JP2006344891A - Organic electroluminescence element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescence element that has excellent luminescence properties (such as wavelength, luminance, quantum yield, drive voltage, etc.) and ruggedness. <P>SOLUTION: The organic electroluminescence element has at least one organic layer between a pair of electrodes, and includes at least one sort of chemical compound in the organic layer, which includes a structure expressed by the common formula (1) (where R<SB>1</SB>to R<SB>4</SB>express a hydrogen atom or substituent, X<SB>1</SB>and X<SB>2</SB>express C or N, m and n express 0 or 1, M expresses metal ion, Y expresses a molecule or a group coordinate with M, p expresses an integer equal to or greater than zero, and A<SB>1</SB>expresses a single bond or a bivalent coupled group). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic electroluminescent device.

Contains materials such as tetradentate platinum complexes such as phenylpyridine platinum complexes and phenoxypyridine platinum complexes (for example, Patent Document 1) and tetradentate platinum complexes such as octaethylporphyrin platinum complexes (for example, Patent Documents 2 and 3). An organic electroluminescent device is disclosed. However, further improvements have been demanded in terms of shortening the emission wavelength and durability.
International Publication No. 04/108857 Pamphlet US Pat. No. 6,303,238 B1 US Pat. No. 6,653,564B1

  An object of the present invention is to provide an organic electroluminescent device having good light emission characteristics (wavelength, luminance, quantum yield, driving voltage, etc.) and durability.

This object has been achieved by the following means.
(1) An organic electroluminescence device having at least one organic layer between a pair of electrodes, wherein the organic layer contains at least one compound containing a structure represented by the following general formula (I) element.
Formula (I)

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. When R ₁ and R ₂ represent a substituent, they may be bonded to each other to form a ring. R ₁ and R ₄ and R ₂ and R ₃ are not bonded to each other to form an aromatic ring. X ₁ and X ₂ represent a carbon atom or a nitrogen atom. m and n represent 0 or 1. When X ₁ or X ₂ represents a nitrogen atom, m or n is 0. M represents a metal ion. Y represents a molecule that coordinates to M or a group that coordinates. p represents an integer of 0 or more. A ₁ represents a single bond or a divalent linking group.

(2) The organic electroluminescent element according to (1), wherein the general formula (I) is represented by the following general formula (II) or (III).
Formula (II)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ each independently represent an atom selected from carbon, nitrogen and silicon. . Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ may have a substituent. A2, A ₃ and A ₄ represents a single bond or a divalent linking group. q represents 0 or 1; X ₁ , X ₂ , R ₁ , R ₂ , M, m, and n are as defined in general formula (I).
General formula (III)

In the formula, Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ and Z ₁₇ each independently represent an atom selected from carbon, nitrogen, oxygen, sulfur and silicon. The bonds between the atoms in the 5-membered ring formed from Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ and N atoms, and Z ₁₄ , Z ₁₅ , Z ₁₆ , Z ₁₇ and N atoms are single bonds or double bonds. To express. Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ and Z ₁₇ may have a substituent. X ₁ , X ₂ , R ₁ , R ₂ , M, m, and n are as defined in general formula (I), and A ₂ , A ₃ , A ₄ , and q are as defined in general formula (II). It is.

(3) The organic electroluminescence device according to (2), wherein the general formula (II) is represented by the following general formula (IIA).
General formula (IIA)

In the formula, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a substituent. R ₁ , R ₂ and M have the same meanings as those in the general formula (I), and A ₂ , A ₃ , A ₄ and q have the same meanings as those in the general formula (II).

(4) The organic electroluminescence device according to (2), wherein the general formula (III) is represented by the following general formula (IIIA).
General formula (IIIA)

In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent. R ₁ , R ₂ and M have the same meanings as those in the general formula (I), and A ₂ , A ₃ , A ₄ and q have the same meanings as those in the general formula (III).

  (5) In the above general formulas (I) to (IIIA), M is selected from nickel, copper, zinc, tin, palladium, and platinum. Organic electroluminescent element.

  (6) In the said general formula (I)-(IIIA), M is selected from palladium and platinum, The organic electroluminescent element in any one of said (1)-(4) characterized by the above-mentioned.

