TW201302768A - Cerium complex and organic electronic element comprising same - Google Patents

Abstract

Provided is a cerium complex having excellent electron-accepting property and hole-accepting property, and represented by the following composition formula(1). (M represents a cerium ion, A represents a carbon atom, a silicon atom, a nitrogen atom, a nitrogen cation, a boron anion, a phosphorus atom or P(=O). When z is 4, m is 1 to 4, when z is 3, m is 1 to 3. D represents a direct bond or a hydrocarbondiyl, G represents a heterocyclic group or a hydrogen atom, L represents a group containing an aromatic 6-member ring having at least two nitrogen atoms, X represents a counter ion, L' represents a monodentate ligand or a bidentate ligand, a represents a number of 1 to 4, b represents a number of 0 to 5, c represents a number of 0 to 5).

Description

Bismuth complex and organic electronic component containing the same

The present invention relates to a ruthenium complex and an organic electronic component containing the ruthenium complex.

It is known that a ruthenium complex of a tetradentate ligand containing a benzimidazole group can be used as a light-emitting material used for a light-emitting layer of an organic electroluminescent device (Non-Patent Document 1).

[Previous Technical Literature] [Non-patent literature]

Non-Patent Document 1: Xiang-Li Zheng, Cheng-Yong Su et al., Angew. Chem. Int. Ed., 46, 7399-7403 (2007)

However, the above-mentioned oxime complexes have low electron acceptability and hole acceptability.

Therefore, an object of the present invention is to provide a ruthenium complex which is excellent in electron acceptability and hole acceptability.

The inventors of the present invention have intensively studied the results, and have completed the inventions [1] to [11] below.

[1] A ruthenium complex represented by the formula (1), (in the formula,

M is a cerium ion.

A is a carbon atom, a halogen atom, a nitrogen atom, a nitrogen cation, a boron anion, a phosphorus atom or P(=O). When A is a carbon atom, a ruthenium atom, a nitrogen cation or a boron anion, z is 4, and m is an integer of 1 to 4. When A is a nitrogen atom, a phosphorus atom or P(=O), z is 3, and m is an integer of 1 to 3.

D is a direct bond or a hydrocarbon diyl group which may have a substituent.

G is a heterocyclic group or a hydrogen atom which may have a substituent.

L is a group containing an aromatic 6-membered ring having two or more nitrogen atoms. If there are a plurality of Ls, each L may be the same or different from each other. If there are several Ds, each D may be the same or different from each other. If there are multiple Gs, each G may be the same or different from each other.

X is a counter ion.

L' represents a single tooth or a 2-dentate ligand.

a is a number from 1 to 4, and b and c are each independently a number from 0 to 5. When a is 2 or more, each A may be the same or different from each other. When b is 2 or more, each X may be the same or different from each other. When c is 2 or more, each L' may be the same or different from each other.

[2] The ruthenium complex according to [1] above, wherein L is a formula (2-1), (2-2) Or the base represented by (2-3), -D’-E-J (2-1)

-D’-J’-E’ (2-2)

-D’-J (2-3) (where,

D' is a direct bond or a hydrocarbon diyl group which may have a substituent.

E is a divalent group having an aromatic 5-membered ring containing a nitrogen atom, or a divalent group having a ring condensed with an aromatic 5-membered ring and an aromatic ring containing a nitrogen atom.

J is a monovalent group having an aromatic 6-membered ring containing two or more nitrogen atoms.

E' is a monovalent group having an aromatic 5-membered ring containing a nitrogen atom, or a monovalent group having a ring condensed with an aromatic ring of a nitrogen-containing atom and an aromatic ring.

J' is a divalent group having an aromatic 6-membered ring containing two or more nitrogen atoms.

The aromatic 5-membered ring, the aromatic 6-membered ring, and the ring condensed from the aromatic 5-membered ring and the aromatic ring may each independently have a substituent. When a plurality of substituents are used, these may be combined with each other. The atoms together form a ring).

[3] The oxime complex according to the above [2], wherein the aromatic 5-membered ring of E or E' is an imidazole ring which may have a substituent.

[4] The oxime complex according to the above [2] or [3], wherein E or E' has a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring, and may have a substituent. Benzimidazole ring.

[5] The oxime complex according to any one of the above [1] to [4] wherein L is a group represented by formula (3) or formula (4), (in the formula,

R ² is a monovalent group, and n is an integer of 0 to 2.

When n is 2, each R ² may be the same or different from each other, and 2 R ² may together form a ring together with the carbon atom to which they are bonded.

D' and J are synonymous with the above)

(in the formula,

p is an integer from 0 to 4.

When p is 2 or more, each R ² may be the same or different from each other, and two R ² bonded to adjacent carbon atoms may together form a ring together with the carbon atom to which they are bonded. R ² , D' and J are synonymous with the above).

[6] The ruthenium complex according to any one of the above [1] to [5] wherein A is a nitrogen atom.

The oxime complex according to any one of the above-mentioned [2], wherein J is a monovalent group represented by the formula (5), (in the formula,

R ³ is a hydrogen atom or a monovalent group. Each R ³ may be the same or different from each other. Q is a nitrogen atom or C(R ³ )).

[8] The ruthenium complex according to any one of the above [1] to [7], which is represented by the composition formula (6) or the composition formula (7), (in the formula,

R ⁴ is a hydrogen atom or a monovalent group, and G' is a heterocyclic group which may have a substituent.

Each R ⁴ may be the same or different from each other. When there are a plurality of G's, each G' may be the same or different from each other, and m' is an integer of 1 to 3.

D, R ² , R ³ , Q, n, M, X, L', b and c are synonymous with the above.

If there are multiple Qs, each Q can be the same or different from each other)

(wherein R ⁴ , G', D, R ² , R ³ , Q, p, m', M, X, L', b and c are synonymous with the above).

[9] The ruthenium complex according to any one of the above [1] to [8], which is represented by the composition formula (7-1), (in the formula,

R ⁵ is a hydrogen atom or a hydrocarbyl group which may have a substituent.

R ² , R ³ , R ⁴ , Q, p, m', M, X, L', b and c are synonymous with the above).

[10] A composition comprising the ruthenium complex and the charge transporting material according to any one of the above [1] to [9].

[11] An organic film comprising the ruthenium complex according to any one of the above [1] to [9].

[12] An organic electronic component comprising the ruthenium complex according to any one of [1] to [9] above.

[13] A compound represented by the formula (8).

(wherein G', D, R ² , R ³ , R ⁴ , Q, p and m' are synonymous with the above).

The ruthenium complex of the present invention exhibits high electron acceptability and hole acceptability. Therefore, charge recombination can be promoted on the ruthenium complex, and excellent luminescence characteristics can be exhibited in the organic electroluminescence device.

The invention is described below.

