WO2012161205A1

WO2012161205A1 - Cerium complex and organic electronic element comprising cerium complex

Info

Publication number: WO2012161205A1
Application number: PCT/JP2012/063140
Authority: WO
Inventors: 悠輔倉持; 小林　憲史; 東村　秀之
Original assignee: 住友化学株式会社
Priority date: 2011-05-25
Filing date: 2012-05-23
Publication date: 2012-11-29
Also published as: TW201302768A; JP2013006833A

Abstract

The purpose of the present invention is to provide a cerium complex that has excellent electron acceptability and excellent hole acceptability, and the present invention provides a cerium complex represented by composition formula (1). (In the formula, 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 a P(=O) group; when z = 4, m = 1-4 and when z = 3, m = 1-3; D represents a direct bond or a hydrocarbondiyl group; G represents a heterocyclyl group or a hydrogen atom; L represents a group that contains an aromatic six-membered ring having two or more nitrogen atoms; X represents a counter ion; L' represents a monodentate or bidentate ligand; a represents a number of 1-4; b represents a number of 0-5; and c represents a number of 0-5.)

Description

Cerium complex and organic electronic device containing the cerium complex

The present invention relates to a cerium complex and an organic electronic device including the cerium complex.

A cerium complex using a tetradentate ligand containing a benzimidazolyl group is known as a light-emitting material used for a light-emitting layer of an organic electroluminescence element (Non-patent Document 1).

However, the above-described cerium complex has low electron acceptability and hole acceptability.

Therefore, an object of the present invention is to provide a cerium complex having excellent electron accepting properties and hole accepting properties.

As a result of intensive studies, the present inventors have completed the following [1] to [11].
[1] Composition formula (1):

(Where
M is a cerium ion.
A is a carbon atom, a silicon atom, a nitrogen atom, a nitrogen cation, a boron anion, a phosphorus atom, or P (═O). When A is a carbon atom, a silicon 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 hydrocarbondiyl group which may have a substituent.
G is a heterocyclyl group which may have a substituent, or a hydrogen atom.
L is a group containing an aromatic 6-membered ring having two or more nitrogen atoms. When a plurality of L are present, each L may be the same as or different from each other. When a plurality of D are present, each D may be the same as or different from each other. When a plurality of G are present, each G may be the same as or different from each other.
X is a counter ion.
L ′ is a monodentate or bidentate 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 as or different from each other. When b is 2 or more, each X may be the same as or different from each other. When c is 2 or more, each L ′ may be the same as or different from each other. )
A cerium complex represented by:
[2] The cerium complex according to the above [1], wherein L is a group represented by the formula (2-1), (2-2) or (2-3).
-D'-EJ (2-1)
-D'-J'-E '(2-2)
-D'-J (2-3)
(Where
D ′ is a direct bond or a hydrocarbondiyl group which may have a substituent.
E is a divalent group having a 5-membered aromatic ring containing a nitrogen atom or a divalent group having a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring.
J is a monovalent group having an aromatic 6-membered ring containing two or more nitrogen atoms.
E ′ is a monovalent group having a 5-membered aromatic ring containing a nitrogen atom or a monovalent group having a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with 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 in which the aromatic 5-membered ring is condensed with the aromatic ring may each independently have a substituent, and when there are a plurality of substituents Together, they may form a ring with the atoms to which they are attached. )
[3] The cerium complex according to the above [2], wherein the aromatic 5-membered ring which E or E ′ has is an imidazole ring which may have a substituent.
[4] The above [2] or [3], wherein the ring in which an aromatic 5-membered ring containing a nitrogen atom of E or E ′ is condensed with an aromatic ring is an optionally substituted benzimidazole ring The cerium complex described in 1.
[5] L is the formula (3):

(Where
R ² is a monovalent group, and n is an integer of 0-2.
When n is 2, each R ² may be the same as or different from each other, and two R ² may be combined to form a ring together with the carbon atom to which each is bonded.
D ′ and J have the same meaning as described above. )
Or, formula (4):

(Where
p is an integer of 0-4.
when p is 2 or more, each R ² may being the same or different, two R ² bound to adjacent carbon atoms are taken together the carbon atoms bonded thereto And may form a ring. R ² , D ′ and J have the same meaning as described above. )
The cerium complex according to any one of the above [1] to [4], which is a group represented by the formula:
[6] The cerium complex according to any one of the above [1] to [5], wherein A is a nitrogen atom.
[7] J is the formula (5):

(In the formula, R ³ is a hydrogen atom or a monovalent group. Each R ³ may be the same as or different from each other. Q is a nitrogen atom or C (R ³ ). .)
The cerium complex according to any one of the above [2] to [6], which is a monovalent group represented by the formula:
[8] Composition formula (6):

(Where
R ⁴ is a hydrogen atom or a monovalent group, and G ′ is a heterocyclyl group which may have a substituent.
Each R ⁴ may be the same as or different from each other. When a plurality of G ′ are present, each G ′ may be the same as or different from each other.
m ′ is an integer of 1 to 3.
D, R ² , R ³ , Q, n, M, X, L ′, b and c represent the same meaning as described above.
When a plurality of Q are present, each Q may be the same as or different from each other. )
Or composition formula (7):

(In the formula, R ⁴ , G ′, D, R ² , R ³ , Q, p, m ′, M, X, L ′, b and c represent the same meaning as described above.)
The cerium complex according to any one of the above [1] to [7] represented by
[9] Composition formula (7-1):

(Where
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 represent the same meaning as described above. )
The cerium complex according to any one of the above [1] to [8] represented by
[10] A composition comprising the cerium complex according to any one of [1] to [9] above and a charge transport material.
[11] An organic film containing the cerium complex according to any one of [1] to [9].
[12] An organic electronic device comprising the cerium complex according to any one of [1] to [9].
[13] A compound represented by formula (8).