(7) In the general formulas (II) to (IIIA), A ₂ , A ₃ , A ₄ are a single bond, —C (R ₁₅ ) (R ₁₆ ) —, —C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R ₂₂ )-, -N (R ₂₅ )-, -O-, -S-, -SO-, -SO _2- , -CO -(R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₅ each independently represents a hydrogen atom or a substituent) The organic electroluminescent element according to any one of (2) to (6).

In the present invention, the organic electroluminescent device containing the compounds represented by the general formulas (I) to (IIIA) in the organic layer is excellent in emission characteristics (wavelength, luminance, quantum yield, driving voltage, etc.). Further, when the compound in the present invention is a complex using a ligand that is connected by, for example, A ₂ , A _3, and A ₄ and can be bonded to a metal atom by four atoms, the durability is particularly improved. Since it is an excellent complex containing an organic ligand, it has excellent vapor deposition properties.

  In the present specification, the compounds represented by the general formulas (I), (II), (III), (IIA) and (IIIA) are used synonymously with “the compound of the present invention”. Moreover, the organic electroluminescent element which has an organic layer containing the compound of this invention is used synonymously with "the element of this invention." In this specification, the substituent group A is defined as follows.

(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 1 carbon atoms). , And the example propargyl and 3-pentynyl.),

  An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl and the like), amino. Group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc. An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably ) Has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, and the like.

  An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). ,

  An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group ( Preferably it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino, etc., and a sulfonylamino group (preferably 1 to 1 carbon atoms). 30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably C0-30, more preferably) Has 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms. Amoiru, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),

  A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like), alkylthio. A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolyl Oh, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.),

  A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably having 1 carbon atom). To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, a ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid amide groups (preferably C1-C30, more preferably carbon number) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide That.), Hydroxy group, a mercapto group, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or more preferably fluorine atom),

  Cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, As, for example, nitrogen atom, oxygen atom, sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl), silyloxy group (Preferably 3 to 40 carbon atoms, more preferably 3 to 3 carbon atoms. , Particularly preferably 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  The general formula (I) will be described.

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. The substituent is selected from the substituent group A. When R ₁ and R ₂ represent a substituent, they may be bonded to each other to form a ring. However, R ₁ and R ₄ and R ₂ and R ₃ are not bonded to each other to form an aromatic ring.
Preferred groups for R ₁ , R ₂ , R ₃ and R ₄ are alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, halogen atom, cyano group, sulfo group, carboxyl group, heterocyclic group, silyl group, more preferably alkyl group, cycloalkyl group, aryl group , An alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a cyano group, and a heterocyclic group, and more preferably an alkyl group, an aryl group, and a heterocyclic group.

In the general formula (I), Y represents a coordination molecule or group. p represents an integer of 0 or more. When p represents an integer of 1 or more and Y can be substituted, Y and R ₃ or Y and R ₄ may be bonded to each other. When p represents an integer of 2 or more, a plurality of Y may be the same or different, and when a plurality of Y have a substituent, Y and R ₃ or Y and R ₄ or Y are bonded to each other. May be. The bond between Y and M may be any bond. When Y is a coordinated neutral molecule, the bond between M and Y is represented by a dotted line and represents a coordinate bond. When Y represents a coordinating group, the bond between M and Y is represented by a solid line and represents a coordinate bond.

  Regarding coordination bonds, for example, Gengo Matsubayashi, Hideo Kurosawa, Masaaki Haga, Takayuki Matsushita, “Chemistry of Complexes and Organometallics”, pages 32-35 (Maruzen Co., Ltd.), “Basic Complex Chemistry Research Group” And the latest development ", page 11 (Kodansha Scientific), etc.

Examples of the coordinating molecule include water, carbon monoxide, nitrosyl, and amine (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms. , Ammonia, tetramethylethylenediamine, cyclohexanediamine, etc.), alkenes (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as cyclooctadiene) ), Ether (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as diethyl ether and diphenyl ether), thioether (preferably having 2 to 2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as diethyl sulfide And heterocycles (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridine, bipyridine, quinoline, phenanthroline, etc.), organic Phosphorus compounds (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 18 carbon atoms, and examples thereof include triphenylphosphine, triethylphosphine, tri-t-butylphosphine and the like. ), Sulfoxide (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 18 carbon atoms, such as dimethyl sulfoxide), urea (preferably having 1 to 2 carbon atoms). 30, more preferably 1-20 carbon atoms, particularly preferably 1-18 carbon atoms, such as urea. It is.), And the like.
The coordinating molecule is preferably carbon monoxide, alkene, thioether, heterocycle, organophosphorus, or sulfoxide, more preferably carbon monoxide, alkene, heterocycle, or organophosphorus compound, more preferably alkene or Heterocycle.