In the present specification, the phrase "may have a substituent" means a case where a hydrogen atom of a compound or a group described later is unsubstituted, and a case where a part or all of the hydrogen atom is substituted with a substituent. . Examples of the "substituent" include a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbonthio group, a halogen atom, a cyano group, a decylamino group, a quinone imine group, an unsubstituted silyl group, a substituted decyl group, a decyl group, and an alkyl group. An oxycarbonyl group, an alkoxysulfonyl group, an alkoxyphosphoryl group, an unsubstituted phosphino group, a substituted phosphino group, an unsubstituted phosphine oxide group, a substituted phosphorus oxide group, Unsubstituted amino group, substituted amine group, hydroxyl group, mercapto, carboxyl group, sulfo group, phosphate group, phosphite group, nitro group, -NH ^- , -O ^- , -S ^- , -COO ^- And -SO ₃ ^- , -HPO ₄ ^- and -H ₂ PO ₃ ^{- are} preferably a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbonthio group, a halogen atom, a cyano group or a decyl group which may have a substituent, and more preferably a hydrocarbon group.

In addition, in the present specification, when there are a plurality of identical symbols in the same formula, the bases may be the same or different.

When the above group is a group containing a carbon atom and does not contain an aromatic ring, the number of carbon atoms is usually from 1 to 30, and preferably from 1 to 20, more preferably from 1 to 10.

When the above group is a group containing a carbon atom and containing an aromatic ring, the number of carbon atoms is usually from 2 to 36, and preferably from 3 to 26, more preferably from 6 to 16. [0011]

The hydrocarbon group may, for example, be a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group. , dodecyl, 2-ethylhexyl, 3,7-dimethyloctyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl (norbornyl), benzyl, α,α-dimethylbenzyl, 1-phenylethyl, 2-phenylethyl, vinyl, propenyl, butenyl, oleyl, eicosylpentenyl (eicosapentaenyl), docosahexaenyl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl, phenyl, 2-tolyl, 4-tolyl, 4-trifluoromethylphenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, terphenyl, 3,5-di Phenylphenyl, 3,4-diphenylphenyl, pentaphenylphenyl, 4-(2,2-diphenylvinyl)phenyl, 4-(1,2,2-triphenylethylene Phenyl, fluorenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, 2-indenyl, 9-phenanthryl, 1-pyrenyl, chrysenyl, thick Naphthacenyl and coronyl, and preferably methyl , ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, 2- Ethylhexyl, 3,7-dimethyloctyl, benzyl, α,α-dimethylbenzyl, 1-phenylethyl, 2-phenylethyl, vinyl, propenyl, butenyl , phenyl, 2-tolyl, 4-tolyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, terphenyl, anthracenyl, 1-naphthyl or 2-naphthyl, And methyl, ethyl, tert-butyl, 1-propyl, 1-butyl, 2-butyl, isobutyl, pentyl, hexyl, octyl, decyl, ten Diki, 2-ethylhexyl, benzyl, α,α-dimethylbenzyl, vinyl, butenyl, phenyl, 2-tolyl or 4-tolyl is more preferred, but methyl Further, ethyl, 1-propyl, hexyl, 2-ethylhexyl, tert-butyl or vinyl is more preferred.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a 1-propoxy group, a 2-propoxy group, a 1-butoxy group, a 2-butoxy group, an isobutoxy group, and a third butoxy group. Pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, 2-ethylhexyloxy, 3,7-dimethyloctyloxy, cyclopropoxy, cyclopentyloxy, Cyclohexyloxy, 1-adamantyloxy, 2-adamantyloxy, norbornyloxy, benzyloxy, α,α-dimethylbenzyloxy, 2-phenylethoxy, 1- Phenylethoxy, phenoxy, octylphenoxy, 1-naphthyloxy and 2-naphthyloxy, and methoxy, ethoxy, 1-propoxy, 2-propoxy, 1 -butoxy, 2-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, dodecyloxy, 2-ethylhexyloxy Or 3,7-dimethyloctyloxy is more preferred, and more preferably methoxy, ethoxy or 1-propoxy.

Examples of the hydrocarbonthio group include a methylthio group, an ethylthio group, a 1-propylthio group, a 2-propylthio group, a 1-butylthio group, a 2-butylthio group, an isobutylthio group, a third butylthio group, Butylthio, hexylthio, octylthio, decylthio, dodecylthio, 2-ethylhexylthio, 3,7-dimethyloctylthio, cyclopropylthio, cyclopentylthio, Cyclohexylthio, 1-adamantanethio, 2-adamantanethio, norbornylthio, benzylthio, α,α-dimethylbenzylthio, 2-phenylethylthio, 1- Phenylethylthio, phenylthio, octylphenylthio, 1-naphthylthio and 2-naphthylthio, and are methylthio, ethylthio, 1-propylthio, 2-propylthio, 1 -butylthio, 2-butylthio, isobutylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, More preferably, 2-ethylhexylthio or 3,7-dimethyloctylthio is more preferably a methylthio group, an ethylthio group or a 1-propylthio group.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom or a chlorine atom.

The mercaptoamine group may, for example, be a mercaptoamine group, an etidamine group, a propylamine group, a butylammonium group, a benzamidine group, a trifluoroacetamido group, a pentafluorobenzamide group, or a dimethyl group. Anthranyl, diethylamino, dipropylamino, dibutylammonium, benzoylamino, bis(trifluoroacetamido) and bis(pentafluorobenzamide), It is preferably a methionine group, an acetamino group, a propylamine group, a butylammonium group or a benzylamino group.

The quinone imine group is a group obtained by removing a hydrogen atom bonded to a nitrogen atom from a quinone imine.

The quinone imine group may, for example, be an N-succinimide group, an N-quinone imine group or a benzophenone quinone imide group, and is preferably an N-quinone imine group.

The substituted fluorenyl group is a decyl group in which 1 to 3 hydrogen atoms in the decyl group are substituted with 1 to 3 groups selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.

The substituted decyl group may, for example, be a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a triisopropyl decyl group, a dimethyl isopropyl decyl group, a diethyl isopropyl decyl group, Third butyl dimethyl decyl, pentyl dimethyl decyl, octyl dimethyl decyl, heptyl dimethyl decyl, octyl dimethyl decyl, 2-ethylhexyl dimethyl Base alkyl, mercapto dimethyl decyl, decyl dimethyl decyl, 3,7 dimethyl octyl-dimethyl decyl, lauryl dimethyl decyl, triphenyl decyl, three -p-dimethylphenyldecyl, tris(benzyl)decyl, diphenylmethyldecyl, The third butyl diphenyl fluorenyl group and the dimethyl phenyl fluorenyl group are preferably a trimethyl decyl group, a triethyl decyl group or a tripropyl decyl group.

The mercapto group can be exemplified by, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, an isobutyl group, a pentamidine group, a benzamidine group, a trifluoroethenyl group, and a pentafluorobenzhydryl group, and is preferably an acetamidine group. Base or benzamidine.

The alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a second butoxycarbonyl group or a third group. Oxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, 3,7-dimethyl The octyloxycarbonyl group and the dodecyloxycarbonyl group are preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group or an isobutoxycarbonyl group.