(In the formula, G ′, D, R ² , R ³ , R ⁴ , Q, p and m ′ represent the same meaning as described above.)

The cerium complex of the present invention exhibits high electron acceptor and hole acceptability. Accordingly, charge recombination can be promoted on the cerium complex, and excellent light emission characteristics can be exhibited in the organic electroluminescence device.

The present invention will be described below.
In the present specification, “which may have a substituent” means that the hydrogen atom constituting the compound or group described immediately after that is unsubstituted and a part of the hydrogen atom or It means both when all are substituted by substituents. As the “substituent”, for example, hydrocarbyl group, hydrocarbyloxy group, hydrocarbylthio group, halogen atom, cyano group, amide group, imide group, unsubstituted silyl group, substituted silyl group, acyl group, alkoxycarbonyl group, Alkoxysulfonyl group, alkoxyphosphoryl group, unsubstituted phosphino group, substituted phosphino group, unsubstituted phosphine oxide group, substituted phosphine oxide group, unsubstituted amino group, substituted amino group, hydroxyl group, mercapto group, carboxyl group, a sulfo group, a phosphoric acid group, phosphorous acid group, a nitro ^{^{^{group, -NH -, -O -, -S}}} -, -COO -, -SO 3 -, -HPO 4 -, and -H ₂ PO ₃ ^- Preferably, a hydrocarbyl group, a hydrocarbyloxy group, a hydrocarbylthio group, a halogen atom, a cyano group, Is a silyl group which may have a substituent, more preferably a hydrocarbyl group.
Further, in the present specification, when there are a plurality of the same symbols in the same formula, they may be the same or different.

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

When the substituent is a group containing a carbon atom and an aromatic ring, the number of carbon atoms is usually 2 to 36, preferably 3 to 26, and more preferably 6 to 16 It is.

Examples of the hydrocarbyl group include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Decyl, dodecyl, 2-ethylhexyl, 3,7-dimethyloctyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl, benzyl, α, α-dimethyl Benzyl, 1-phenethyl, 2-phenethyl, vinyl, propenyl, butenyl, oleyl, eicosapentaenyl, docosahexaenyl, 2,2-diphenylvinyl, 1,2,2- Triphenylvinyl group, 2-phenyl-2-propenyl group, phenyl group, 2-tolyl group, 4-tolyl Group, 4-trifluoromethylphenyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, terphenyl group, 3,5-diphenylphenyl group, 3,4-diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 2-anthryl group Group, 9-phenanthryl group, 1-pyrenyl group, chrycenyl group, naphthacenyl group, and coronyl group, preferably methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl Group, 3,7-dimethyloctyl group, benzyl group, α, α-dimethylbenzyl group, 1-phenethyl group, 2-phenethyl group, vinyl group, propenyl group, butenyl group, phenyl group, 2-tolyl group, 4 -Tolyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, terphenyl group, fluorenyl group, 1-naphthyl group or 2-naphthyl group, more preferably a methyl group, an ethyl group, tert-butyl group, 1-propyl group, 1-butyl group, 2-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-ethylhexyl group, benzyl group, α, α- A dimethylbenzyl group, a vinyl group, a butenyl group, a phenyl group, a 2-tolyl group, or a 4-tolyl group, more preferably a methyl group, an ethyl group, or a 1-propyl group. A pill group, a hexyl group, a 2-ethylhexyl group, a tert-butyl group, or a vinyl group.

Examples of the hydrocarbyloxy group include methoxy group, ethoxy group, 1-propyloxy group, 2-propyloxy group, 1-butyloxy group, 2-butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyl Oxy group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, cyclopropyloxy group, cyclopentyloxy group, cyclohexyloxy group, 1-adamantyloxy group, 2- Adamantyloxy group, norbornyloxy group, benzyloxy group, α, α-dimethylbenzyloxy group, 2-phenethyloxy group, 1-phenethyloxy group, phenoxy group, octylphenoxy group, 1-naphthyloxy group, and 2-Naphtilo A methoxy group, preferably a methoxy group, an ethoxy group, a 1-propyloxy group, a 2-propyloxy group, a 1-butyloxy group, a 2-butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, Hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, or 3,7-dimethyloctyloxy group, more preferably methoxy group, ethoxy group, or 1-propyloxy It is a group.

Examples of the hydrocarbylthio group include methylthio group, ethylthio group, 1-propylthio group, 2-propylthio group, 1-butylthio group, 2-butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, octylthio group. Group, decylthio group, dodecylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group, cyclopropylthio group, cyclopentylthio group, cyclohexylthio group, 1-adamantylthio group, 2-adamantylthio group, norbornylthio group Benzylthio group, α, α-dimethylbenzylthio group, 2-phenethylthio group, 1-phenethylthio group, phenylthio group, octylphenylthio group, 1-naphthylthio group, and 2-naphthylthio group, preferably , Methylthio group , Ethylthio group, 1-propylthio group, 2-propylthio group, 1-butylthio group, 2-butylthio group, isobutylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, 2-ethylhexylthio group, or 3,7-dimethyloctylthio group, more preferably methylthio group, ethylthio group, or 1-propylthio group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom or a chlorine atom.

Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, Examples thereof include a ditrifluoroacetamide group and a dipentafluorobenzamide group, preferably a formamide group, an acetamido group, a propioamide group, a butyroamide group, or a benzamide group.

An imide group is a group obtained by removing a hydrogen atom bonded to the nitrogen atom from an imide.
Examples of the imide group include an N-succinimide group, an N-phthalimide group, and a benzophenone imide group, and an N-phthalimide group is preferable.