When Y represents a coordinating group, the group has the same meaning as the substituent selected from the substituent group A described above.
As the coordinating group, an aryl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, halogen atom, cyano group, sulfo group, A carboxyl group and a heterocyclic group, more preferably an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and a cyano group, and still more preferably an aryl group, an arylthio group, and an aryloxy group.

In the general formula (I), X ₁ and X ₂ represent a carbon atom or a nitrogen atom. m and n represent 0 or 1. However, when X ₁ or X ₂ represents a nitrogen atom, m or n is 0.

  M represents a metal ion. The metal ion represents an element after the third period in the periodic table (preferably an element after the third period, more preferably an element from Group 3 to Group 16 after the third period), such as magnesium or aluminum. , Scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony , Tellurium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, Sumiumu, iridium, platinum, mercury, thallium, lead, bismuth and the like, preferably, zinc, tin, copper, nickel, palladium, platinum, more preferably palladium, platinum.

In the general formula (I), A ₁ represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, but a divalent linking group containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a germanium atom, a selenium atom, or a phosphorus atom is particularly preferable. A group selected from the linking group group A is particularly preferred.

  Linking group A

In the linking group A, R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ (R _{15 to} R ₂₆ ) are each Independently represents a hydrogen atom or a substituent. When R _{15 to} R ₂₆ represent a substituent, the substituent has the same meaning as the substituent selected from the substituent group A. When R _{15 to} R ₂₆ can be substituted, they may further have a substituent, R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ , R ₁₈ and R ₁₉ , R ₁₉ and R ₂₀ , R ₁₇ and R ₁₉ , R ₁₇ and R ₂₀ , R ₁₈ and R ₂₀ , R ₂₁ and R ₂₂ or R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

A ₁ is preferably a single bond or a substituent selected from the linking group group A, of which a single bond, -C (R ₁₅ ) (R ₁₆ )-, -C (R ₁₇ ) (R ₁₈ ) C ( R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R ₂₂ )-, -N (R ₂₅ )-, -O-, -S-, -SO-, -SO ₂ -or -CO- Preferably, a single bond, -C (R ₁₅ ) (R ₁₆ )-, -C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R ₂₂ )-, Or -O- is more preferable, and a single bond or -C (R ₁₅ ) (R ₁₆ )-is more preferable.

In the —C (R ₁₅ ) (R ₁₆ ) —, R ₁₅ and R ₁₆ are preferably a hydrogen atom or a substituent selected from the following substituent group B.

(Substituent group B)
The substituent is an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, a hydroxy group, or a mercapto group, more preferably an alkyl group or a cycloalkyl group. , An aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, more preferably an alkyl group and an aryl group.

In the -C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are preferably a hydrogen atom or a substituent selected from the substituent group B. is there.

In the —Si (R ₂₁ ) (R ₂₂ ) —, R ₂₁ and R ₂₂ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —Ge (R ₂₃ ) (R ₂₄ ) —, R ₂₃ and R ₂₄ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —N (R ₂₅ ) —, R ₂₅ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group. is there.

In the above -P (R ₂₆ )-, R ₂₆ has the same meaning as the preferred range of R _{25 in} the above -N (R ₂₅ )-.

  The relationship of the general formula in the present invention is as follows. The general formula (I) is preferably the general formula (II) or (III). The general formula (II) is preferably the general formula (IIA). The general formula (III) is preferably the general formula (IIIA).

The general formula (II) will be described. Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ each independently represent an atom selected from carbon, nitrogen and silicon. Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ are preferably carbon or nitrogen atoms.

In the general formula (II), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ have a substituent selected from the substituent group A. It may be. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group A heterocyclic group or a silyl group, more preferably a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a heterocyclic group, particularly preferably an alkyl group. Group, alkoxy group, amino group That.