The alkoxysulfonyl group may, for example, be methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl, isobutoxy. Sulfonyl, second butoxysulfonyl, third butoxysulfonyl, pentoxysulfonyl, hexyloxysulfonyl, heptoxysulfonyl, octyloxysulfonyl, 2-ethylhexyloxysulfonyl, nonyloxysulfonyl, decyloxysulfonyl, 3,7-dimethyloctyloxysulfonyl and dodecyloxysulfonyl, and preferably Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl or isobutoxysulfonyl.

The alkoxyphosphonium group may, for example, be a dimethoxyphosphonium group, a diethoxyphosphonium group, a dipropoxyphosphonium group, a diisopropoxyphosphonium group or a dibutoxyphosphonium group. And an oxirane phosphonium group, and is preferably a dimethoxyphosphonium group.

a substituted phosphino group, wherein one or two hydrogen atoms in the phosphino group are selected from the group consisting of alkane One or two substituted phosphino groups in the group of aryl, aryl and aralkyl groups.

The substituted phosphino group may, for example, be a phenylphosphino group, a diphenylphosphino group, a methylphosphino group, a dimethylphosphino group, an ethylphosphino group, a diethylphosphino group, a propylphosphino group or a dipropylphosphino group. And a butylphosphino group and a dibutylphosphino group, and are preferably a diphenylphosphino group, a dimethylphosphino group, a diethylphosphino group, a dipropylphosphino group or a dibutylphosphino group.

The substituted phosphine oxide group is a phosphine oxide group in which one or two hydrogen atoms in the phosphine oxide group are substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.

The substituted phosphine oxide group may, for example, be a phenylphosphine oxide group, a diphenylphosphine oxide group, a methylphosphine oxide group, a dimethylphosphine oxide group, an ethylphosphine oxide group, a diethylphosphine oxide group or a propyl group. a phosphino group, a dipropylphosphine oxide group, a butylphosphine oxide group and a dibutylphosphine oxide group, and is preferably a diphenylphosphine oxide group, a dimethylphosphine oxide group, a diethylphosphine oxide group or a dipropyl group. A phosphine oxide group or a dibutylphosphine oxide group.

The substituted amine group is an amine group in which 1 to 2 hydrogen atoms in the amine group are substituted with 1 to 2 groups selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.

The substituted amine group may, for example, be a phenylamino group, a diphenylamino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group or a dipropylamino group. , butylamino and dibutylamino, and preferably diphenylamino, methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino or two Butylamine group.

When the substituent is -NH ^- , -O ^- , -S ^- , -COO ^- , -SO ₃ ^- , -HPO ₄ ^- or -H ₂ PO ₃ ^- , the substituent may also have a relative ion. The relative ions may, for example, be lithium ions, sodium ions, potassium ions, barium ions, strontium ions and ammonium ions, and are preferably sodium ions, potassium ions or ammonium ions.

<铈合化合物>

The oxime complex of the present invention is a ruthenium complex represented by the above composition formula (1).

In the above composition formula (1), M is a cerium ion. The valence of the cerium ion is preferably trivalent because it can make the luminescence intensity of the cerium ion excellent.

In the above composition formula (1), X is a relative ion. The counter ion is a counter ion that neutralizes the total charge of the cesium ion and L. Although it is usually an anion, when L has a negative charge of two or more valences, it may be a cation. In other words, the electric charge of the entire composition formula (1) may be made zero.

Examples of the cation include lithium ions, sodium ions, potassium ions, ion ions, cerium ions, and ammonium ions.

Examples of the anion include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, acetate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, Hexafluoroantimony ion, hexafluoroarsenic ion, methanesulfonate ion, trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, dodecylbenzenesulfonate ion, tetraphenylboric acid Salt ions and tetrakis(pentafluorophenyl) borate ions.

The relative ion represented by X is preferably fluoride ion, chloride ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimony ion, hexafluoroarsenic ion, methanesulfonate ion , trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, dodecylbenzenesulfonate ion, tetraphenylborate ion or tetrakis(pentafluorophenyl)borate ion, And should be chloride ion, nitrate ion, perchlorate ion, Tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, tetraphenylborate ion or tetra (five) Fluorophenyl) borate ion, with perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, trifluoroacetate ion or tetraphenylborate ion, more preferably Tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, or tetraphenylborate ions are particularly preferred.

In the above composition formula (1), L' is a single or two-dentate ligand. The monodentate or the 2-dentate ligand represented by L' is usually an atomic group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a phosphorus atom, and examples thereof include water, methanol, and ethanol. Acetone, tetrahydrofuran, dimethyl hydrazine, triaryl phosphine oxide, trialkyl phosphine oxide, pyridine, quinoline, pyrazole, imidazole, Oxazole, thiazole, benzimidazole, benzo Azole, benzothiazole, three (triazine), pyrimidine, pyridyl (pyrazine), bipyridine, biquinoline, bipyridyl, phenanthroline, triarylphosphine, trialkylphosphine and trialkylamine.

In the above composition formula (1), a is a number from 1 to 4, and is preferably 1 or 2, and more preferably 2. When a is 2 or more, each A may be the same or different from each other. If there are a plurality of Ls, each L may be the same or different from each other. b is a number from 0 to 5, and is preferably a number from 0 to 3, and more preferably 1 or 3. When b is 2 or more, each X may be the same or different from each other. c is a number from 0 to 5, and is preferably a number from 0 to 2, and more preferably 0. When c is 2 or more, each L' may be the same or different from each other.

In the above composition formula (1), a combination of a, b and c is in the middle of the complex The coordination number of the metal ion and the valence of the ligand are related, and in order to form a stable complex structure, it is preferably a=2, b=3, and c=0.

In the above composition formula (1), A is a carbon atom, a ruthenium atom, a nitrogen cation, a boron anion, a nitrogen atom, a phosphorus atom or P(=O). When A is a carbon atom, a halogen atom, a nitrogen cation or a boron anion, z is 4, and m is an integer of 1 to 4. When z is 4, m is preferably an integer of 2 to 4, and more preferably 2 or 3. When A is a nitrogen atom, a phosphorus atom or P(=O), z is 3, and m is 1 to 3. When z is 3, m is preferably 2 or 3.

In order to form a stable complex structure, A is preferably a carbon atom, a halogen atom, a nitrogen atom, a phosphorus atom or P(=O), and is preferably a carbon atom or a nitrogen atom, and more preferably a nitrogen atom.

In the above composition formula (1), D is a direct bond or a hydrocarbon diradical which may have a substituent, and G is a heterocyclic group or a hydrogen atom which may have a substituent. It is preferable that at least one of D in the above formula (1) and D' in the above formulae (2-1), (2-2) and (2-3) is not a direct bond.

