetrayl group, ethanoanthracene-2,3,6,7-tetrayl group, ethanoanthracene-2,3,5,6-tetrayl group, anthraquinone-1,2 , 5,6-tetrayl group, anthraquinone-2,3,6,7-tetrayl group, anthraquinone-2,3,5,6-tetrayl group, biphenylene-1,2,5,6-tetrayl group, biphenylene-2 , 3,6,7-tetrayl group, biphenylene-1,2,7,8-tetrayl group, biphenylene-1,4,5,8-tetrayl group, pyrene-1,2,6,7-tetrayl group, pyrene -4,5,9,10-tetrayl group, pyrene-1,5,6,10-tetrayl group, pyrene-1,2,7,8-tetrayl group, pyrene-1,8,9,10-teto Yl group, pyrene-1,3,4,10-tetrayl group, perylene-1,2,7,8-tetrayl group, perylene-2,3,8,9-tetrayl group, perylene-3,4,9, 10-tetrayl group, perylene-1,2,5,6-tetrayl group, perylene-2,3,4,5-tetrayl group, biphenyl-2,2 ′, 3,3′-tetrayl group, biphenyl-3, 3 ′, 4,4′-tetrayl group, diphenyl ether-2,2 ′, 3,3′-tetrayl group, diphenyl ether-3,3 ′, 4,4′-tetrayl group, diphenyl sulfide-2,2 ′, 3 , 3′-tetrayl group, diphenyl sulfide-3,3 ′, 4,4′-tetrayl group, diphenyl disulfide-2,2 ′, 3,3′-tetrayl group, diphenyl disulfide-3,3 ′, 4,4 '-Tetrayl group, dipheny Acetylene-2,2 ′, 3,3′-tetrayl group, diphenylacetylene-3,3 ′, 4,4′-tetrayl group, stilbene-2,2 ′, 3,3′-tetrayl group, stilbene-3, 3 ′, 4,4′-tetrayl group, diphenylamine-2,2 ′, 3,3′-tetrayl group, diphenylamine-3,3 ′, 4,4′-tetrayl group, diphenylphosphine-2,2 ′, 3 , 3′-tetrayl group, diphenylphosphine-3,3 ′, 4,4′-tetrayl group, benzophenone-2,2 ′, 3,3′-tetrayl group, benzophenone-3,3 ′, 4,4′- Tetrayl group, p-terphenyl-2,2 ′ ′, 3,3 ′ ′-tetrayl group, p-terphenyl-3,3 ′ ′, 4,4 ′ ′-tetrayl group, binaphthyl-2,2 ′, 3,3′-tetrayl group, binaphthyl-3,3 ′, 4,4′-tetra Yl group, binaphthyl-4,4 ′, 5,5′-tetrayl group, binaphthyl-5,5 ′, 6,6′-tetrayl group, binaphthyl-6,6 ′, 7,7′-tetrayl group, binaphthyl- 7,7 ′, 8,8′-tetrayl group, phenazine-1,2,5,6-tetrayl group, phenazine-2,3,6,7-tetrayl group, phenazine-2,3,5,6-tetrayl Group, phenazine-1,5,9,10-tetrayl group, phenazine-1,4,5,10-tetrayl group, thianthrene-1,2,5,6-tetrayl group, thianthrene-2,3,6,7 -Tetrayl group, thianthrene-2,3,5,6-tetrayl group, thianthrene-1,5,9,10-tetrayl group, thianthrene-1,4,5,10-tetrayl group, 2,2'-bipyridine- 3,3 ', 4,4'-tetry Group, 2,2′-bipyridine-4,4 ′, 5,5′-tetrayl group, 2,2′-bipyridine-5,5 ′, 6,6′-tetrayl group, 3,3′-bipyridine-4 , 4 ′, 5,5′-tetrayl group, 3,3′-bipyridine-5,5 ′, 6,6′-tetrayl group, 4,4′-bipyridine-2,2 ′, 3,3′-tetrayl Group, 2,2′-bithiophene-3,3 ′, 4,4′-tetrayl group, 2,2′-bithiophene-4,4 ′, 5,5′-tetrayl group, 3,3′-bithiophene-4 , 4 ′, 5,5′-tetrayl group, 2,2′-bipyrrole-3,3 ′, 4,4′-tetrayl group, 2,2′-bipyrrole-4,4 ′, 5,5′-tetrayl Group, 3,3′-bipyrrole-4,4 ′, 5,5′-tetrayl group and the like.