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

Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group, tert-butyldimethylsilyl group, pentyldimethylsilyl group, and hexyldimethyl. Silyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, triphenylsilyl Group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, and dimethylphenylsilyl group. Methylsilyl group, triethylsilyl group, or a tripropylsilyl group.

Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group, and preferably an acetyl group or It is a benzoyl group.

Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl Group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, and dodecyloxycarbonyl group Preferably, methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butto Aryloxycarbonyl group, or a isobutoxycarbonyl group.

Examples of the alkoxysulfonyl group include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, isopropyloxysulfonyl group, butoxysulfonyl group, isobutoxysulfonyl group, sec-butoxysulfonyl group, tert-butoxysulfonyl group, pentyloxysulfonyl Group, hexyloxysulfonyl group, heptyloxysulfonyl group, octyloxysulfonyl group, 2-ethylhexyloxysulfonyl group, nonyloxysulfonyl group, decyloxysulfonyl group, 3,7-dimethyloctyloxysulfonyl group, and dodecyloxysulfonyl group Preferably, methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, isopropyloxysulfonyl group, butto Shisuruhoniru group, or a isobutoxy sulfonyl group.

Examples of the alkoxyphosphoryl group include a dimethoxyphosphoryl group, a diethoxyphosphoryl group, a dipropyloxyphosphoryl group, a diisopropyloxyphosphoryl group, a dibutoxyphosphoryl group, and an ethylenedioxyphosphoryl group, preferably a dimethoxyphosphoryl group. It is.

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

Examples of the substituted phosphino group include a phenylphosphino group, a diphenylphosphino group, a methylphosphino group, a dimethylphosphino group, an ethylphosphino group, a diethylphosphino group, a propylphosphino group, a dipropylphosphino group, Examples thereof include a butylphosphino group and a dibutylphosphino group, and a diphenylphosphino group, a dimethylphosphino group, a diethylphosphino group, a dipropylphosphino group, or a dibutylphosphino group is preferable.

The substituted phosphine oxide group is a phosphine oxide 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 arylalkyl group. It is a group.

Examples of substituted phosphine oxide groups include phenylphosphine oxide groups, diphenylphosphine oxide groups, methylphosphine oxide groups, dimethylphosphine oxide groups, ethylphosphine oxide groups, diethylphosphine oxide groups, propylphosphine oxide groups, and dipropylphosphine oxide groups. , A butylphosphine oxide group, and a dibutylphosphine oxide group, preferably a diphenylphosphine oxide group, a dimethylphosphine oxide group, a diethylphosphine oxide group, a dipropylphosphine oxide group, or a dibutylphosphine oxide group.

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

Examples of the substituted amino group include a phenylamino group, a diphenylamino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, a butylamino group, and a dibutylamino group. And preferably a diphenylamino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a dipropylamino group, or a dibutylamino group.

When the substituent is —NH ⁻ , —O ⁻ , —S ⁻ , —COO ⁻ , —SO ₃ ⁻ , —HPO ₄ ⁻ , or —H ₂ PO ₃ ^— , the substituent is a counter ion. You may have. Examples of the counter ion include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, and ammonium ion, preferably sodium ion, potassium ion, or ammonium ion.

<Cerium complex>
The cerium complex of the present invention is a cerium complex represented by the composition formula (1).

In the composition formula (1), M is cerium ion. The valence of cerium ions is preferably trivalent because the emission intensity of the cerium complex is excellent.

In the composition formula (1), X is a counter ion. The counter ion is a counter ion that neutralizes the total charge of the cerium ion and L, and is usually an anion, but may be a cation when L has a negative charge of 2 or more. That is, it is only necessary that the total charge of the entire composition formula (1) is zero.

Examples of the cation include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, and ammonium ion.

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, hexafluoro Antimony ion, hexafluoroarsenic ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion, trifluoroacetic acid ion, benzenesulfonic acid ion, p-toluenesulfonic acid ion, dodecylbenzenesulfonic acid ion, tetraphenylborate ion, tetrakis ( Pentafluorophenyl) borate ion.

The counter ion represented by X is preferably fluoride ion, chloride ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimony ion, hexafluoroarsenic ion, methane Sulfonate ion, trifluoromethanesulfonate ion, trifluoroacetate ion, benzenesulfonate ion, paratoluenesulfonate ion, dodecylbenzenesulfonate ion, tetraphenylborate ion, or tetrakis (pentafluorophenyl) borate ion, More preferably, chloride ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ON, trifluoroacetate ion, benzenesulfonate ion, p-toluenesulfonate ion, tetraphenylborate ion, or tetrakis (pentafluorophenyl) borate ion, more preferably perchlorate ion, tetrafluoroborate ion, Hexafluorophosphate ion, trifluoromethanesulfonate ion, trifluoroacetate ion or tetraphenylborate ion, particularly preferably tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion or tetraphenylborate ion Ion.

In the composition formula (1), L ′ is a monodentate or bidentate ligand. The monodentate or bidentate 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. For example, water, methanol, Ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, triarylphosphine oxide, trialkylphosphine oxide, pyridine, quinoline, pyrazole, imidazole, oxazole, thiazole, benzimidazole, benzoxazole, benzothiazole, triazine, pyrimidine, pyrazine, bipyridine, biquinoline, Examples include terpyridine, phenanthroline, triarylphosphine, trialkylphosphine, and trialkylamine.

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

In the composition formula (1), the combination of a, b and c is related to the coordination number of the central metal ion of the complex and the valence of the ligand, and forms a stable complex structure. B = 3 and c = 0 are preferred.

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

Since A forms a stable complex structure, it is preferably a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, or P (═O), more preferably a carbon atom or a nitrogen atom, still more preferably. Is a nitrogen atom.