In the general formula (II), A ₂ , A ₃ and A ₄ represent a single bond or a divalent linking group. The linking group is not particularly limited, but is preferably a single bond or a divalent linking group containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a germanium atom, a selenium atom, or a phosphorus atom, A single bond or a group selected from the linking group group A is more preferable, and a single bond, -C (R ₁₅ ) (R ₁₆ )-, -C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R ₂₂ )-, -N (R ₂₅ )-, -O-, -S-, -SO-, -SO _2- , or -CO-, more preferably a single bond , -C (R ₁₅ ) (R ₁₆ )-or -O- is particularly preferred. A ₂ , A ₃ or A ₄ is -C (R ₁₅ ) (R ₁₆ )-, -C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R _{When 22} )-, -Ge (R ₂₃ ) (R ₂₄ )-, -N (R ₂₅ )-and -P (R ₂₆ )-are represented, the preferred range is synonymous with the preferred range described for A ₁ above. It is. However, in the general formula (II), when m or n represents 1 and R ₁ , R ₂ , A ₃ or A ₄ can be substituted, A ₃ and R ₁ or A ₄ and R ₂ are bonded to each other. Does not form an aromatic ring. q represents 0 or 1, and is preferably 1.
In the general formula (II), R ₁ , R ₂ , X ₁ , X ₂ , M, m and n are as defined in the general formula (I).

The general formula (III) will be described. In the general formula (III), Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ and Z ₁₇ (Z _{10 to} Z ₁₇ ) are each independently carbon, nitrogen, oxygen, sulfur. And an atom selected from silicon, and a carbon or nitrogen atom is preferred. Z _{10 to} Z ₁₇ may have a substituent. In the general formula (III), R ₁ , R ₂ , X ₁ , X ₂ , M, m and n are as defined in the general formula (I), and A ₂ , A ₃ , A ₄ and q are the general formula It is synonymous with those in (II), and the preferred range is also the same.
In the general formula (III), the bonds between the atoms in the 5-membered ring formed from Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ and N atoms, and Z ₁₄ , Z ₁₅ , Z ₁₆ , Z ₁₇ and N atoms are Represents a single bond or a double bond.

The general formula (IIA) will be described. In the general formula (IIA), R ₁ , R ₂ and M have the same meaning as those in the general formula (I), and A ₂ , A ₃ , A ₄ and q have the same meaning as those in the general formula (II). . R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ (R _{5 to} R ₁₀ ) each independently represent a hydrogen atom or a substituent. The substituent is synonymous with a substituent selected from Substituent Group A. Preferred examples of R _{5 to} R ₁₀ include a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfonylamino group, and a sulfamoyl group. Group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Sulfino group, heterocyclic group, silyl group, more preferably a hydrogen atom, alkyl group, aryl group, alkoxy group, amino group, sulfonyl group, halogen atom, cyano group, nitro group, heterocyclic group, most Preferably a hydrogen atom, an alkyl group, an aryl group, an alcohol Xyl group and amino group. When R _{5 to} R ₁₀ can be further substituted, they may have a substituent. R ₅ and R ₆ , R ₆ and R ₇ , R ₅ and R ₇ , R ₈ and R ₉ , R ₈ and R ₁₀ , and R ₉ and R ₁₀ on the same pyridine ring are bonded to each other to form a ring. May be.

The general formula (IIIA) will be described. In general formula (IIIA), R ₁ , R ₂ , and M have the same meaning as those in general formula (I), and A ₂ , A ₃ , A ₄ , and q have the same meaning as those in general formula (III). It is. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ (R _{11 to} R ₁₄ ) each independently represent a hydrogen atom or a substituent. The substituent is synonymous with a substituent selected from Substituent Group A. Preferred examples of R _{11 to} R ₁₄ include a hydrogen atom, alkyl group, cycloalkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group. Group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring And a silyl group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom and a cyano group, and still more preferably a hydrogen atom, an alkyl group and an aryl group. When R _{11 to} R ₁₄ can be further substituted, they may have a substituent.