  Among these, from the viewpoint of ease of synthesis or luminous performance, benzene-1,2,4,5-tetrayl group, benzene-1,2,3,4-tetrayl group, naphthalene-1,2 are preferable. , 5,6-tetrayl group, naphthalene-2,3,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, naphthalene-1,4,5,8-tetrayl group, biphenyl-2 , 2 ′, 3,3′-tetrayl group, biphenyl-3,3 ′, 4,4′-tetrayl group, diphenyl ether-2,2 ′, 3,3′-tetrayl group, diphenyl ether-3,3 ′, 4 , 4′-tetrayl group, diphenyl sulfide-2,2 ′, 3,3′-tetrayl group, diphenyl sulfide-3,3 ′, 4,4′-tetrayl group, diphenylamine-2,2 ′, 3,3 ′ -Tetrayl group, diphe Luamine-3,3 ′, 4,4′-tetrayl group, diphenylphosphine-2,2 ′, 3,3′-tetrayl group, diphenylphosphine-3,3 ′, 4,4′-tetrayl group, benzophenone-2 , 2 ′, 3,3′-tetrayl group, benzophenone-3,3 ′, 4,4′-tetrayl group, 2,2′-bipyridine-3,3 ′, 4,4′-tetrayl group, 2,2 '-Bipyridine-4,4', 5,5'-tetrayl group, 2,2'-bipyridine-5,5 ', 6,6'-tetrayl group, 3,3'-bipyridine-4,4', 5 , 5′-tetrayl group, 3,3′-bipyridine-5,5 ′, 6,6′-tetrayl group, 4,4′-bipyridine-2,2 ′, 3,3′-tetrayl group, 2,2 '-Bithiophene-3,3', 4,4'-tetrayl group, 2,2'-bithiophene-4,4 ', 5,5'-tetrayl group, 3 3′-bithiophene-4,4 ′, 5,5′-tetrayl group, 2,2′-bipyrrole-3,3 ′, 4,4′-tetrayl group, 2,2′-bipyrrole-4,4 ′, 5,5′-tetrayl group, 3,3′-bipyrrole-4,4 ′, 5,5′-tetrayl group, more preferably benzene-1,2,4,5-tetrayl group, benzene-1 , 2,3,4-tetrayl group, naphthalene-1,2,5,6-tetrayl group, naphthalene-2,3,6,7-tetrayl group, naphthalene-1,2,7,8-tetrayl group, naphthalene -1,4,5,8-tetrayl group, biphenyl-2,2 ′, 3,3′-tetrayl group, biphenyl-3,3 ′, 4,4′-tetrayl group, particularly preferably benzene- 1,2,4,5-tetrayl group, naphthalene-1,2,5,6-tetrayl , Naphthalene-2,3,6,7-tetrayl group, naphthalene-1,4,5,8-tetrayl group, biphenyl-2,2 ′, 3,3′-tetrayl group, biphenyl-3,3 ′, 4 , 4′-tetrayl group and the like.

  Ar may have a substituent, such as a halogen atom, a hydroxyl group, a hydrocarbon oxy group, a mercapto group, a hydrocarbon mercapto group, an amino group, a hydrocarbon amino group, a nitro group, a cyano group, Examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. In the case of substitution with an alkyl group, alkenyl group, cycloalkyl group, aryl group or aralkyl group, specific examples and preferred examples thereof are the same as those for R shown below.

  In the above formula (I), R represents a hydrocarbon group which may be substituted, and a plurality of R may be the same or different.