In the composition formula (1), D is a direct bond or a hydrocarbondiyl group which may have a substituent, and G is a heterocyclyl group which may have a substituent or a hydrogen atom. is there. It is preferable that at least one of D in the composition formula (1) and D ′ in the formulas (2-1), (2-2), and (2-3) is not a direct bond.

The hydrocarbon diyl group of the hydrocarbon diyl group which may have a substituent represented by D usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably It is 1 to 10, more preferably 1 to 5. Examples of the hydrocarbon diyl group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, methylethylene group, methylpropylene group, ethylethylene group, ethylpropylene group, and methylbutylene. Group, ethylhexylene group, dimethyloctylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, adamantanediyl group, norbornanediyl group, phenylenemethylene group, vinylene group, propenylene group, butenylene group, diphenylvinylene group, Phenylvinylene group, phenylpropenylene group, phenylene group, methylphenylene group, biphenyldiyl group, terphenyldiyl group, tetraphenylphenylene group, (2,2-diphenylvinyl) phenylene group, (1,2,2- (Riphenylvinyl) phenylene group, fluorenediyl group, naphthylene group, anthrylene group, phenanthrylene group, and pyrenediyl group, preferably methylene group, ethylene group, propylene group, butylene group, methylethylene group, methylpropylene Group, ethylethylene group, ethylpropylene group, methylbutylene group, ethylhexylene group, phenylenemethylene group, vinylene group, propenylene group or phenylene group, more preferably methylene group, ethylene group, propylene group, butylene. Group, methylethylene group, methylpropylene group, vinylene group or propenylene group, more preferably methylene group, ethylene group, propylene group, butylene group, methylethylene group or methylpropylene group, particularly preferred Is Ren group, an ethylene group, or a propylene group. When a plurality of D are present, each D may be the same as or different from each other. The “hydrocarbon diyl group” is also referred to as a “hydrocarbylene group”.

In the composition formula (1), G is a heterocyclyl group which may have a substituent, or a hydrogen atom. The heterocyclyl group means the remaining atomic group excluding one hydrogen atom directly bonded to the carbon atom or nitrogen atom constituting the ring of the heterocyclic compound. Examples of the heterocyclyl group of the heterocyclyl group optionally having a substituent represented by G include a piperidinyl group, piperazinyl group, benzofuryl group, furyl group, benzothienyl group, thienyl group, benzopyrrolyl group, pyrrolyl group, Examples include benzoimidazolyl group, imidazolyl group, benzopyrazolyl group, pyrazolyl group, benzoxazolyl group, oxazolyl group, benzothiazolyl group, thiazolyl group, quinolyl group, and pyridyl group, preferably benzofuryl group, furyl group, benzothienyl group Group, thienyl group, benzopyrrolyl group, pyrrolyl group, benzimidazolyl group, imidazolyl group, benzopyrazolyl group, pyrazolyl group, benzoxazolyl group, oxazolyl group, benzothiazolyl group, thiazolyl group, quinolyl group, or pyridyl group More preferably, it is a benzimidazolyl group, an imidazolyl group, a benzopyrazolyl group, a pyrazolyl group, a benzoxazolyl group, an oxazolyl group, a benzothiazolyl group, a thiazolyl group, a quinolyl group, or a pyridyl group, and more preferably a benzoimidazolyl group, It is an imidazolyl group, a pyrazolyl group or a pyridyl group, and particularly preferably a benzoimidazolyl group or an imidazolyl group. When there are a plurality of Gs, they may be the same or different.

In the compositional formula (1), L is a group containing a six-membered aromatic ring having two or more nitrogen atoms in the structure. Examples of the aromatic 6-membered ring having two or more nitrogen atoms include pyrazine, pyrimidine, pyridazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,2, 3,4-tetrazine, 1,2,3,5-tetrazine, and 1,2,4,5-tetrazine are preferable, and a cerium complex having high hole accepting property and high electron accepting property can be obtained. , Pyrazine, pyrimidine, pyridazine or 1,3,5-triazine, more preferably pyrazine, pyrimidine or 1,3,5-triazine, still more preferably pyrimidine or 1,3,5 5-triazine, particularly preferably pyrimidine. L is preferably a group represented by the above formula (2-1), (2-2), or (2-3) because it can form a stable cerium complex. The group represented by -1) is more preferable.

In the above formulas (2-1), (2-2), and (2-3), D ′ is a direct bond or an optionally substituted hydrocarbondiyl group, preferably a substituent. It is a hydrocarbon diyl group which may have. Examples of the hydrocarbon diyl group and preferred examples of the hydrocarbon diyl group which may have a substituent, and the hydrocarbon diyl group of the hydrocarbon diyl group which may have a substituent represented by D above , But particularly preferred is a methylene group. Of the plurality of D ', at least one of them is preferably not a direct bond, and more preferably, all D's are optionally substituted hydrocarbondiyl groups.

In the above formula (2-1), E represents a divalent group having a 5-membered aromatic ring containing a nitrogen atom, or a divalent group having a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring. It is a group. Examples of E include imidazolyl, oxazolyl, thiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzimidazolyl, benzoxazolyl, and benzthiazolyl A divalent group in which one hydrogen atom is removed from the hydrogen atom to form a stable complex, preferably an imidazolyl group, an oxazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, or a benzthiazolyl group Are each a divalent group obtained by removing one hydrogen atom, more preferably an imidazolyl group or a divalent group obtained by removing one hydrogen atom from each of a benzimidazolyl group.