Among the hydrocarbon diradicals which may have a substituent represented by D, the hydrocarbon diradical usually has 1 to 30 carbon atoms, and preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5. Examples of the hydrocarbon diyl group include, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a methyl group, a methyl group, a methyl group, and an ethyl group. Base, ethyl propyl, methyl butyl, ethyl hexyl, dimethyl octyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantane diyl, norbornyl diyl, benzene Methyl, vinyl, propenyl, butenyl, diphenylvinyl, phenylvinyl, phenyl propylene, phenyl, methylphenyl, biphenyldiyl, Joint three Phenyldiyl, tetraphenylphenylene, (2,2-diphenylvinyl)phenyl, (1,2,2-triphenylvinyl)phenyl, fluorenyl, naphthyl , 蒽 蒽, phenanthrene and fluorenyl, and preferably methylene, ethyl, propyl, butyl, methyl ethyl, methyl propyl, ethyl ethyl, ethyl Propyl propyl, methyl butyl, ethyl hexyl, phenylmethylene, vinyl, propylene or phenyl, methylene, ethyl, propyl, butyl, Methyl extended ethyl, methyl propyl, vinyl or propylene is preferred, and methylene, ethyl, propyl, butyl, methyl or ethyl The base is more preferred, and methylene, ethyl or propyl is preferred. If there are multiple Ds, each D may be the same or different from each other. Further, the "hydrocarbon diradical" may also be referred to as a "hydrocarbon group."

In the above composition formula (1), G is a heterocyclic group or a hydrogen atom which may have a substituent. The heterocyclic group means an atomic group which is left after removal of one hydrogen atom directly bonded to a carbon atom or a nitrogen atom of a ring constituting the heterocyclic compound. Among the heterocyclic groups which may have a substituent represented by G, the heterocyclic group may, for example, be piperidinyl or piperidin Piperazinyl, benzofuranyl, furyl, benzothienyl, thienyl, benzopyrrolyl, pyrrolyl, benzimidazolyl, imidazolyl, benzopyrazole, pyrazolyl, benzo Azolyl, Azolyl, benzothiazolyl, thiazolyl, quinolyl and pyridyl, and preferably benzofuranyl, furyl, benzothienyl, thienyl, benzopyrrolyl, pyrrolyl, benzimidazolyl, Imidazolyl, benzopyrazole, pyrazolyl, benzo Azolyl, Azolyl, benzothiazolyl, thiazolyl, quinolinyl or pyridyl, benzimidazolyl, imidazolyl, benzopyrazole, pyrazolyl, benzo Azolyl, The azole group, the benzothiazolyl group, the thiazolyl group, the quinolyl group or the pyridyl group are more preferably a benzimidazolyl group, an imidazolyl group, a pyrazolyl group or a pyridyl group, and a benzimidazolyl group or an imidazolyl group is particularly preferred. If G is plural, they may be the same or different from each other.

In the above composition formula (1), L is a group containing an aromatic 6-membered ring having two or more nitrogen atoms in its structure. An aromatic 6-membered ring having two or more nitrogen atoms, for example, pyridyl Pyrimidine (pyridazine), 1, 2, 3-three 1,2,4-three 1,3,5-three 1,2,3,4-four 1,2,3,5-four And 1, 2, 4, 5 - four In order to obtain a ruthenium complex with high hole acceptability and high electron acceptability, it should be pyridine. Pyrimidine Or 1,3,5-three Pyridyl , pyrimidine or 1,3,5-three More preferably, with pyrimidine or 1,3,5-three More preferably, and pyrimidine is especially preferred. Since a stable ruthenium complex can be formed, L is preferably a group represented by the above formula (2-1), (2-2) or (2-3), and is further represented by the above formula (2-1). good.

In the above formulae (2-1), (2-2) and (2-3), D' is a direct bond or a hydrocarbon diyl group which may have a substituent, and is preferably a hydrocarbon diyl group which may have a substituent. Among the hydrocarbon diradicals which may have a substituent, the hydrocarbon diradical is the same as the preferred embodiment of the hydrocarbon diradical in the hydrocarbon diradical which may have a substituent represented by the above D, but is preferably a methylene group. Of the plurality of D', preferably at least one of them is not a direct bond, and it is more preferable that all of D' is a hydrocarbon group which may have a substituent.

In the above formula (2-1), E is a divalent group having an aromatic 5-membered ring containing a nitrogen atom, or a divalent group having a ring condensed with an aromatic 5-membered ring containing a nitrogen atom and an aromatic ring. E can be enumerated, for example, from imidazolyl, Azyl, thiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzimidazolyl, benzo The divalent group after removing one hydrogen atom from the azolyl group and the benzothiazolyl group is preferably an imidazolyl group, in order to form a stable ruthenium complex. Azyl, thiazolyl, benzimidazolyl, benzo A divalent group after removing one hydrogen atom by an azolyl group or a benzothiazolyl group, respectively.

In the above formulae (2-1) and (2-3), J is a monovalent group having an aromatic 6-membered ring containing two or more nitrogen atoms. J is preferably a group obtained by removing one hydrogen atom from an aromatic 6-membered ring containing two or more nitrogen atoms. An aromatic 6-membered ring containing two or more nitrogen atoms, for example, pyridyl Ring, pyrimidine ring, anthracene Ring, 1, 2, 3-three Ring, 1, 2, 4-three Ring, 1,3,5-three Ring, 1, 2, 3, 4-four Ring, 1, 2, 3, 5 - four Ring and 1,2,4,5-four Ring, in order to obtain a high-hole acceptability and high electron acceptability of the ruthenium complex, which should be pyridine Ring, pyrimidine ring, anthracene Ring or 1,3,5-three Ring Ring, pyrimidine ring, anthracene Ring or 1,3,5-three Ring is better, with pyrimidine ring or 1,3,5-three The ring is better, and the pyrimidine ring is especially preferred.

In the above formula (2-2), E' is a monovalent group having an aromatic 5-membered ring containing a nitrogen atom, or a monovalent group having a ring condensed with an aromatic 5-membered ring containing a nitrogen atom and an aromatic ring. E' can be enumerated, for example, imidazolyl, Azyl, thiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzimidazolyl, benzo Azolyl and benzothiazolyl, in order to form a stable ruthenium complex, it is preferably an imidazolyl group, Azyl, thiazolyl, benzimidazolyl, benzo The azole group or the benzothiazolyl group is more preferably an imidazolyl group or a benzimidazolyl group.

In the above formula (2-2), J' is a divalent group having an aromatic 6-membered ring having two or more nitrogen atoms. Examples and preferred examples of the aromatic 6-membered ring are the same as those of the aromatic 6-membered ring described in J.

The aromatic 5-membered ring, the aromatic 6-membered ring, and the ring composed of the aromatic 5-membered ring and the aromatic ring contained in E, J, E' and J' can each independently have a The substituent, if the substituent is plural, the substituents together with the atoms to which they are bonded form a ring.

In order to make the hole accepting capacitance and electron acceptability higher, J and E' should not form a bond with M (that is, it should not be located at M).

Examples of the formula (2-1) include a group represented by the following formula (3).