  The hydrocarbon group usually has about 1 to 20 carbon atoms. Examples thereof include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2-methyl group. Alkyl groups such as -1-propyl group, 2-methyl-2-propyl group, pentyl group, hexyl group, decyl group, and eicosyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group; ethynyl group, propynyl group, Alkynyl groups such as butynyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group; cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group, cyclohexenyl group; phenyl group 2-tolyl group, 3-tolyl group, 4-tolyl group, xylyl group, mesityl group, biphenyl group, Aryl groups such as til group, indenyl group and fluorenyl group; aralkyl groups such as benzyl group and xylyl group are mentioned, preferably alkyl group, aryl group and aralkyl group, more preferably aryl group and aralkyl group, More preferably, it is an aryl group.

  When the hydrocarbon group has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a hydrocarbon oxy group, a mercapto group, a hydrocarbon mercapto group, an amino group, a hydrocarbon amino group, a nitro group, and a cyano group. Can be mentioned.

  The hydrocarbon oxy group, hydrocarbon mercapto group, and hydrocarbon amino group are hydroxyl groups, mercapto groups, and amino groups in which hydrogen atoms are substituted with hydrocarbon groups. Specific examples and preferred examples of hydrocarbon groups in that case Are the same as those of R.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably they are a fluorine atom and a chlorine atom, More preferably, it is a fluorine atom.

In the formula (I), examples of the structure represented by Ar (PR ₂ ) ₄ include the structures exemplified below.

  In the formula (I), b represents a number of 1 or more, and when the polynuclear complex represented by the formula (I) is a mixture, it is represented as an average value. b is preferably a number of 1 to 100, more preferably a number of 1 to 20, still more preferably a number of 1 to 9, and particularly preferably a number of 1 to 5.

  As for the ratio of a and b, from the viewpoint of the stability of the complex, the upper limit of a / b is preferably 3, more preferably 2.5, and even more preferably 2. Further, the lower limit of a / b is preferably 0.3, more preferably 0.5, and even more preferably 1.

  Further, regarding the relationship between a and b, from the viewpoint of the stability of the complex, a-2 ≦ b ≦ a + 1 is preferable, and a-1 ≦ b ≦ a is more preferable. More preferably, it is b.

  In the formula (I), Q represents a ligand having a coordination atom selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. May be different. Q coordinates to M's vacant coordination position. The ligand may be either a monodentate ligand or a polydentate ligand. When the ligand is a polydentate ligand, the plurality of coordination atoms may be the same or different. Among the ligands, a ligand having a coordination atom selected from nitrogen, oxygen and phosphorus is preferable, and a ligand having a coordination atom selected from nitrogen and phosphorus is more preferable.

