JP2009267245A - Organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent device wherein the increase in a driving voltage with the elapse of time is small. <P>SOLUTION: In the organic electroluminescent device, an organic layer contains a compound represented by a general formula (I) wherein each of X<SP>1</SP>to X<SP>8</SP>, X<SP>11</SP>to X<SP>13</SP>, X<SP>16</SP>, and Z<SP>1</SP>to Z<SP>4</SP>independently represents a carbon atom, a nitrogen atom, or a phosphorus atom and each of X<SP>14</SP>and X<SP>15</SP>independently represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electroluminescent element (hereinafter also referred to as “organic EL element” or “element”) that can emit light by converting electric energy into light.

  Organic electroluminescent elements (organic EL elements) are actively researched and developed because they can emit light with high brightness when driven at a low voltage. An organic electroluminescent element has an organic layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode recombine in the organic layer, and the generated exciton energy is used for light emission. To do.

  In recent years, the use of phosphorescent light emitting materials has led to higher efficiency of devices. As phosphorescent materials, iridium complexes and platinum complexes are known (see, for example, Patent Document 1 and Patent Document 2). However, no device has been developed that has both high efficiency and high durability. At present, the development of compatible phosphorescent materials is eagerly desired.

Further, as a phosphorescent material, an organic electroluminescent element containing a platinum complex having a tetradentate ligand composed of three six-membered rings and one five-membered ring in a light-emitting layer is known (for example, Patent Document 3). And Patent Document 4).
US Pat. No. 6,303,238 International Publication No. 00/57676 Pamphlet JP 2006-261623 A JP 2008-37848 A

The organic electroluminescent elements using the platinum complexes described in Patent Documents 3 and 4 have a problem that when driven at high luminance, the driving voltage increases with time and the power consumption increases.
An object of the present invention is to provide an organic electroluminescent device in which the drive voltage does not increase with time even when driven at high brightness.

  As a result of investigations to solve the above-mentioned problems, the present inventors have found that an organic electroluminescent element containing a compound represented by the general formula (I) in an organic layer solves the above-mentioned problems. That is, the above problem can be solved by the following means.

[1] An organic electroluminescent device having an organic layer including at least a light emitting layer between a pair of electrodes, wherein the compound represented by the following general formula (I) is contained in at least one of the organic layers Organic electroluminescent device.

In which X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁶ , Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ¹⁴ and X ¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³ are represent 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. M represents a divalent metal ion. MZ ¹ , MZ ² , MZ ³ and MZ ⁴ represent a coordination bond or a covalent bond. L ¹ represents a divalent linking group.

[2] The organic electroluminescent element as described in [1] above, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

In the formula, X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁶ , Z ¹¹ , Z ¹² , and Z ¹⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ³⁴ and X ³⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. Ring Q ¹³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The bond between ring Q ¹³ and Pt, Pt—Z ¹¹ , Pt—Z ¹² , and Pt—Z ¹⁴ represent a coordination bond or a covalent bond. L ² represents a divalent linking group.

[3] The organic electroluminescent element as described in [2] above, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-a).

In the formula, X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁶ , Z ³¹ , Z ³² , and Z ³⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁷⁴ and X ⁷⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁴ , and X ⁷⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. A broken line expressing a bond between the ring Q ³³ and Pt represents a coordinate ^{bond, Pt-Z 31, Pt-} Z 32, and Pt-Z ^34, represents a coordination or covalent bonds. L ⁴ represents a divalent linking group.

[4] The organic electroluminescence according to [3], wherein the compound represented by the general formula (II-a) is a compound represented by the following general formula (II-a-1) element.

In the formula, X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , and X ¹¹⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹¹⁴ and X ¹¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , X ¹¹⁴ , and X ¹¹⁵ are each independently replaced if further replaceable It may have a group. Ring Q ⁵³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The solid line representing the bond between ring Q ⁵¹ , ring Q ⁵² , ring Q ⁵³ , and ring Q ⁵⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁶ represents a divalent linking group.

[5] The organic electroluminescent element as described in [2] above, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-b).

In the formula, X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , X ⁹⁵ , Z ⁴¹ , Z ⁴² , and Z Each of ⁴⁴ independently represents a carbon atom, a nitrogen atom or a phosphorus atom. X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , and X ⁹⁵ are each independently replaced if further replaceable It may have a group. A solid line expressing a bond between the ring Q ³³ and Pt represents a covalent ^{bond, Pt-Z 41, Pt-} Z 42, and Pt-Z ^44, represents a coordination or covalent bonds. L ⁵ represents a divalent linking group.