In the formula (3), R ² is a monovalent group. Examples and preferred examples of the monovalent group represented by R ² are the same as the above-mentioned substituent examples and preferred examples, and among these, a hydrocarbon group is preferred, and a methyl group, an ethyl group, and a 1-propyl group are preferable. Preferably, hexyl, 2-ethylhexyl, tert-butyl or vinyl is preferred. n is an integer of 0 to 2, and is preferably 0 or 1, and more preferably 0. When n is 2, each R ² may be the same or different from each other, and two R ² together may form a ring together with the carbon atom to which they are bonded. D' and J are synonymous with the above.

Other examples of the formula (2-1) include a group represented by the following formula (4).

In the formula (4), p is an integer of 0 to 4, and is preferably 0 or 1, and more preferably 0. When p is 2 or more, each R ² may be the same or different from each other, and two R ² bonded to adjacent carbon atoms may together form a ring together with the carbon atom to which they are bonded. R ² , D' and J are synonymous with the above.

In order to further improve the electron acceptability of the ruthenium complex, the above J is preferably a monovalent group represented by the following formula (5).

In the formula (5), R ³ is a hydrogen atom or a monovalent group. Each R ³ may be the same or different from each other. Examples and preferred examples of the monovalent group represented by R ³ are the same as the above-mentioned substituent examples and preferred examples, and among these, a hydrocarbon group is particularly preferable, and a methyl group, an ethyl group, and a 1-propyl group are preferable. The base, hexyl, 2-ethylhexyl, tert-butyl or vinyl is most preferred. Q is a nitrogen atom or C(R ³ ).

An example of the ruthenium complex of the present invention is a ruthenium complex represented by the following composition formula (6).

In the composition formula (6), R ⁴ is a hydrogen atom or a monovalent group. Examples and preferred examples of the monovalent group represented by R ⁴ are the same as the above-mentioned substituent examples and preferred examples, and among these, a hydrocarbon group is particularly preferred, and a methyl group, an ethyl group, and a 1-propyl group are preferable. The base, hexyl, 2-ethylhexyl, tert-butyl or vinyl is most preferred. In the case where R ⁴ is a monovalent group, it is more preferable to use R ⁴ as a hydrogen atom. m' is an integer of 1 to 3, and is preferably 2 or 3. D, R ² , R ³ , Q, n, M, X, L', b and c are synonymous with the above. If Q is plural, they may be the same or different from each other.

In the composition formula (6), G' is a heterocyclic group which may have a substituent, and examples thereof and preferred examples are the same as the preferred examples of the heterocyclic group in the heterocyclic group which may have a substituent represented by G .

In another example of the ruthenium complex of the present invention, a ruthenium complex represented by the following composition formula (7) can be mentioned.

In the composition formula (7), R ⁴ , G′, D, R ² , R ³ , Q, p, m′, M, X, L′, b and c are synonymous with the above.

A preferred example of the ruthenium complex represented by the above formula (7) is a ruthenium complex represented by the following composition formula (7-1).

In the composition formula (7-1), R ⁵ is a hydrogen atom or a hydrocarbon group which may have a substituent. The hydrocarbon group represented by R ⁵ is preferably a methyl group, an ethyl group, a 1-propyl group, a hexyl group or a 2-ethylhexyl group. R ⁴ , R ² , R ³ , Q, p, m', M, X, L', b and c are synonymous with the above.

The oxime complex of the present invention is preferably in the following composition formulas (B-1) to (B-8). The 铈 complex is shown. In order to further improve the hole acceptability and electron acceptability of the ruthenium complex, the ruthenium complex represented by the following composition formulas (B-5) to (B-8) is more preferable, and the following composition formula (B-7) ) The bismuth complex represented by (B-8) is even better.

The ruthenium complex of the present invention generally exhibits blue luminescence.

<Method for producing bismuth complex>

The ruthenium complex of the present invention can be produced according to a known method used in the synthesis of a complex. For example, a compound as a ligand and a phosphonium salt are mixed in a solvent at room temperature. Then, the obtained precipitate is recovered, or the solvent is distilled off from the reaction liquid, and then it can be easily obtained.

Examples of the onium salt include ruthenium (III) chloride, ruthenium (III) nitrate, and ruthenium (III) trifluoromethanesulfonate. Further, the cerium salt may be used singly or in combination of two or more.

The ratio of the compound to be used as a ligand to the onium salt used in the above mixing is usually determined so that the number of coordination atoms is from 6 to 12, preferably eight, per 1 atom.

The temperature and the reaction time at the time of the above mixing can be usually produced by stirring at room temperature for about 1 hour, but the temperature can be raised to a temperature at which the solvent can be refluxed to shorten the reaction time.

The above mixing is usually carried out under an inert gas (for example, nitrogen, argon) atmosphere.

The solvent to be used in the above mixing may, for example, be an aqueous solvent such as a buffer solution or an organic solvent, but is preferably an organic solvent. Further, one type of solvent may be used alone or two or more types may be used in combination.

The organic solvent may, for example, be a nitrile solvent such as acetonitrile or benzonitrile; chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene or o-dichlorobenzene; Halogen-like solvent; tetrahydrofuran, two An ether solvent such as an alkane; an aromatic hydrocarbon solvent such as toluene or xylene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-decane, n-decane, etc. An aliphatic hydrocarbon solvent; a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; an ester solvent such as ethyl acetate, butyl acetate or ethyl cellosolve acetate; , ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hex Polyols such as diols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol; hydrazine-based solvents such as dimethyl hydrazine; and N-methyl-2-pyrrolidine A guanamine solvent such as N-methyl-2-pyrrolidene or N,N-dimethylformamide, and is preferably methanol, ethanol, chloroform, dichloromethane or acetonitrile.

The relative ions of the ruthenium complex of the present invention can be easily exchanged into arbitrary counter ions by a method such as ion exchange chromatography or salting out. In the salting-out method, for example, a saturated solution of the salt of the ion to be exchanged may be added to the solution of the ruthenium complex obtained by the above method, and the thus-produced precipitate may be recovered. The complex of ions.

<composition>

The ruthenium complex of the present invention can be used as it is, or can be used in combination with a charge transport material to form a composition. This composition is usually in a liquid or solid shape at 25 °C.

The charge transporting material refers to a material responsible for transporting charges in an element such as an organic electroluminescent device (also referred to as a "light emitting device"), which is a hole transporting material and an electron transporting material. The charge transporting material can be classified into a low molecular organic compound and a high molecular organic compound (for example, a polymer compound, an oligomer). The polymer compound and the oligomer are preferably conjugated.

The above-mentioned hole transporting material may be a known material such as a ruthenium and a derivative, an aromatic amine and a derivative thereof, a carbazole derivative, a polyparaphenylene derivative or the like as a hole transporting material of an organic electroluminescent device. .

The above electron transporting material can be used, for example, Diazole derivatives, three Derivatives, quinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, hydrazine and its derivatives, tetracyanoquinodimethane and its derivatives, anthrone Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. as electron transport materials for organic electroluminescent elements It is a known material.