Here, as monodentate ligands, phosphines such as triphenylphosphine, tri (p-tolyl) phosphine, tri (p-methoxyphenyl) phosphine, tri (p-fluorophenyl) phosphine; pyridine, picoline, p- Pyridines such as t-butylpyridine and quinoline; nitrogen-containing heterocyclic compounds such as pyrrole, pyrazole and imidazole; triethylamine, tripropylamine, tributylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, piperidine, piperazine, aniline , N-methylaniline, N, N-dimethylaniline, diphenylamine and other amines; diethyl ether, tetrahydrofuran, tetrahydropyran, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether Ethers such as tellurium; sulfides such as dimethyl sulfide, diethyl sulfide, and tetrahydrothiophene; thiolates such as methanethiolate, ethanethiolate, 2-propanethiolate, 2-methyl-2-propanethiolate, and benzenethiolate, and their substitution The one with the group is mentioned. As the substituent, specific examples and preferred examples are the same as those in Ar.
As the polydentate ligand, bis (diphenylphosphino) methane, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) benzene, bis (diphenylphosphino) naphthalene, Diphosphines such as bis (diphenylphosphino) biphenyl and bis (diphenylphosphino) binaphthyl; diimines such as bipyridine, phenanthroline, neocuproin, bathophenanthroline and bathocuproin; and carbochelates such as acetate, propionate, pivalonate and benzoate; , Β-diketonates such as 1,3-diphenyl-1,3-propanedionate, 1,1,1,3,3,3-hexafluoroacetylacetonate; ethanedithiolate, propanedi Dithiolates such as oleate and benzenedithiolate; having different coordination atoms such as diphenylphosphino-2-pyridine, 2-diphenylphosphino-2-dimethylamino-1,1-biphenyl, 2-aminoethyl-diphenylphosphine Bidentate ligand; tridentate ligand such as 2,6-bis (2-pyridyl) pyridine, diethylenetriamine, 1,4,7-triazacyclononane; triethylenetetramine, 1,4,7,10- Examples thereof include tetradentate ligands such as tetraazacyclododecane and 1,4,8,11-tetraazacyclotetradecane, and those having a substituent added thereto. As the substituent, specific examples and preferred examples are the same as those in Ar.
Among the ligands represented by Q, preferred are phosphines, pyridines, nitrogen-containing heterocyclic compounds, amines, ethers, diphosphines, diimines, β-diketonates, different coordination atoms. More preferred are phosphines, pyridines, amines, ethers, diphosphines, diimines, bidentate ligands having different coordination atoms, and more preferred are , Pyridines, ethers, diphosphines, diimines, and bidentate ligands having different coordination atoms.

In the formula (I), c is a number of 0 or more, and when the polynuclear complex represented by the formula (I) is a mixture, it is represented as an average value, and an analytical method for obtaining a molar ratio with b (for example, ¹ H NMR). Preferably it is a number of 0-100, More preferably, it is a number of 0-20, More preferably, it is a number of 0-10, Most preferably, it is a number of 0-4.

  X is a counter ion. Examples of the counter ion include a counter anion and a counter cation, and those containing a counter anion are preferable from the viewpoint of keeping the complex neutral.

  The counter anion is preferably a Bronsted acid conjugate base, more preferably a Bronsted acid conjugate base containing a hetero atom. Examples of the counter anion include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, acetate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, Methanesulfonate ion, trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, dodecylbenzenesulfonate ion, tetraphenylborate ion, tetrakis (pentafluorophenyl) borate ion, these ions And a polymer compound containing a repeating unit having the following structure, preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, tetrafluoroborate ion, hexa Le Oro phosphate ion, trifluoromethanesulfonate ion, a tetraphenylborate ion, tetrakis (pentafluorophenyl) borate ion.

  As the counter cation, a metal cation such as an alkali metal or an alkaline earth metal, a quaternary ammonium ion, a quaternary phosphonium ion, a polymer compound containing a repeating unit having a structure of these ions, or the like can be preferably used. Is a quaternary ammonium ion or a quaternary phosphonium ion.

  d is a number of 0 or more, and is determined so as to maintain neutrality as the polynuclear complex represented by the formula (I). When the polynuclear complex represented by the formula (I) is a mixture, it is represented as an average value. . d is preferably a number from 0 to 100, more preferably a number from 0 to 20, even more preferably a number from 0 to 10, and particularly preferably a number from 0 to 6.

Specific examples of the polynuclear complex of the present invention include the complexes shown below.
Each of them has a charge of (m + 1) +, and X in the formula (I) is omitted in the figure below. a, b and c are as defined above, c ¹ and c ² are numbers of 0 or more (usually, c ¹ and c ² are integers of 0 or more), and c ¹ + c ² = c.

The polynuclear complex of the present invention includes, for example, a ligand Q (for example, 1,2-bis (diphenylphosphino) benzene or tetrahydrofuran) and a metal salt corresponding to M (for example, tetrakis (acetonitrile) copper (I) trifluoro). And then reacting with a ligand compound Ar (PR ₂ ) ₄ (for example, 1,2,4,5-tetrakis (diphenylphosphino) benzene). It can manufacture by making it react.