[6] The organic electroluminescence as described in [5] above, wherein the compound represented by the general formula (II-b) is a compound represented by the following general formula (II-b-1) element.

In which X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each independently a carbon atom, Represents a nitrogen atom or a phosphorus atom. X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each replaced independently It may have a group. The solid line representing the bond between ring Q ⁶¹ , ring Q ⁶² , ring Q ⁶³ , and ring Q ⁶⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁷ represents a divalent linking group.

[7] The organic electroluminescent element as described in [1] above, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (III).

In the formula, X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁶ , Z ²¹ , Z ²² , and Z ²⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁵⁴ and X ⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. Ring Q ²³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. Coupling ring Q ²³ and Pt represents a covalent ^{bond, Pt-Z 21, Pt-} Z 22, and Pt-Z ^24, represents a coordination or covalent bonds. L ³ represents a divalent linking group.

[8] The organic electroluminescent element as described in [7] above, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-a).

In the formula, X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , and X ¹⁵⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹⁵⁴ and X ¹⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , X ¹⁵⁴ , and X ¹⁵⁵ are each independently replaced if possible It may have a group. Ring Q ⁷³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. A solid line representing a bond between ring Q ⁷¹ , ring Q ⁷² , ring Q ⁷³ , and ring Q ⁷⁴ and Pt represents a covalent bond, and a broken line represents a coordination bond. L ⁸ represents a divalent linking group.

[9] General formula (I), general formula (II), general formula (II-a), general formula (II-a-1), general formula (II-b), general formula (II-b-1) The organic material according to any one of [1] to [8] above, wherein the light emitting layer contains at least one of compounds represented by general formula (III) and general formula (III-a): Electroluminescent device.
[10] The organic electroluminescent element as described in any one of [1 to 9] above, wherein a material having at least one deuterium atom is contained in at least one of the organic layers.
[11] The organic material according to [10], wherein the material having at least one deuterium atom is a material having at least one deuterium atom and containing either a carbazole skeleton or an indole skeleton. Electroluminescent device.

  According to the present invention, it is possible to provide an organic electroluminescent element that has little increase in drive voltage with time even when driven at high brightness and is excellent in power consumption. Therefore, 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. .

  Hereinafter, preferred embodiments of the organic EL element according to the present invention will be described.

  The organic EL device according to the present invention has an organic layer including at least a light emitting layer between a pair of electrodes. The organic layer may be a layer made of only an organic compound or a layer containing both an organic compound and an inorganic compound. The organic layer may include 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 and the like in addition to the light emitting layer. Each layer may have other functions. Each layer may be formed of a plurality of layers.

  As an aspect of stacking the organic layers, an aspect in which the hole transport layer, the light emitting layer, and the electron transport layer are stacked in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer and / 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.

At least one of the organic layers contains the metal complex represented by the general formula (I).
The function of the metal complex represented by the general formula (I) is not limited, and can be used as a light-emitting material, a host material, an exciton block material, a charge block material, or a charge transport material. Of these, the use as a light emitting material, a host material, and a charge transport material is more preferable, the use as a light emitting material and a host material is still more preferable, and the use as a light emitting material is most preferable.

  Further, the layer containing the compound represented by the general formula (I) can be contained in any of the organic layers described above, but the compound represented by the general formula (I) can be incorporated into the light emitting layer. It is preferable to contain.

When the light emitting layer contains the compound represented by the general formula (I), it is more preferably contained in the light emitting layer as the light emitting material or the host material, more preferably contained in the light emitting layer as the light emitting material. It is particularly preferable to contain it in the light emitting layer together with the host material.
When contained in the light emitting layer as a light emitting material, the content of the compound represented by the general formula (I) is preferably in the range of 0.1% by mass or more and 60% by mass or less with respect to the total mass of the light emitting layer. The range of 0.2 mass% or more and 50 mass% or less is more preferable, the range of 0.3 mass% or more and 40 mass% or less is more preferable, and the range of 0.5 mass% or more and 30 mass% or less is the most preferable.
When the compound represented by the general formula (I) is contained in the light emitting layer as a light emitting material, the compound represented by the general formula (I) and a phosphorescent material described later can be used in combination. In this case, the content of the compound represented by the general formula (I) is preferably in the range of 0.1% by mass to 60% by mass with respect to the total mass of the phosphorescent light emitting material, and is 0.2% by mass to 50% by mass. A range of not more than mass% is more preferable, a range of not less than 0.3% by mass and not more than 40% by mass is further preferable, and a range of not less than 0.5% by mass and not more than 35% by mass is most preferable.