In the above formulas (2-1) and (2-3), J is a monovalent group having an aromatic 6-membered ring containing two or more nitrogen atoms. Preferably, J is a group obtained by removing one hydrogen atom from an aromatic 6-membered ring containing two or more nitrogen atoms. Examples of aromatic 6-membered rings containing two or more nitrogen atoms include pyrazine ring, pyrimidine ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine Ring, 1,2,3,4-tetrazine ring, 1,2,3,5-tetrazine ring and 1,2,4,5-tetrazine ring, which have high hole acceptability and high electron acceptability. Therefore, it is preferably a pyrazine ring, a pyrimidine ring, a pyridazine ring, or a 1,3,5-triazine ring, and more preferably a pyrazine ring, a pyrimidine ring, or 1,3,5. A triazine ring, more preferably a pyrimidine ring or a 1,3,5-triazine ring, and particularly preferably a pyrimidine ring.

In the above formula (2-2), E ′ is a monovalent group having a monovalent group having an aromatic 5-membered ring containing a nitrogen atom or a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring. It is the basis of. Examples of E ′ include imidazolyl, oxazolyl, thiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzimidazolyl, benzoxazolyl, and benzthiazolyl. Group, and forms a stable complex, and is preferably an imidazolyl group, an oxazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, or a benzthiazolyl group, more preferably an imidazolyl group, or Benzimidazolyl group.

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

Rings that are included in E, J, E ′, and J ′, in which the aromatic 5-membered ring, aromatic 6-membered ring, and aromatic 5-membered ring are condensed with the aromatic ring may each independently have a substituent. When there are a plurality of substituents, the substituents may be combined together to form a ring with the atoms to which they are bonded.

J and E ′ are preferably not forming a bond with M (not coordinated to M), because the hole acceptability and electron acceptability of the cerium complex are higher.

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

In 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 examples and preferred examples of the substituent described above, and among them, the hydrocarbyl group is particularly preferred, and the methyl group, ethyl group, 1-propyl group are preferred. The group, hexyl group, 2-ethylhexyl group, tert-butyl group or vinyl group is particularly preferred. n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. When n is 2, each R ² may be the same as or different from each other, and two R ² may be combined to form a ring together with the carbon atom to which each is bonded. D ′ and J represent the same meaning as described above.

Still another example of the formula (2-1) includes a group represented by the following formula (4).

In the formula (4), p is an integer of 0 to 4, preferably 0 or 1, more preferably 0. when p is 2 or more, each R ² may being the same or different, two R ² bound to adjacent carbon atoms are taken together the carbon atoms bonded thereto And may form a ring. R ² , D ′ and J represent the same meaning as described above.

The above-mentioned J is preferably a monovalent group represented by the following formula (5) because the electron acceptability of the cerium complex is further improved.

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

Examples of the cerium complex of the present invention include a cerium 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 examples and preferred examples of the substituent described above. Among them, the hydrocarbyl group is particularly preferred, and the methyl group, ethyl group, 1-propyl group are preferred. The group, hexyl group, 2-ethylhexyl group, tert-butyl group or vinyl group is particularly preferred. R ⁴ is preferably a hydrogen atom rather than a monovalent group. m ′ is an integer of 1 to 3, and preferably 2 or 3. D, R ² , R ³ , Q, n, M, X, L ′, b and c represent the same meaning as described above. When there are a plurality of Qs, they may be the same or different.

In the compositional formula (6), G ′ is a heterocyclyl group which may have a substituent, and examples and preferred examples thereof are heterocyclyl groups in the heterocyclyl group which may have a substituent represented by G. These are the same as the examples and preferred examples.

Other examples of the cerium complex of the present invention include a cerium complex represented by the following composition formula (7).

In the composition formula (7), R ⁴ , G ′, D, R ² , R ³ , Q, p, m ′, M, X, L ′, b and c represent the same meaning as described above.

Preferred examples of the cerium complex represented by the composition formula (7) include a cerium complex represented by the following composition formula (7-1).

In the composition formula (7-1), R ⁵ represents a hydrogen atom or a hydrocarbyl group which may have a substituent. The hydrocarbyl 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 represent the same meaning as described above.

As the cerium complex of the present invention, cerium complexes represented by the following composition formulas (B-1) to (B-8) are preferable. Since the hole-accepting property and electron-accepting property of the cerium complex are higher, cerium complexes represented by the following composition formulas (B-5) to (B-8) are more preferable, and the following composition formula is more preferable. These are cerium complexes represented by (B-7) to (B-8).

The cerium complex of the present invention usually emits blue light.

<Method for producing cerium complex>
The cerium complex of the present invention can be produced by a known method used for complex synthesis. For example, a compound serving as a ligand and a cerium salt are mixed in a solvent at room temperature. Then, it can manufacture easily by collect | recovering the obtained precipitation or distilling a solvent off from a reaction liquid.

Examples of the cerium salt include cerium chloride (III), cerium nitrate (III), and cerium trifluoromethanesulfonate (III). In addition, a cerium salt may be used individually by 1 type, or may use 2 or more types together.

The ratio of the compound used as the ligand used in the above mixing and the cerium salt is determined so that the number of coordination atoms with respect to one cerium atom is usually 6 to 12, preferably 8. To do.

The mixing temperature and reaction time can be usually produced by stirring for about 1 hour at room temperature, but the reaction time can be shortened by raising the temperature to a temperature at which the solvent is refluxed.

The above mixing is usually performed in an inert gas (for example, nitrogen gas, argon gas) atmosphere.

Examples of the solvent used for the mixing include aqueous solvents such as buffer solutions and organic solvents, and organic solvents are preferable. In addition, a solvent may be used individually by 1 type, or may use 2 or more types together.

Examples of the organic solvent include nitrile solvents such as acetonitrile and benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, tetrahydrofuran and dioxane. Ether solvents such as toluene, aromatic hydrocarbon solvents such as toluene and xylene, fats such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane Aromatic hydrocarbon solvents, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and its derivatives such as ethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, Examples include alcohol solvents such as cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. Methanol, ethanol, chloroform, dichloromethane, or acetonitrile Is preferred.