In the composition of the present invention, the content of the above-mentioned ruthenium complex is usually 0.01 to 300 parts by mass based on 100 parts by mass of the charge transporting material, and is preferably 0.1 to a good balance in hole acceptance and electron acceptability. 150 parts by mass, and more preferably 1 to 50 parts by mass.

In the composition of the present invention, one type of the above-mentioned ruthenium complex and the above-mentioned charge transport material may be used alone or two or more types may be used in combination.

<organic film>

The organic film of the present invention contains the above-described ruthenium complex. The organic film of the present invention can be easily formed into a film by a coating method such as an inkjet printing method, using a solution obtained by mixing the above-mentioned ruthenium complex with a solvent.

The organic film of the present invention can be used, for example, as a light-emitting film, a conductive film, and an organic semiconductor film.

The thickness of the organic film of the present invention is preferably from 1 nm to 500 nm, and more preferably from 5 nm to 200 nm.

<organic electronic components>

The organic electronic component of the present invention contains the above-described ruthenium complex. The organic electronic component of the present invention may, for example, be a light-emitting device having a layer containing the above-described ruthenium complex, a switching element having a layer containing the above-described ruthenium complex, and a photovoltaic having a layer containing the above-described ruthenium complex. Conversion component.

[Light-emitting element]

The light-emitting element usually has a light-emitting layer between electrodes composed of an anode and a cathode. The light-emitting element may contain a layer other than the light-emitting layer to improve luminous efficiency and durability. Examples of the layer other than the light-emitting layer include a charge transport layer, a charge stop layer, a charge injection layer, and a buffer layer. Each layer may have only one layer or two or more layers in the light-emitting element.

The luminescent layer is a layer having an illuminating function.

The charge transport layer is a collective term for the electron transport layer and the hole transport layer. The hole transport layer is a layer having a function of transporting holes. The electron transport layer is a layer that has the function of transporting electrons.

The charge blocking layer is a layer having a function of blocking holes or electrons in the light emitting layer, wherein a layer that transports electrons and blocks the holes is called a hole blocking layer, and a layer that transports holes and blocks electrons is called an electron. Block layer.

The buffer layer may be a layer which is adjacent to the anode and contains a conductive polymer compound.

The structure of the light-emitting element includes the following structures a) to q).

a) anode / luminescent layer / cathode b) anode / hole transport layer / luminescent layer / cathode c) anode / luminescent layer / electron transport layer / cathode d) anode / luminescent layer / hole blocking layer / cathode e) anode / hole transport layer / luminescent layer / electron transport layer / cathode f) anode / charge injection layer / luminescent layer / cathode g) anode / luminescent layer / charge Injection layer/cathode h) anode/charge injection layer/light-emitting layer/charge injection layer/cathode i) anode/charge injection layer/hole transport layer/light-emitting layer/cathode j) anode/hole transport layer/light-emitting layer/charge Injection layer/cathode k) anode/charge injection layer/hole transport layer/light-emitting layer/charge injection layer/cathode 1) anode/charge injection layer/light-emitting layer/electron transport layer/cathode m) anode/light-emitting layer/electron transport Layer/charge injection layer/cathode n) anode/charge injection layer/light-emitting layer/electron transport layer/charge injection layer/cathode o) anode/charge injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode p) Anode/hole transport layer/light-emitting layer/electron transport layer/charge injection layer/cathode q) anode/charge injection layer/hole transport layer/light-emitting layer/electron transport layer/charge injection layer/cathode (above a) to q In the middle, "/" means that each layer is adjacent to the layer. Further, the light-emitting layer, the hole transport layer, and the electron transport layer may be used alone or in two or more layers.

The charge transport layer disposed adjacent to the electrode has a function of improving the efficiency of injecting charge from the electrode and has a effect of lowering the driving voltage of the light emitting element. The layer of fruit is generally referred to as a charge injection layer. The light-emitting element including the charge injection layer includes a light-emitting element having a charge injection layer adjacent to the cathode, and a light-emitting element having a charge injection layer adjacent to the anode.

In the light-emitting element, an insulating layer may be provided adjacent to the electrode to improve adhesion to the electrode or to improve charge injection from the electrode. Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. The thickness of the insulating layer is usually 2 nm or less. The light-emitting element including the insulating layer includes a light-emitting element including the insulating layer adjacent to the cathode, and a light-emitting element including the insulating layer adjacent to the anode.

The light-emitting layer is a layer containing the above-described ruthenium complex or the above composition. Among the light-emitting layers, other light-emitting materials may be contained. Other luminescent materials include naphthalene derivatives, hydrazine and its derivatives, hydrazine and its derivatives, polymethines, xanthenes, coumarins, and anthocyanins. (cyanine)-like pigments, metal complexes of 8-hydroxyquinoline and its derivatives, aromatic amines, tetraphenylcyclopentadiene and its derivatives, and tetraphenylbutadiene and its derivatives .

The material used for the hole transport layer may, for example, be a polyvinyl carbazole or a derivative thereof, a polydecane or a derivative thereof, a polyoxyalkylene derivative having an aromatic amine compound group in a side chain or a main chain, or a pyrazole. Pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline and its derivatives, polyaminophen and its derivatives, polypyrrole And derivatives thereof, poly(p-phenylenevinyl) and derivatives thereof, and poly(2,5-thienyl extended vinyl) and derivatives thereof.

The thickness of the hole transport layer is set to make the luminous efficiency or photoelectric efficiency The thickness which reaches a moderate value with respect to the driving voltage is usually 1 nm to 1 μm, and preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

Materials used for the electron transport layer include, for example, Diazole derivatives, quinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, hydrazine and its derivatives, tetracyanoquinodimethane and its derivatives, anthrone derivative , diphenyldicyanoethylene and its derivatives, biphenyl hydrazine derivatives, metal complexes of 8-hydroxyquinoline and derivatives, polyquinoline and its derivatives, polyquine Polyquinoxaline and its derivatives, as well as polyfluorene and its derivatives.

The thickness of the electron transport layer is set to a thickness such that the luminous efficiency or the photoelectric efficiency and the driving voltage reach a moderate value, and is usually 1 nm to 1 μm, and preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

Each layer is formed on an adjacent layer or substrate. Examples of the formation method include a vacuum deposition method (resistance heating vapor deposition method, electron beam method, etc.), a sputtering method, an LB method, a molecular layering method, and a coating method. In order to simplify the process, a coating method is preferred.

Examples of the coating method include spin coating, casting method, dip coating, gravure coating, bar coating, roll coating, spray coating, screen printing, and flexographic printing. Printing), offset printing, and inkjet printing are preferably roll coating, spray coating, flexographic printing or ink jet printing.

The light-emitting element of the present invention is usually formed using a substrate. An electrode is formed on one side of the substrate, and layers of the element are formed on the other side. Examples of the substrate include a substrate made of glass, plastic, fluorenone, or a polymer film. Substrate.