  The polynuclear complex of the present invention preferably has a light-emitting property, and more preferably has a phosphorescence-emitting property from the viewpoint of light emission efficiency.

The light emitting device of the present invention includes the multinuclear complex of the present invention.
As the light-emitting element of the present invention, in a light-emitting element in which a single-layer or multiple-layer thin film layer having at least a light-emitting layer is sandwiched between a pair of electrodes composed of an anode and a cathode, at least one of the thin-film layers is The thing containing the polynuclear complex of this invention is mentioned.

  As content of the multinuclear complex of this invention in the thin film layer containing the multinuclear complex of this invention, it is 0.1-100 weight% normally with respect to the weight of the whole layer, and 0.1-30 weight% is 0.1 to 30 weight%. Preferably, 0.5 to 15% by weight is more preferable, and 1 to 10% by weight is particularly preferable. As the light emitting device of the present invention, the light emitting layer preferably contains the polynuclear complex of the present invention as a material for emitting light.

Examples of the light emitting device of the present invention include a single layer type (anode / light emitting layer / cathode), and this light emitting layer contains the polynuclear complex of the present invention. In addition, as a layer configuration of the multilayer light emitting element,
(A) anode / hole injection layer / (hole transport layer) / light emitting layer / cathode (b) anode / light emitting layer / electron injection layer / (electron transport layer) / cathode (c) anode / hole injection layer / (Hole transport layer) / light emitting layer / electron injection layer / (electron transport layer) / cathode and the like.
In the above (a) to (c), (hole transport layer) and (electron transport layer) indicate that these layers may or may not exist at the positions.

  The anode of the light emitting device of the present invention supplies holes to a hole injection layer, a hole transport layer, a light emitting layer and the like, and it is effective to have a work function of 4.5 eV or more. As the material of the anode, metals, alloys, metal oxides, electrically conductive compounds, mixtures thereof, and the like can be used. Specifically, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), metals such as gold, silver, chromium, and nickel, and these conductive metal oxides and metals And an inorganic conductive material such as copper iodide and copper sulfide, an organic conductive material such as polyaniline, polythiophene [PEDOT] and polypyrrole, and a laminate of these with ITO.

  The cathode of the light emitting device of the present invention supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer and the like. As the material of the cathode, metals, alloys, metal halides, metal oxides, electrically conductive compounds, mixtures thereof, and the like can be used. Specific examples of cathode materials include alkali metals (Li, Na, K, etc.) and their fluorides and oxides, alkaline earth metals (Mg, Ca, Ba, Cs, etc.), their fluorides and oxides, gold Silver, lead, aluminum, alloys and mixed metals (sodium-potassium alloy, sodium-potassium mixed metal, lithium-aluminum alloy, lithium-aluminum mixed metal, magnesium-silver alloy, magnesium-silver mixed metal, etc.), indium, And rare earth metals such as ytterbium.

  The hole injection layer and the hole transport layer of the light emitting device of the present invention have any one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. If it is, Known materials can be appropriately selected and used for the hole injection layer and the hole transport layer. Specific examples of materials used for these layers include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives. , Imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amines Compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organosilane derivatives, polynuclear complexes of the present invention, and the like Coalescence, and the like. Examples of the material include conductive polymer oligomers such as aniline copolymers, thiophene oligomers, and polythiophene. The material may be a single component or a composition comprising a plurality of components. Further, the hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. May be.

  The electron injection layer and the electron transport layer of the light emitting device of the present invention have any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. I just need it. Known materials can be appropriately selected and used for the electron injection layer and the electron transport layer. Specific examples of materials used for these layers include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, and fluorenone. Derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic ring tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives , 8-quinolinol derivative metal complexes, metal phthalocyanines, various metal complexes represented by metal complexes having benzoxazole or benzothiazole as a ligand, organic silane derivatives, the polynuclear complex of the present invention, and the like. In addition, the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

  In the light-emitting element of the present invention, an insulator or a semiconductor inorganic compound can also be used as a substance constituting the electron injection layer and the electron transport layer. If the electron injection layer and the electron transport layer are made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved. Such an insulator is selected from the group consisting of alkali metal chalcogenides (hereinafter “chalcogenide” includes oxides), alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. At least one metal compound can be used. Specifically, preferred alkaline earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS, and CaSe. Further, as a semiconductor constituting the electron injection layer and the electron transport layer, at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn is used. One kind alone or a combination of two or more kinds of oxides, nitrides, oxynitrides, and the like may also be included.