The counter ion X of the cerium complex of the present invention can be easily exchanged for an arbitrary counter ion by using a method such as ion exchange chromatography or salting out. In the salting-out method, for example, a saturated solution of a salt of an ion to be exchanged is added to the solution of the cerium complex obtained by the above-described method, and a target counter ion is recovered by collecting a precipitate formed thereby. The complex with it can be obtained.

<Composition>
The cerium complex of the present invention can be used as it is or mixed with a charge transport material and used as a composition. This composition is usually liquid or solid at 25 ° C.

The charge transport material refers to a material responsible for charge transport in an element such as an organic electroluminescence element (also referred to as “light emitting element”), and is a hole transport material and an electron transport material. The charge transport material can be classified into a low molecular organic compound and a high molecular organic compound (for example, a high molecular compound or an oligomer). The polymer compound and the oligomer are preferably conjugated.

As the hole transport material, for example, materials known as hole transport materials for organic electroluminescence devices such as fluorene and derivatives thereof, aromatic amine and derivatives thereof, carbazole derivatives, polyparaphenylene derivatives, and the like can be used. it can.

Examples of the electron transport material include oxadiazole derivatives, triazine derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, Known materials can be used as electron transport materials for organic electroluminescence devices, such as fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline and derivatives thereof.

In the composition of the present invention, the content of the cerium complex is usually 0.01 to 300 parts by mass with respect to 100 parts by mass of the charge transport material, and the balance between hole acceptability and electron acceptability is improved. Therefore, it is preferably 0.1 to 150 parts by mass, and more preferably 1 to 50 parts by mass.

In the composition of the present invention, each of the cerium complex and the charge transport material may be used alone or in combination of two or more.

<Organic film>
The organic film of the present invention contains the cerium complex. The organic film of the present invention can be easily formed by, for example, a coating method such as an ink jet printing method using a solution obtained by mixing the cerium complex and a solvent.

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

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

<Organic electronic device>
The organic electronic device of the present invention contains the cerium complex. Examples of the organic electronic device of the present invention include a light emitting device having a layer containing the cerium complex, a switching device having a layer containing the cerium complex, and a photoelectric conversion device having a layer containing the cerium complex.

[Light emitting element]
A light emitting element usually has a light emitting layer between electrodes composed of an anode and a cathode. This light emitting element may contain layers other than a light emitting layer, in order to improve luminous efficiency and durability. Examples of the layer other than the light emitting layer include a charge transport layer, a charge blocking layer, a charge injection layer, and a buffer layer. Each layer may be included in the light emitting element only in one layer, or may be included in two or more layers.

The light emitting layer is a layer having a function of emitting light.

The charge transport layer is a general term for an electron transport layer and a hole transport layer. The hole transport layer is a layer having a function of transporting holes. The electron transport layer is a layer having a function of transporting electrons.

The charge blocking layer is a layer having a function of confining holes or electrons in the light emitting layer, and among them, a layer that transports electrons and confines holes is called a hole blocking layer, and a layer that transports holes and confines electrons. Is called an electron blocking layer.

Examples of the buffer layer include a layer containing a conductive polymer compound adjacent to the anode.

Examples of the structure of the light emitting device include the following structures a) to q).
a) anode / light emitting layer / cathode b) anode / hole transport layer / light emitting layer / cathode c) anode / light emitting layer / electron transport layer / cathode d) anode / light emitting layer / hole blocking layer / cathode e) anode / Hole transport layer / light emitting layer / electron transport layer / cathode f) anode / charge injection layer / light emitting layer / cathode g) anode / light emitting 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 l) 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 / emission 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), “/” represents each layer Indicates that they are stacked adjacent to each other. Note that each of the light-emitting layer, the hole transport layer, and the electron transport layer may be used alone or in combination of two or more layers. )

Among the charge transport layers provided adjacent to the electrodes, a layer having a function of improving the charge injection efficiency from the electrodes and having an effect of lowering the driving voltage of the light emitting element is generally called a charge injection layer. Examples of the light emitting device including the charge injection layer include a light emitting device including a charge injection layer adjacent to the cathode and a light emitting device including a charge injection layer adjacent to the anode.

In the light-emitting element, an insulating layer may be provided adjacent to the electrode in order to improve adhesion with 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. As a light emitting element provided with an insulating layer, the light emitting element provided with the said insulating layer adjacent to a cathode and the light emitting element provided with the said insulating layer adjacent to an anode are mentioned, for example.

The light emitting layer is a layer containing the cerium complex or the composition. The light emitting layer may contain other light emitting materials. Other luminescent materials include, for example, naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-based, xanthene-based, coumarin-based, and cyanine-based pigments, metal complexes of 8-hydroxyquinoline and its derivatives, Aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof may be mentioned.

Examples of the material used for the hole transport layer include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, And triphenyldiamine derivatives, polyaniline and derivatives thereof, polyaminophen and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, and poly (2,5-thienylene vinylene) and derivatives thereof. .

The thickness of the hole transport layer is set so that the light emission efficiency or photoelectric efficiency and the driving voltage are appropriate values, and is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

Examples of materials used for the electron transport layer include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone. Derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

The thickness of the electron transport layer is set so that the light emission efficiency or photoelectric efficiency and the driving voltage are appropriate values, and is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. It is.

Each layer is formed on an adjacent layer or substrate. 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, and coating method. preferable.

Examples of the coating method include spin coating, casting, dip coating, gravure coating, bar coating, roll coating, spray coating, screen printing, flexographic printing, offset printing, and inkjet printing. And a roll coating method, a spray coating method, a flexographic printing method, or an ink jet printing method is preferable.