The anode and the cathode contained in the light-emitting element of the present invention are generally transparent or translucent, but it is preferred that the anode be transparent or translucent.

Examples of the material used for the anode include a conductive gold oxide film, a translucent metal film, and an organic transparent conductive film, and are preferably indium oxide, zinc oxide, tin oxide, and the like (indium ‧ tin Oxide (ITO), indium ‧ zinc ‧ oxide, etc., 锑 ‧ tin ‧ oxide, NESA, gold, platinum, silver, copper, polyaniline and its derivatives, and polyaminophenol and its derivatives.

Examples of the method for forming the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

The thickness of the anode is set in consideration of light transmittance and conductivity, and is usually 10 nm to 10 μm, and preferably 20 nm to 1 μm, and more preferably 40 nm to 500 nm.

The material used for the cathode is preferably a material having a small work function, and examples thereof include lithium, sodium, potassium, rubidium, cesium, cesium, magnesium, calcium, strontium, barium, aluminum, strontium, vanadium, zinc, bismuth, indium, bismuth. a metal such as ruthenium, osmium, iridium or osmium; an alloy of two or more metals selected from the group consisting of such metals; one or more metals selected from the group of such metals, and gold, An alloy of one or more metals in a group of silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; graphite; graphite intercalation compound.

Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, and a laminate method in which a metal thin film is thermocompression bonded. Further, a cathode having a laminated structure of two or more layers may be formed.

The thickness of the cathode is set in consideration of conductivity and durability, usually 10 nm to 10 μm, and preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

In the light-emitting element of the present invention, in order to use the external protective element for a long period of time, a protective layer or a protective cover for protecting the light-emitting element may be formed after the cathode is formed.

The charge injection layer includes a layer containing a conductive polymer, a layer containing a material having an ionization potential of an intermediate value of a hole transport material contained in the anode material and the hole transport layer, and a layer containing A layer of a material having an electron affinity of an intermediate value of a cathode material and an electron transporting material contained in the electron transporting layer.

Examples of the material used for the charge injection layer include polyaniline and its derivatives, polyamine phenol and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, and polythiophene-based vinylene. And its derivatives, polyquinoline and its derivatives, polyquine A conductive polymer such as a porphyrin or a derivative thereof, a polymer having an aromatic amine structure in a main chain or a side chain, a metal phthalocyanine, and carbon.

The thickness of the charge injection layer is usually from 1 nm to 100 nm, and is preferably from 1 nm to 50 nm, more preferably from 1 nm to 10 nm.

The light-emitting elements are used for backlights, illuminations, and the like for planar light sources, segment displays, dot matrix displays, liquid crystal displays.

[Photoelectric Conversion Element]

The photoelectric conversion element usually has an anode, a cathode, and a charge separation layer. The charge separation layer is located between the anode and the cathode. The photoelectric conversion element may also have any layer other than the charge separation layer between the anode and the cathode. Contains the above 铈 The complex or a layer of the above composition may be contained in the charge separation layer or may be contained in any layer other than the charge separation layer.

The materials and examples of the cathode and the anode are the same as those of the cathode and the anode described in the section of the light-emitting element. The shape of the anode and the cathode is not limited, and may be a comb shape. The anode and the cathode may be either transparent or translucent.

The charge separation layer of the photoelectric conversion element usually contains an electron-donating compound and an electron-accepting compound.

The electron-donating compound can be exemplified by a conjugated polymer compound. The conjugated polymer compound may, for example, be a conjugated polymer compound containing a thiophenediyl group and a conjugated polymer compound containing a fluorenyl group.

Examples of the electron accepting compound include fullerenes and fullerene derivatives.

The photoelectric conversion element is usually formed on a substrate. An example of the substrate is the same as the example of the substrate used in the light-emitting element.

The photoelectric conversion element is preferably a solar cell.

<compound>

The present invention provides a compound represented by the following formula (8).

In the formula (8), R ⁴ , G′, D, R ² , R ³ , Q, p and m′ are synonymous with the above.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited.

<Synthesis Example 1>

Tris(2-benzimidazolylmethyl)amine (hereinafter abbreviated as "ntb") was synthesized according to the description of Inorganica Chimica Acta 231, 109-114 (1995). Specifically, ntb was obtained by heating o-phenylenediamine, nitrilotriacetic acid, and propylene glycol at 144 to 154 ° C for 24 hours and refluxing.

<Synthesis Example 2>

2-Chloro-4,6-di-t-butylpyrimidine was synthesized according to the description of Angew. Chem. Int. Ed. 47, 8246-8250 (2008). Specifically, a solution of 2,4,6-trichloropyrimidine and copper iodide in tetrahydrofuran was cooled to 0 ° C, and a third butyl magnesium chloride was added thereto, and the mixture was stirred at 0 ° C for 2 hours to obtain 2-chloro-4. 6-Di-t-butylpyrimidine.

<Example 1>

‧ Synthesis of compound (C-1)

In a Schlenk tube, tris(dibenzylideneacetone)dipalladium(0) (46 mg, 0.043 mmol), tripotassium phosphate (363 mg, 1.71 mmol), 2-chloro-4,6- Di-t-butylpyrimidine (429 mg, 1.89 mmol), 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl -1,1'-biphenyl (82 mg, 0.17 mmol) and ntb (231 mg, 0.567 mmol), after replacing the gas in the Schlenk tube with argon, de-dehydrated toluene (5 mL) was added. Then, it was heated to 50 ° C in an oil bath, and in this case, it was stirred for 7.5 hours, and then heated to 110 ° C, in which case it was stirred for 5 hours. Water was added to the obtained reaction liquid to stop the reaction. After adding chloroform, extraction, and washing the obtained organic layer twice with water, it dried over anhydrous magnesium sulfate, and the solvent was evaporated by the evaporator. The obtained residue is purified by an alumina column chromatography alumina filter (developing liquid: chloroform) to obtain a yellow oily substance (255 mg) of the compound of the above formula (C-1) (compound (C-1)) (255 mg) , yield: 31.8%).

The NMR data of the compound (C-1) are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ (ppm) = 8.36 (2H, d, J = 7.8Hz), 7.80 (2H, d, J = 6.6Hz), 7.66 (1H, d, J = 7.5Hz), 7.59 (1H, d, J = 7.8 Hz), 7.33 (4H, m), 7.20 (2H, m), 7.15 (2H, s), 5.04 (4H, s), 4.64 (2H, s), 2.25 (1H) , s), 1.34 (36H, s).

‧ Synthesis of 铈 complex (B-7)

Compound (C-1) (64 mg, 0.080 mmol) and ruthenium (III) trifluoromethanesulfonate (22 mg, 0.037 mmol) were placed in a flask, and the gas in the flask was replaced with argon gas, and then chloroform (1 mL) was added thereto. Stir at room temperature for 2 hours. Then, the solvent in the reaction liquid was concentrated to dryness under reduced pressure. Extraction with dichloromethane The obtained residue was filtered, and the solvent was distilled off to obtain a hydrazine complex (B-7). The ruthenium complex (B-7) is a ruthenium complex represented by the above formula (B-7), and when ultraviolet rays (365 nm) are irradiated onto the complex, blue light emission is exhibited.