  When the metal complex represented by the general formula (I) is used for a layer other than the light emitting layer (for example, a charge transport layer), the layer is preferably contained in an amount of 10% by mass to 100% by mass, and 30% by mass. More preferably, it is contained in an amount of 100% by mass to 100% by mass.

Next, general formula (I), general formula (II), general formula (II-a), general formula (II-a-1), general formula (II-b), general formula (II-b-1) The compounds represented by general formula (III) and general formula (III-a) (hereinafter, these may be collectively referred to as “a metal complex having a specific structure”) will be described.
In these general formulas (I) and the like, the coordination bond represents a bond formed between a neutral ligand and a metal, and the covalent bond is between an anionic ligand and a metal cation. Means a bond formed by
Moreover, the hydrogen atom in the description regarding the metal complex having the following specific structure includes an isotope (deuterium atom and the like), and atoms constituting other substituents also include the isotope.

  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, trifluoromethyl, pentafluoroethyl, etc.), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms). For example, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as vinyl, And allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 3 carbon atoms) , More preferably from 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as 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). To 20, particularly preferably 1 to 12 carbon atoms, for example 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 which X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁶ , Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ¹⁴ and X ¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³ are represent 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. M represents a divalent metal ion. MZ ¹ , MZ ² , MZ ³ and MZ ⁴ represent a coordination bond or a covalent bond. L ¹ represents a divalent linking group.

In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁶ , Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom, preferably a carbon atom or a nitrogen atom.
X ¹⁴ and X ¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, preferably a carbon atom, a nitrogen atom or an oxygen atom, more preferably a carbon atom or a nitrogen atom, most Preferably it is a carbon atom.

Substituent group A when X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ can be further substituted Each of the substituents selected from the substituents containing may be independently present. 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. , Alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic group 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, a cyano group, a fluorine atom, and a heterocyclic ring, and more preferably a methyl group. Group, trifluoromethyl group Fluorine atom, a methoxy group, an aryl group, a cyano group.

Ring Q ³ are represent 5-membered ring, bonds between atoms forming a 5-membered ring represents a single bond or a double bond. The bond between the atoms forming the 5-membered ring may be any combination of a single bond and a double bond.

  M represents a divalent metal ion. Although it does not specifically limit as a bivalent metal ion, Platinum ion, palladium ion, nickel ion, ruthenium ion, copper ion, zinc ion etc. are mentioned, Platinum ion, palladium ion, nickel ion, copper ion are preferred, platinum ion Palladium ion and nickel ion are more preferable, and platinum ion is particularly preferable.

MZ ¹ , MZ ² , MZ ³ and MZ ⁴ represent a coordination bond or a covalent bond. That is, any two of the bonds of MZ ¹ , MZ ² , MZ ³ , and MZ ⁴ represent a coordination bond, and the other two represent a covalent bond.

L ¹ represents a divalent linking group. Although it does not specifically limit as a bivalent coupling group, The bivalent coupling group which consists of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, and a germanium atom is especially preferable, It selects from the following coupling group group A The group is particularly preferred.
Linking group A:

In the linking group group A, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , and R ⁹² (R ^{81 to} R ⁹² ) are Each independently represents a hydrogen atom or a substituent selected from substituents including substituent group A. When R ^{81 to} R ⁹² represent a substituent, the substituent is preferably a substituent selected from the substituent group A. When R ^{81 to} R ⁹² can be substituted, they may further have a substituent, and R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , R ⁸⁵ and R ⁸⁶ , R ⁸³ and R ⁸⁵ , R ⁸³ and R ⁸⁶ , R ⁸⁴ and R ⁸⁶ , or R ⁹⁰ and R ⁹¹ may be bonded to each other to form a ring.