The light emitting device of the present invention is usually formed using a substrate. An electrode is formed on one surface of the substrate, and each layer of the element is formed on the other surface. Examples of the substrate include a substrate made of a material such as glass, plastic, and silicon, and a substrate made of a polymer film.

The anode and cathode included in the light emitting device of the present invention are usually transparent or translucent, but the anode is preferably transparent or translucent.

Examples of the material used for the anode include a conductive metal oxide film, a translucent metal thin film, and an organic transparent conductive film. Preferably, indium oxide, zinc oxide, tin oxide, and a composite thereof ( Indium tin oxide (ITO), indium zinc oxide, etc.), antimony tin oxide, NESA, gold, platinum, silver, copper, polyaniline and derivatives thereof, and polyaminophen and derivatives thereof.

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 electric conductivity, and is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 40 nm to 500 nm.

The material used for the cathode is preferably a material having a small work function, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium. Metals such as samarium, europium, terbium and ytterbium; alloys of two or more metals selected from the group consisting of those metals; one or more metals selected from the group consisting of these metals and gold, silver, platinum , Copper, manganese, titanium, cobalt, nickel, tungsten, and an alloy with one or more metals selected from the group consisting of tin; graphite; and graphite intercalation compounds.

Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, and a laminating 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 electric conductivity and durability, and is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm.

In the light emitting device of the present invention, a protective layer or a protective cover for protecting the light emitting device may be formed after forming the cathode in order to protect the device from the outside and use it stably for a long time.

Examples of the charge injection layer include a layer containing a conductive polymer, a layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer, and a cathode material. Examples thereof include a layer containing a material having an electron affinity with a value intermediate to that of the electron transport material contained in the electron transport layer.

Examples of the material used for the charge injection layer include polyaniline and derivatives thereof, polyaminophen and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof. Derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines, and carbon.

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

The light emitting element is useful for a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, illumination, and the like.

[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 have an arbitrary layer other than the charge separation layer between the anode and the cathode. The layer containing the cerium complex or the composition may be contained in the charge separation layer or in any layer other than the charge separation layer.

The materials and examples of the cathode and the anode are the same as the materials and examples 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 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.

Examples of the electron donating compound include conjugated polymer compounds. Examples of the conjugated polymer compound include a conjugated polymer compound containing a thiophenediyl group and a conjugated polymer compound containing a fluorenediyl group.

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

The photoelectric conversion element is usually formed on a substrate. The example of a board | substrate is the same as the example of the board | substrate used for a 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 formula (8), R ⁴ , G ′, D, R ² , R ³ , Q, p, and m ′ represent the same meaning as described above.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples.

<Synthesis Example 1>
Tris (2-benzimidazolylmethyl) amine (hereinafter referred to as “ntb”) was synthesized according to the description of Inorganica Chimica Acta 231, 109-114 (1995). Specifically, ntb was obtained by heating and refluxing o-phenylenediamine, nitrilotriacetic acid, and propylene glycol at 144 to 154 ° C. for 24 hours.

<Synthesis Example 2>
2-Chloro-4,6-di-tert-butylpyrimidine is described in Angew. Chem. Int. Ed. 47, 8246-8250 (2008). Specifically, a tetrahydrofuran solution of 2,4,6-trichloropyrimidine and copper iodide was cooled to 0 ° C., tert-butylmagnesium chloride was added thereto, and the mixture was stirred at 0 ° C. for 2 hours to give 2- Chloro-4,6-di-tert-butylpyrimidine was obtained.

<Example 1>
Synthesis of compound (C-1)

Tris (dibenzylideneacetone) dipalladium (0) (46 mg, 0.043 mmol), tripotassium phosphate (363 mg, 1.71 mmol), 2-chloro-4,6-di-tert-butylpyrimidine (429 mg) was added to the Schlenk tube. , 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) were added, and the gas in the Schlenk tube was replaced with argon gas, and then dehydrated toluene (5 mL) was added. Then, it heated to 50 degreeC with the oil bath, after stirring for 7.5 hours, it heated to 110 degreeC and stirred for 5 hours as it was. Water was added to the resulting reaction solution to stop the reaction. Chloroform was added thereto for extraction, and the obtained organic layer was washed twice with water and then dried over anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator. The obtained residue is purified by alumina column alumina chromatography (developing solution: chloroform) to obtain the compound represented by the above formula (C-1) (compound (C-1)) as a yellow oily substance. (255 mg, yield: 31.8%).

The NMR data of the compound (C-1) is shown below.
¹ H NMR (300 MHz, CDCl ₃ ) δ (ppm) = 8.36 (2H, d, J = 7.8 Hz), 7.80 (2H, d, J = 6.6 Hz), 7.66 (1H, d, J = 7.5 Hz), 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 cerium complex (B-7) After adding compound (C-1) (64 mg, 0.080 mmol) and cerium (III) trifluoromethanesulfonate (22 mg, 0.037 mmol) to the flask, After replacing the gas with argon gas, chloroform (1 mL) was added, and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent in the reaction solution was concentrated to dryness under reduced pressure. The obtained residue was extracted with dichloromethane, the extract was filtered and the solvent was distilled off to obtain a cerium complex (B-7). The cerium complex (B-7) is a cerium complex represented by the above formula (B-7). When this complex was irradiated with ultraviolet rays (365 nm), it emitted blue light.

<Comparative Example 1>
Synthesis of cerium complex (D-1) The following formula (D-1):

A cerium complex represented by the formula (Cerium complex (D-1)) is obtained from Angew. Chem. Int. Ed. 46, 7399-7403 (2007).

[LUMO and HOMO levels of cerium complexes]
In order to compare the LUMO level and the HOMO level of the cerium complex (B-7) of Example 1 and the cerium complex (D-1) of Comparative Example 1, a semi-empirical molecule was obtained using WinMOPAC3.9 from Fujitsu Limited. The LUMO level and HOMO level of each cerium complex after the structure optimization by the orbital calculation PM5 method was obtained with the following partial structure.