  The compound of the present invention may be a low molecular compound, or may be a polymer such as an oligomer compound or a polymer compound. When it is a polymer, the mass average molecular weight (in terms of polystyrene) is preferably 1000 to 5000000, more preferably 2000 to 1000000, and still more preferably 3000 to 100,000. In the case of a polymer, the structure represented by each general formula may be included in the polymer main chain, or may be included in the polymer side chain. The polymer compound may be a homopolymer compound or a copolymer. The compound of the present invention is preferably a low molecular compound.

  The compound of the present invention can be applied to an organic layer of an organic electroluminescence device, and includes a light emitting material, a host material, a hole injection material, a hole transport material, an electron transport material, a hole block material, an electron block material, and an exciton. It can be used for any of the block materials. The compound of the present invention is preferably a hole injection material, a hole transport material, an electron block material, a host material, or a light emitting material, more preferably a host material or a light emitting material, and further preferably a light emitting material. . When the compound of the present invention is used as a light emitting material, ultraviolet light emission, visible light light emission, or infrared light emission may be used, and fluorescence light emission or phosphorescence light emission may be used.

<Method for Synthesizing Compound of the Present Invention>
The compound of the present invention can be synthesized by various methods. For example, a ligand or a compound containing a dissociated product thereof and a metal ion may be a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, In the presence of a sulfone solvent, a sulfoxide solvent, water, etc.) or in the absence of a solvent, in the presence of a base (inorganic or organic various bases such as sodium methoxide, t-butoxy potassium, triethylamine, Potassium carbonate, etc.), or below room temperature in the absence of a base, or heated (in addition to normal heating, a method using a mantle heater, a method of heating with a microwave, etc. is also effective) Can do.

  The compound of the present invention can be prepared by using, for example, a corresponding acetylene compound and a suitable metal ion source as described above with reference to the method described in J. Chem. Soc., Dalton Trans., 1981-1987, (1981). Although it can synthesize | combine by making it react under, it is not limited to the method quoted here.

  The reaction time for synthesizing the compound of the present invention varies depending on the activity of the reaction and is not particularly limited, but is preferably 1 minute to 5 days, more preferably 5 minutes to 3 days, and more preferably 10 minutes to 24 hours. preferable.

  The reaction temperature for synthesizing the compound of the present invention varies depending on the activity of the reaction and is not particularly limited, but is preferably 0 ° C. or higher and 300 ° C. or lower, more preferably 5 ° C. or higher and 250 ° C. or lower, and more preferably 10 ° C. or higher and 200 ° C. or lower. preferable.

  In the synthesis of the compound of the present invention, the ligand forming the partial structure of the target complex is preferably 0.1 equivalent to 10 equivalent, more preferably 0.3 equivalent to the compound containing the metal ion M. It can be synthesized by adding ~ 6 equivalents, more preferably 0.5 equivalents ~ 4 equivalents. Examples of the compound containing the metal ion M include halides (for example, chloride, bromide, etc.), carboxylates (for example, acetate, etc.), diketonates (for example, acetylacetonate, etc.), and organic ligands. The compound (for example, dichlorocyclooctadienyl etc.) to contain or those hydrates are mention | raise | lifted.

  Although the specific example of the compound of this invention is shown, this invention is not limited to these.

<Organic electroluminescent device>
The organic electroluminescent element of the present invention will be described in detail. The element of the present invention has a cathode and an anode on a substrate, and has at least one organic layer (a light emitting layer when there is one organic layer) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  In the element of the present invention, the function of the organic layer is not particularly limited, but besides the light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole block layer, an electron block layer, An exciton block layer, a protective layer, etc. may be sufficient. In addition to the light emitting layer, the element of the present invention has a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole block layer, an electron block layer, an exciton block layer, a protective layer, and the like. May be. Each of these layers may also have other functions.

  In the present invention, as the layer stacking mode, a mode in which a hole transport layer, a light emitting layer, and an electron transport layer are stacked in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. Specific examples thereof include zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and poly (chlorotrifluoroethylene).
For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light-emitting element, but is preferably configured on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is detailed in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode is usually only required to have a function as an electrode for injecting electrons into the organic layer, and the shape, structure, size and the like are not particularly limited, and are known according to the use and purpose of the device. It can select suitably from electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode forming position is not particularly limited, and may be formed on the entire organic layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Organic layer>
The organic layer in the present invention will be described.
The organic electroluminescent element of the present invention has at least one organic layer (a light emitting layer when the organic layer is a single layer), and other organic layers other than the light emitting layer include hole transport as described above. Examples include layers such as a layer, an electron transport layer, a charge blocking layer, a hole injection layer, and an electron injection layer.