L ¹ is preferably a substituent selected from the linking group group A, of which —C (R ⁸¹ ) (R ⁸² ) —, —C (R ⁸³ ) (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ )-, -Si (R ⁸⁷ ) (R ⁸⁸ )-, -N (R ⁸⁹ )-, -O-, -S-, -SO-, -SO _2- , or -CO- are preferred, and -C (R ⁸¹ ) (R ⁸² )-, -C (R ⁸³ ) (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ )-, -Si (R ⁸⁷ ) (R ⁸⁸ )-, -O-, or -S -Is more preferable, and -C ( ^R81 ) ( ^R82 )-, -C ( ^R83 ) ( ^R84 ) C ( ^R85 ) ( ^R86 ) ^-is more preferable.

In the —C (R ⁸¹ ) (R ⁸² ) —, R ⁸¹ and R ⁸² 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 alkyloxy group, an aryloxy group, a hydroxy group, a mercapto group, or a halogen atom, more preferably an alkyl group. , A cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, an aryloxy group and a halogen atom, more preferably an alkyl group and an aryl group.

In the above -C (R ⁸³ ) (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ )-, R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are preferably a hydrogen atom or a substituent selected from the substituent group B. is there.

In the —Si (R ⁸⁷ ) (R ⁸⁸ ) —, R ⁸⁷ and R ⁸⁸ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —Ge (R ⁹⁰ ) (R ⁹¹ ) —, R ⁹⁰ and R ⁹¹ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —N (R ⁸⁹ ) —, R ⁸⁹ 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.

In the above -P (R ⁹² ) —, R ⁹² has the same ^{meaning as} the preferred range of R ⁸⁹ .

General formula (I), general formula (II), general formula (II-a), general formula (II-a-1), general formula (II-b), general formula (II-b-1), general formula The relationship between (III) and general formula (III-a) is as follows.
The metal complex represented by the general formula (I) is preferably a metal complex represented by the general formula (II) or a metal complex represented by the general formula (III).
The metal complex represented by the general formula (II) is preferably a metal complex represented by the general formula (II-a) or a metal complex represented by the general formula (II-b).
The metal complex represented by the general formula (II-a) is preferably a metal complex represented by the general formula (II-a-1).
The metal complex represented by the general formula (II-b) is preferably a metal complex represented by the general formula (II-b-1).
The metal complex represented by the general formula (III) is preferably a metal complex represented by the general formula (III-a).

One of the preferable embodiments of the metal complex represented by the general formula (I) is a metal complex represented by the general formula (II).
The metal complex represented by the general formula (II) will be described.

In the formula, X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁶ , Z ¹¹ , Z ¹² , and Z ¹⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ³⁴ and X ³⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. Ring Q ¹³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The bond between ring Q ¹³ and Pt, Pt—Z ¹¹ , Pt—Z ¹² , and Pt—Z ¹⁴ represent a coordination bond or a covalent bond. L ² represents a divalent linking group.

In formula ^{(II), X 21, X} 22, X 23, X 24, X 25, X 26, X 27, X 28, X 31, X 32, X 33, X 34, X 35, X 36, Z ¹¹ , Z ¹² , Z ¹⁴ , and L ² are X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X in the general formula (I) It is synonymous with ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , Z ¹ , Z ² , Z ⁴ , and L ¹ , and the preferred range is also synonymous.

Ring ^Q13 represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring represents a single bond or a double bond. The bond between the atoms forming the 5-membered ring may be any combination of a single bond and a double bond.

The bond between ring Q ¹³ and Pt, Pt—Z ¹¹ , Pt—Z ¹² , and Pt—Z ¹⁴ represent a coordination bond or a covalent bond. Any two of the bonds of ring Q ¹³ and Pt and the bonds of Pt—Z ¹¹ , Pt—Z ¹² , and Pt—Z ¹⁴ represent a coordination bond, and the other two represent a covalent bond.

One of the preferable embodiments of the metal complex represented by the general formula (II) is a metal complex represented by the general formula (II-a).
The metal complex represented by the general formula (II-a) will be described.

In the formula, X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁶ , Z ³¹ , Z ³² , and Z ³⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁷⁴ and X ⁷⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁴ , and X ⁷⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. A broken line expressing a bond between the ring Q ³³ and Pt represents a coordinate ^{bond, Pt-Z 31, Pt-} Z 32, and Pt-Z ^34, represents a coordination or covalent bonds. L ⁴ represents a divalent linking group.