According to Table 1, the partial structure of the cerium complex (B-7) of Example 1 has a LUMO level 0.63 eV lower than the partial structure of the cerium complex (D-1) of Comparative Example 1. This indicates that the cerium complex (B-7) has higher hole accepting properties and electron accepting properties than the cerium complex (D-1). Therefore, it can be seen that the cerium complex (B-7) exhibits excellent emission characteristics on the light-emitting element.

The cerium complex of the present invention is useful as a material for light-emitting elements, switching elements, photoelectric conversion elements, magnetic materials, biological probes, contrast agents, additives, modifiers, catalysts, and the like.

Claims

Composition formula (1):

(Where
M is a cerium ion.
A is a carbon atom, a silicon atom, a nitrogen atom, a nitrogen cation, a boron anion, a phosphorus atom, or P (═O). When A is a carbon atom, a silicon 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 hydrocarbondiyl group which may have a substituent.
G is a heterocyclyl group which may have a substituent, or a hydrogen atom.
L is a group containing an aromatic 6-membered ring having two or more nitrogen atoms.
When a plurality of L are present, each L may be the same as or different from each other. When a plurality of D are present, each D may be the same as or different from each other. When a plurality of G are present, each G may be the same as or different from each other.
X is a counter ion.
L ′ is a monodentate or bidentate 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, the plurality of A may be the same or different. When b is 2 or more, the plurality of X may be the same or different. When c is 2 or more, a plurality of L ′ may be the same or different. )
A cerium complex represented by:
The cerium complex according to claim 1, wherein L is a group represented by the formula (2-1), (2-2) or (2-3).
-D'-EJ (2-1)
-D'-J'-E '(2-2)
-D'-J (2-3)
(Where
D ′ is a direct bond or a hydrocarbondiyl group which may have a substituent.
E is a divalent group having a 5-membered aromatic ring containing a nitrogen atom or a divalent group having a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with an aromatic ring.
J is a monovalent group having an aromatic 6-membered ring containing two or more nitrogen atoms.
E ′ is a monovalent group having a 5-membered aromatic ring containing a nitrogen atom or a monovalent group having a ring in which an aromatic 5-membered ring containing a nitrogen atom is condensed with 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 in which the aromatic 5-membered ring is condensed with the aromatic ring may each independently have a substituent, and when there are a plurality of substituents Together, they may form a ring with the atoms to which they are attached. )
The cerium complex according to claim 2, wherein the aromatic 5-membered ring of E or E 'is an imidazole ring which may have a substituent.
The cerium complex according to claim 2, wherein the ring in which an aromatic 5-membered ring containing a nitrogen atom of E or E 'is condensed with an aromatic ring is a benzimidazole ring which may have a substituent.
L is the formula (3):

(Where
R 2 is a monovalent group, and n is an integer of 0-2.
When n is 2, each R 2 may be the same as or different from each other, and two R 2 may be combined to form a ring together with the carbon atom to which each is bonded.
D ′ and J have the same meaning as described above. )
Or, formula (4):

(Where
p is an integer of 0-4.
when p is 2 or more, each R 2 may being the same or different, two R 2 bound to adjacent carbon atoms are taken together the carbon atoms bonded thereto And may form a ring.
R 2 , D ′ and J have the same meaning as described above. )
The cerium complex according to claim 1, which is a group represented by the formula:
The cerium complex according to claim 1, wherein A is a nitrogen atom.
J is the formula (5):

(Where
R 3 is a hydrogen atom or a monovalent group. Each R 3 may be the same as or different from each other.
Q is a nitrogen atom or C (R 3 ). )
The cerium complex according to claim 2, which is a monovalent group represented by the formula:
Composition formula (6):

(Where
R 4 is a hydrogen atom or a monovalent group, and G ′ is a heterocyclyl group which may have a substituent.
Each R 4 may be the same as or different from each other. When a plurality of G ′ are present, each G ′ may be the same as or different from each other.
m ′ is an integer of 1 to 3.
D, R 2 , R 3 , Q, n, M, X, L ′, b and c represent the same meaning as described above.
When a plurality of Q are present, each Q may be the same as or different from each other. )
Or composition formula (7):

(In the formula, R 4 , G ′, D, R 2 , R 3 , Q, p, m ′, M, X, L ′, b and c represent the same meaning as described above.)
The cerium complex of Claim 1 represented by these.
Composition formula (7-1):

(Where
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 represent the same meaning as described above. )
The cerium complex of Claim 1 represented by these.
A composition comprising the cerium complex according to claim 1 and a charge transport material.
An organic film containing the cerium complex according to claim 1.
An organic electronic device comprising the cerium complex according to claim 1.
The compound represented by Formula (8).

(Where
R 3 is a hydrogen atom or a monovalent group.
m ′ is an integer of 1 to 3.
A plurality of R 3 may be the same or different.
Q is a nitrogen atom or C (R 3 ). When a plurality of Q are present, each Q may be the same as or different from each other.
R 4 is a hydrogen atom or a monovalent group.
G ′ is a heterocyclyl group which may have a substituent.
Each R 4 may be the same as or different from each other. When a plurality of G ′ are present, each G ′ may be the same as or different from each other.
R 2 is a monovalent group.
p is an integer of 0-4.
Each p may be the same as or different from each other. When a plurality of R 2 are present, each R 2 may be the same or different from each other, and when two R 2 are bonded to adjacent carbon atoms, they are taken together, You may form the ring with the carbon atom to which each couple | bonds.
D is a direct bond or a hydrocarbondiyl group which may have a substituent. When a plurality of D are present, each D may be the same as or different from each other. )