  Moreover, in this invention, the reducing dopant may be added to the interface area | region with the thin film which contact | connects a cathode. Preferred reducing dopants include alkali metals, alkaline earth metal oxides, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metals. And at least one compound selected from the group consisting of rare earth metal oxides or rare earth metal halides, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes.

  The light-emitting layer of the light-emitting element of the present invention can inject holes from the anode or the hole injection layer when an electric field is applied, and can inject electrons from the cathode or the electron injection layer. It has a function of moving holes) by the force of an electric field, a field of recombination of electrons and holes, and a function of connecting this to light emission. The light emitting layer of the light emitting device of the present invention preferably contains the multinuclear complex of the present invention, and may contain a host material using the multinuclear complex as a guest material. Examples of the host material include those having a fluorene skeleton, those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And the like. The host material T1 (energy level of the lowest triplet excited state) is preferably larger than that of the guest material, and more preferably the difference is larger than 0.2 eV. The host material may be a low molecular compound or a high molecular compound. In addition, a light-emitting layer in which the host material is doped with the host material can be formed by mixing and applying the host material and a light-emitting material such as the polynuclear complex, or by co-evaporation.

  In the light emitting device of the present invention, a method for forming each layer is not particularly limited, and a known method can be used. Specific examples of the forming method include a vacuum deposition method (resistance heating deposition method, electron beam method, etc.), sputtering method, LB method, molecular lamination method, coating method (casting method, spin coating method, bar coating method, Blade coating method, roll coating method, gravure printing, screen printing, ink jet method, etc.]. Among these, it is preferable to form a film by coating because the manufacturing process can be simplified. In the coating method, the polynuclear complex of the present invention can be mixed with a solvent to prepare a coating solution, and the coating solution can be formed on a desired layer (or electrode) by coating and drying. The coating liquid may contain a resin as a host material and / or a binder, and the resin can be dissolved in a solvent or dispersed. As the resin, a non-conjugated polymer (for example, polyvinyl carbazole) or a conjugated polymer (for example, a polyolefin-based polymer) can be used. More specifically, for example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin. , Polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like. The solution may contain an antioxidant, a viscosity modifier and the like as subcomponents depending on the purpose.

  As the solvent of the solution, a stable one in which the components of the thin film are uniformly dissolved or dispersed can be appropriately selected from known solvents. Examples of such solvents include alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), organic chlorines (chloroform, 1,2-dichloroethane, etc.), and aromatic hydrocarbons (benzene, toluene). , Xylene, etc.], aliphatic hydrocarbons [normal hexane, cyclohexane, etc.], amides [dimethylformamide, etc.], sulfoxides [dimethyl sulfoxide, etc.] and the like. The solvent may be a single component or a mixture of a plurality of components.

  In the ink jet method, known components can be used for ink ejection and reproducibility. For example, a solvent having a high boiling point (such as anisole or bicyclohexylbenzene) can be used as a component in order to suppress evaporation from the nozzle. Moreover, it is preferable that the viscosity of the solution used as the ink is selected from 1 to 100 mPa · s by selecting the components.

  The preferred film thickness of each organic layer of the light emitting device of the present invention varies depending on the type of material and the layer structure and is not particularly limited, but in general, if the film thickness is too thin, defects such as pinholes are likely to occur. If it is too high, a high applied voltage is required and the efficiency is deteriorated. Therefore, the range of several nm to 1 μm is usually preferable.