In the general formula (II-a), X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , Z ³¹ , Z ³² , Z ³⁴ , and L ⁴ represent X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ^{32 in} the general formula (II). , X ³³ , X ³⁴ , X ³⁵ , X ³⁶ , Z ¹¹ , Z ¹² , Z ¹⁴ , and L ² , and the preferred range is also the same.

Ring ^Q33 represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring represents a single bond or a double bond, and may be any combination of a single bond and a double bond.

Coupling ring Q ³³ and Pt represents a coordinate ^{bond, Pt-Z 21, Pt-} Z 22 and Pt-Z ^24, represents a coordinate bond or covalent bond. One of the bonds of Pt-Z ²¹ , Pt-Z ²² , and Pt-Z ²⁴ represents a coordination bond, and the other two represent a covalent bond.

The metal complex represented by the general formula (II-a) is preferably a metal complex represented by the general formula (II-a-1).
The metal complex represented by the general formula (II-a-1) will be described.

In the formula, X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , and X ¹¹⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹¹⁴ and X ¹¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , X ¹¹⁴ , and X ¹¹⁵ are each independently replaced if further replaceable It may have a group. Ring Q ⁵³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The solid line representing the bond between ring Q ⁵¹ , ring Q ⁵² , ring Q ⁵³ , and ring Q ⁵⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁶ represents a divalent linking group.

In formula (II-a-1), X 101, X 102, X 103, X 104, X 105, X 106, X 107, X 108, X 111, X 112, X 113, X 114, X 115, X ¹¹⁶ and L ⁶ are represented by the formula (II-a): X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , and L ⁴ , and the preferred range is also the same.

Ring ^Q53 represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring represents a single bond or a double bond, and may be any combination of a single bond and a double bond.

Ring Q ⁵¹ and Pt, and a solid line expressing a bond between the ring Q ⁵⁴ and Pt represents a covalent bond, a broken line expressing a bond between the ring Q ⁵² and Pt, and ring Q ⁵³ and Pt represents a coordinate bond.

One of the preferable embodiments of the metal complex represented by the general formula (II) is a metal complex represented by the general formula (II-b).
The metal complex represented by the general formula (II-b) will be described.

In the formula, X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , X ⁹⁵ , Z ⁴¹ , Z ⁴² , and Z Each of ⁴⁴ independently represents a carbon atom, a nitrogen atom or a phosphorus atom. X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , and X ⁹⁵ are each independently replaced if further replaceable It may have a group. A solid line expressing a bond between the ring Q ³³ and Pt represents a covalent ^{bond, Pt-Z 41, Pt-} Z 42, and Pt-Z ^44, represents a coordination or covalent bonds. L ⁵ represents a divalent linking group.

In formula ^{(II-b), X 81} , X 82, X 83, X 84, X 85, X 86, X 87, X 88, X 91, X 92, X 93, Z 41, Z 42, and Z ⁴⁴ and L ⁵ are X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , Z ¹¹ , Z in the general formula (II) ^12, Z ^14, and L ² in the above formula preferred ranges thereof are also the same.

X ⁹⁴ and X ⁹⁵ each independently represent an atom selected from carbon, nitrogen or phosphorus, preferably a carbon atom or a nitrogen atom.

When X ⁹⁴ and X ⁹⁵ can be further substituted, each may independently have a substituent selected from the substituents including the substituent group A. 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. , Alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic group 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, a cyano group, a fluorine atom, and a heterocyclic ring, and more preferably a methyl group. Group, trifluoromethyl group Fluorine atom, a methoxy group, an aryl group, a cyano group.

Coupling ring Q ⁴³ and Pt represents a covalent ^{bond, Pt-Z 21, Pt-} Z 22 and Pt-Z ^24, represents a coordinate bond or covalent bond. Any two of the bonds of Pt-Z ²¹ , Pt-Z ²² , and Pt-Z ²⁴ represent a coordination bond, and the other represents a covalent bond.

The metal complex represented by the general formula (II-b) is preferably a metal complex represented by the general formula (II-b-1).
The metal complex represented by the general formula (II-b-1) will be described.

In which X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each independently a carbon atom, Represents a nitrogen atom or a phosphorus atom. X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each replaced independently It may have a group. The solid line representing the bond between ring Q ⁶¹ , ring Q ⁶² , ring Q ⁶³ , and ring Q ⁶⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁷ represents a divalent linking group.