-Formation of organic layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Light emitting layer-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent materials that can be used in combination with the compounds of the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimides. Derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclohexane Pentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivative metal complexes and Various metal complexes represented by metal complexes of methene derivatives, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.
Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.

  Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.
The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 50 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the element may be protected by a protective layer. As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device. As specific examples, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerizing fluorinated copolymer having a cyclic structure in the copolymer main chain Water absorption of 1% by weight of the water absorbing material, the water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Sealing>
The organic electroluminescent element of the present invention may be sealed entirely using a sealing container. Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

  The organic electroluminescent element of the present invention can be suitably used in the fields of display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. The compounds of the present invention are also applicable to medical uses, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, color filter dyes, color conversion filters, analytical uses, etc. Is possible.

Claims (7)

An organic electroluminescent device having at least one organic layer between a pair of electrodes, wherein the organic layer contains at least one compound containing a structure represented by the following general formula (I).
Formula (I)

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. When R ₁ and R ₂ represent a substituent, they may be bonded to each other to form a ring. R ₁ and R ₄ and R ₂ and R ₃ are not bonded to each other to form an aromatic ring. X ₁ and X ₂ represent a carbon atom or a nitrogen atom. m and n represent 0 or 1. When X ₁ or X ₂ represents a nitrogen atom, m or n is 0. M represents a metal ion. Y represents a molecule that coordinates to M or a group that coordinates. p represents an integer of 0 or more. A ₁ represents a single bond or a divalent linking group. The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (II) or (III).
Formula (II)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ each independently represent an atom selected from carbon, nitrogen and silicon. . Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , Z ₉ and Z ₁₀ may have a substituent. A2, A ₃ and A ₄ represents a single bond or a divalent linking group. q represents 0 or 1; X ₁ , X ₂ , R ₁ , R ₂ , M, m, and n are as defined in general formula (I).
General formula (III)

In the formula, Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ and Z ₁₇ each independently represent an atom selected from carbon, nitrogen, oxygen, sulfur and silicon. The bonds between the atoms in the 5-membered ring formed from Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ and N atoms, and Z ₁₄ , Z ₁₅ , Z ₁₆ , Z ₁₇ and N atoms are single bonds or double bonds. To express. Z ₁₀ , Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ and Z ₁₇ may have a substituent. X ₁ , X ₂ , R ₁ , R ₂ , M, m, and n are as defined in general formula (I), and A ₂ , A ₃ , A ₄ , and q are as defined in general formula (II). It is. The organic electroluminescent element according to claim 2, wherein the general formula (II) is represented by the following general formula (IIA).
General formula (IIA)

In the formula, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a substituent. R ₁ , R ₂ and M have the same meanings as those in the general formula (I), and A ₂ , A ₃ , A ₄ and q have the same meanings as those in the general formula (II). The organic electroluminescent element according to claim 2, wherein the general formula (III) is represented by the following general formula (IIIA).
General formula (IIIA)

In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent. R ₁ , R ₂ and M have the same meanings as those in the general formula (I), and A ₂ , A ₃ , A ₄ and q have the same meanings as those in the general formula (III).   In the said general formula (I)-(IIIA), M is selected from nickel, copper, zinc, tin, palladium, and platinum, The organic electroluminescent element in any one of Claims 1-4 characterized by the above-mentioned.   In the said general formula (I)-(IIIA), M is selected from palladium and platinum, The organic electroluminescent element in any one of Claims 1-4 characterized by the above-mentioned. In the general formulas (II) to (IIIA), A ₂ , A ₃ , A ₄ are a single bond, —C (R ₁₅ ) (R ₁₆ ) —, —C (R ₁₇ ) (R ₁₈ ) C (R ₁₉ ) (R ₂₀ )-, -Si (R ₂₁ ) (R ₂₂ )-, -N (R ₂₅ )-, -O-, -S-, -SO-, -SO _2- , -CO- (R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₅ each independently represents a hydrogen atom or a substituent. The organic electroluminescent element according to any one of 6.