  The light emitting device of the present invention can be used for, for example, an illumination light source, a sign light source, a backlight light source, a display device, a printer head, and the like. As the display device, a known drive technology, drive circuit, or the like can be used to select a segment type, a dot matrix type, or the like.

  Next, other uses of the multinuclear complex of the present invention will be described. The polynuclear complex of the present invention can be used for known uses of the polynuclear complex by appropriately selecting its structure. Examples of such applications include catalysts and magnetic materials. Examples of the catalyst include those used for reactions such as oxidation-reduction reactions.

化合物（１）
２−（ジフェニルホスフィノ）−２'−（Ｎ，Ｎ−ジメチルアミノ）−ビフェニル４０ｍｇをＴＨＦ（２ｍＬ）に溶解し、テトラキス（アセトニトリル）銅（Ｉ）トリフルオロメタンスルホン酸塩４０ｍｇを加え、１時間反応させ、ほぼ無色に近い淡黄色透明の溶液を得た。この溶液を、１，２，４，５−テトラキス（ジフェニルホスフィノベンゼン）４０ｍｇのＴＨＦ（２ｍＬ）溶液に加えると、淡黄色沈殿が生成した。２時間攪拌を継続して反応させた後、ジエチルエーテル（８ｍＬ）を加えて析出させた沈殿を濾過して集め、さらにジエチルエーテル（２ｍL）で２回洗浄し、さらに乾燥させることで化合物（１）を得た。アセトニトリル−ｄ₃で¹Ｈ ＮＭＲを測定し、積分比から２つのリン配位子やＴＨＦ分子の数を決定して、上記化学式の組成であると推定した。これを基にした元素分析計算値Ｃ（６３．４５％）、Ｈ（４．１９％）、Ｎ（０．２１％）／測定値Ｃ（６２．９３％）、Ｈ（４．２０％）、Ｎ（０．３３％）。この化合物の粉末が０．２重量％になるように、ポリメチルメタクリレートの０．８重量％トルエン溶液に懸濁させた液を石英板にスピンコートして薄膜を得て、蛍光分光光度計（ＪＯＢＩＮＹＶＯＮ−ＳＰＥＸ社製、Ｆｌｕｏｒｏｌｏｇ）を用いて、励起波長３５０ｎｍでの発光スペクトルを測定した。発光極大は５６９ｎｍであった。 Example 1

Compound (1)
40 mg of 2- (diphenylphosphino) -2 ′-(N, N-dimethylamino) -biphenyl is dissolved in THF (2 mL), and 40 mg of tetrakis (acetonitrile) copper (I) trifluoromethanesulfonate is added for 1 hour. Reaction was performed to obtain a light yellow transparent solution almost colorless. When this solution was added to a solution of 40 mg of 1,2,4,5-tetrakis (diphenylphosphinobenzene) in THF (2 mL), a pale yellow precipitate was formed. After continuing the reaction for 2 hours, the reaction was continued by adding diethyl ether (8 mL), and the deposited precipitate was collected by filtration, further washed twice with diethyl ether (2 mL), and further dried to give compound (1 ) ¹ H NMR was measured with acetonitrile-d ₃ , and the number of two phosphorus ligands and THF molecules were determined from the integration ratio, and the composition of the above chemical formula was estimated. Elemental analysis calculation values C (63.45%), H (4.19%), N (0.21%) / measured value C (62.93%), H (4.20%) based on this , N (0.33%). A thin film is obtained by spin-coating a liquid suspended in a 0.8% by weight toluene solution of polymethyl methacrylate so that the powder of this compound is 0.2% by weight on a quartz plate. The emission spectrum at an excitation wavelength of 350 nm was measured using JOBLOGY VON-SPEX (Fluorolog). The emission maximum was 569 nm.