<Comparative Example 1>

‧ Synthesis of 铈 complex (D-1)

The ruthenium complex (deuterium complex (D-1)) represented by the following formula (D-1) was synthesized according to the description of Angew. Chem. Int. Ed. 46, 7399-7403 (2007).

[The LUMO level of the complex compound ‧ HOMO level]

In order to compare the LUMO level and the HOMO level of the ruthenium complex (B-7) of Example 1 with the ruthenium complex (D-1) of Comparative Example 1, WinMOPAC3 manufactured by Fujitsu Co., Ltd. .9, after calculating the structure by the semi-empirical molecular orbital PM5 method, according to the following partial structure, the LUMO level and HOMO level of each complex are obtained.

As is clear from Table 1, the partial structure of the ruthenium complex (B-7) of Example 1 had a LUMO level which was 0.63 eV lower than that of the ruthenium complex (D-1) of Comparative Example 1. This indicates that the ruthenium complex (B-7) exhibits higher hole acceptability and electron acceptability than the ruthenium complex (D-1). Therefore, it is understood that the ruthenium complex (B-7) exhibits excellent luminescent properties on the light-emitting element.

(industrial availability)

The ruthenium complex of the present invention is a material used for a light-emitting element, a switching element, a photoelectric conversion element, a magnetic material, a biological probe, a developer, an additive, a modifier, a catalyst, and the like.

Claims (13)

a ruthenium complex represented by the formula (1), (wherein M is a phosphonium ion, and A is a carbon atom, a halogen atom, a nitrogen atom, a nitrogen cation, a boron anion, a phosphorus atom or P(=O); when A is a carbon atom, a halogen atom, a nitrogen cation or a boron anion, z is 4, m is an integer of 1 to 4; when A is a nitrogen atom, a phosphorus atom or P(=O), z is 3, m is an integer of 1 to 3; D is a direct bond or a hydrocarbon which may have a substituent a diradical group, G is a heterocyclic group or a hydrogen atom which may have a substituent, and L is a group containing an aromatic 6-membered ring having two or more nitrogen atoms, and if a plurality of L are present, each L may be the same or different from each other If there are multiple Ds, each D may be the same or different from each other; if there are multiple Gs, each G may be the same or different from each other; X is a counter ion, L' is a single tooth or The codon of 2 teeth, a is the number of 1 to 4, b and c are each independently 0 to 5; when a is 2 or more, plural A can be the same or different; when b is 2 or more The plurality of Xs may be the same or different, and when c is 2 or more, the plurality of L's may be the same or different, respectively. For example, the oxime complex described in claim 1 wherein L is a formula (2-1), (2-2) or (2-3), -D'-EJ (2-1) -D'-J'-E' (2-2) -D'-J (2-3) (wherein D' is a direct bond or a hydrocarbon diradical which may have a substituent, E is a divalent group having an aromatic 5-membered ring containing a nitrogen atom, or has a fragrance of 5 members derived from a nitrogen atom a divalent group of a ring condensed with an aromatic ring; J is a monovalent group having an aromatic 6-membered ring having two or more nitrogen atoms, and E' is a monovalent group having an aromatic 5-membered ring containing a nitrogen atom, or a monovalent group having a ring condensed with an aromatic 5-membered ring containing a nitrogen atom and an aromatic ring; J' is a divalent group having an aromatic 6-membered ring having two or more nitrogen atoms, and the aforementioned aromatic 5-membered ring and the aforementioned aromatic The 6-membered ring, and the ring condensed from the aromatic 5-membered ring and the aromatic ring, may each independently have a substituent, and if there are a plurality of substituents, these may together form a ring together with the respective bonded atoms). The oxime complex according to the second aspect of the invention, wherein the aromatic 5-membered ring of E or E' is an imidazole ring which may have a substituent. The oxime complex according to claim 2, wherein E or E' has a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring, and is a benzoimidazole ring which may have a substituent. . The oxime complex according to claim 1, wherein L is a group represented by formula (3) or formula (4), (wherein R ² is a monovalent group, n is an integer of 0 to 2, and when n is 2, each R ² may be the same or different from each other, and 2 R ² may together be together with the carbon atom to which they are bonded Forming a ring; D' and J are synonymous with the above) (wherein, p is an integer of 0 to 4, and when p is 2 or more, each R ² may be the same or different from each other, and 2 R ² bonded to adjacent carbon atoms may together be together with the carbon atom to which they are bonded Rings are formed; R ² , D', and J are synonymous with the above). The oxime complex according to claim 1, wherein A is a nitrogen atom. The oxime complex according to the second aspect of the patent application, wherein J is a monovalent group represented by the formula (5), (wherein R ³ is a hydrogen atom or a monovalent group, and each R ³ may be the same or different from each other; and Q is a nitrogen atom or C(R ³ )). The oxime complex described in claim 1 of the patent application, which is represented by the composition formula (6) or the composition formula (7), (wherein R ⁴ is a hydrogen atom or a monovalent group, and G' is a heterocyclic group which may have a substituent, and each R ⁴ may be the same or different from each other, and if a plurality of G' are present, each G' may be mutually M is an integer from 1 to 3, and D, R ² , R ³ , Q, n, M, X, L', b, and c are synonymous with the above, and if a plurality of Qs are present, each Q can be the same or different from each other) (wherein R ⁴ , G', D, R ² , R ³ , Q, p, m', M, X, L', b and c are synonymous with the above). The oxime complex described in the first paragraph of the patent application, which is represented by the composition formula (7-1), (wherein R ⁵ is a hydrogen atom or a hydrocarbon group which may have a substituent, and R ² , R ³ , R ⁴ , Q, p, m', M, X, L', b and c are synonymous with the above). A composition comprising the oxime complex and the charge transporting material described in claim 1 of the patent application. An organic film comprising the oxime complex described in claim 1 of the patent application. An organic electronic component comprising the oxime complex described in claim 1 of the patent application. a compound represented by the formula (8), (wherein R ³ is a hydrogen atom or a monovalent group, m' is an integer of 1 to 3, a plurality of R ^{3 's} may be the same or different, and Q is a nitrogen atom or C(R ³ ); if a plurality of are present When Q, each Q may be the same or different from each other; R ⁴ is a hydrogen atom or a monovalent group, and G' is a heterocyclic group which may have a substituent, and each R ⁴ may be the same or different from each other; When G', each G' may be the same or different from each other; R ² is a monovalent group, p is an integer of 0 to 4, and each p may be the same or different from each other; if a plurality of R ² are present, each R ² may be the same or different from each other; if two R ^{2 are} bonded to adjacent carbon atoms, these may together form a ring together with the carbon atom to which they are bonded; D is a direct bond or a hydrocarbon diyl group which may have a substituent ; if there are multiple Ds, each D can be the same or different from each other).