化合物（２）
実施例１と同様にして、２−（ジフェニルホスフィノ）−２'−（Ｎ，Ｎ−ジメチルアミノ）−ビフェニル４０ｍｇの代わりに２，２'−ビス（ジフェニルホスフィノ）−１，１'−ビナフチル６０ｍｇを用いて、化合物（２）を得た。アセトニトリル−ｄ₃で¹Ｈ ＮＭＲを測定し、積分比から２つのリン配位子やＴＨＦ分子の数を決定して、上記化学式の組成であると推定した。これを基にした元素分析計算値Ｃ（６４．４３％）、Ｈ（４．２７％）／測定値Ｃ（６５．９５％）、Ｈ（４．５１％）。
実施例１と同様にして、薄膜を得て、発光スペクトルを測定した。発光極大は５６４ｎｍであった。 Example 2

Compound (2)
In the same manner as in Example 1, instead of 40 mg of 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) -biphenyl, 2,2'-bis (diphenylphosphino) -1,1'- Compound (2) was obtained using 60 mg of binaphthyl. ¹ H NMR was measured with acetonitrile-d ₃ , and the number of two phosphorus ligands and THF molecules were determined from the integration ratio, and the composition of the above chemical formula was estimated. Elemental analysis calculated values C (64.43%), H (4.27%) / measured values C (65.95%), H (4.51%) based on this.
In the same manner as in Example 1, a thin film was obtained and the emission spectrum was measured. The emission maximum was 564 nm.

化合物（３）
実施例１と同様にして、２−（ジフェニルホスフィノ）−２'−（Ｎ，Ｎ−ジメチルアミノ）−ビフェニル４０ｍｇの代わりに１，２−ビス（ジフェニルホスフィノ）ベンゼン４４ｍｇを用いて、化合物（３）を得た。アセトニトリル−ｄ₃で¹Ｈ ＮＭＲを測定し、積分比から２つのリン配位子やＴＨＦ分子の数を決定して、上記化学式の組成であると推定した。これを基にした元素分析計算値Ｃ（６２．７８％）、Ｈ（４．３５％）／測定値Ｃ（６２．６１％）、Ｈ（４．２６％）。実施例１と同様にして、薄膜を得て、発光スペクトルを測定した。５８１ｎｍにピークをもつ発光スペクトルが観測された。 Example 3

Compound (3)
In the same manner as in Example 1, 44 mg of 1,2-bis (diphenylphosphino) benzene was used instead of 40 mg of 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) -biphenyl. (3) was obtained. ¹ H NMR was measured with acetonitrile-d ₃ , and the number of two phosphorus ligands and THF molecules were determined from the integration ratio, and the composition of the above chemical formula was estimated. Elemental analysis calculated values C (62.78%), H (4.35%) / measured values C (62.61%), H (4.26%) based on this. In the same manner as in Example 1, a thin film was obtained and the emission spectrum was measured. An emission spectrum having a peak at 581 nm was observed.

¹ H NMR spectrum of compound (1) in acetonitrile-d ₃ ¹ H NMR spectrum of compound (2) in acetonitrile-d ₃ ¹ H NMR spectrum of compound (3) in acetonitrile-d ₃

Claims (6)

A polynuclear complex represented by the following formula (I).

(In formula (I), M represents a group 11 metal atom or metal ion, a represents a number of 2 or more, and a plurality of M may be the same or different. Ar represents an aromatic ring. And b represents a number of 1 or more, and when a plurality of Ars are present, they may be the same or different, and R represents a hydrocarbon group that may be substituted. A plurality of R may be the same or different, Q represents a ligand having a coordination atom selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom, and c is It is a number greater than or equal to 0. When there are a plurality of Qs, they may be the same or different, X represents a counter ion, and d is a number greater than or equal to 0. When there are a plurality of Xs Each may be the same or different.)   The polynuclear complex according to claim 1, wherein the counter ion contains a counter anion.   The multinuclear complex according to claim 1 or 2, wherein the counter anion is a conjugate base of Bronsted acid.   The multinuclear complex according to any one of claims 1 to 3, wherein M is a copper atom, a copper ion, a silver atom or a silver ion.   The multinuclear complex according to any one of claims 1 to 4, which has a light-emitting property.   The light emitting element containing the polynuclear complex in any one of Claims 1-5.

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