In the general formula (II-b-1), X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , X ¹³⁵ , And L ⁷ are X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , X in the general formula (II-b) ⁹⁵ and L ⁵ , and the preferred range is also the same.

Ring Q ⁶² and Pt, and a solid line expressing a bond between the ring Q ⁶³ and Pt represents a covalent bond, a broken line expressing a bond between the ring Q ⁶¹ and Pt, and ring Q ⁶⁴ and Pt represents a coordinate bond.

One of the preferable embodiments of the metal complex represented by the general formula (I) is a metal complex represented by the general formula (III).
The metal complex represented by the general formula (III) will be described.

In the formula, X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁶ , Z ²¹ , Z ²² , and Z ²⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁵⁴ and X ⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. Ring Q ²³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. Coupling ring Q ²³ and Pt represents a covalent ^{bond, Pt-Z 21, Pt-} Z 22, and Pt-Z ^24, represents a coordination or covalent bonds. L ³ represents a divalent linking group.

In the general formula (III), ^X41 , ^X42 , ^X43 , ^X44 , ^X45 , ^X46 , ^X47 , ^X48 , ^X51 , ^X52 , ^X53 , ^X54 , ^X55 , ^X56 , Z ²¹ , Z ²² , Z ²⁴ , and L ³ are X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X in the general formula (I) It is synonymous with ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , Z ¹ , Z ² , Z ⁴ , and L ¹ , and the preferred range is also synonymous.

Ring ^Q23 represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring represents a single bond or a double bond, and may be any combination of a single bond and a double bond.

Coupling ring Q ²³ and Pt represents a covalent ^{bond, Pt-Z 21, Pt-} Z 22, and Pt-Z ^24, represents a coordination or covalent bonds.

Pt-Z ²¹ , Pt-Z ²² , and Pt-Z ²⁴ represent a coordination bond or a covalent bond. Any two of the bonds of Pt-Z ²¹ , Pt-Z ²² , and Pt-Z ²⁴ represent a coordination bond, and the other represents a covalent bond.

The metal complex represented by the general formula (III) is preferably a metal complex represented by the general formula (III-a).
The metal complex represented by the general formula (III-a) will be described.

In the formula, X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , and X ¹⁵⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹⁵⁴ and X ¹⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , X ¹⁵⁴ , and X ¹⁵⁵ are each independently substituted if further replaceable It may have a group. Ring Q ⁷³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. A solid line representing a bond between ring Q ⁷¹ , ring Q ⁷² , ring Q ⁷³ , and ring Q ⁷⁴ and Pt represents a covalent bond, and a broken line represents a coordination bond. L ⁸ represents a divalent linking group.

In general formula (III-a), X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , X ¹⁵⁴ , X ¹⁵⁵ , X ¹⁵⁶ , And L ⁶ are X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ^{55 in} the general formula (III) , X ⁵⁶ , and L ³ , and the preferred range is also the same.

Ring ^Q83 represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring represents a single bond or a double bond, and may be any combination of a single bond and a double bond.

A solid line representing a bond between rings Q ⁷² and Pt and a ring Q ⁷³ and Pt represents a covalent bond, and a broken line representing a bond between rings Q ⁷¹ and Pt and rings Q ⁷⁴ and Pt represents a coordination bond.

Specific examples of the metal complex represented by the general formula (I) are illustrated below, but the present invention is not limited thereto.
In the following specific examples, the compound represented by the general formula (I) is represented by the following general formula (A) and used for Q ^A , Q ^B , Q ^C , Q ^D , and L in the general formula (A). The partial structure group which can do is shown.
M and L in the partial structures Q ^A , Q ^B , Q ^C , and Q ^D correspond to M and L in the general formula (A), respectively. Q is, Q in which Q moiety represented by ^A] represents Q ^B, Q in the [partial structure represented by Q ^B] represents Q ^A, the partial structure represented by [Q ^C Q in] represents Q ^D, Q in the partial structure] represented by [Q ^D represents Q ^C.

In the following partial structure group, partial structure group can be used for Q ^A is a [QB60CN], and a partial structure group represented by [QB61CC].
Partial structure group can be used for Q ^B is a partial structure group represented by [QT60CN], and [QT61CC].
Partial structure group can be used for Q ^C is [QT51CC], a [QT51CN], [QT50CN], in partial structure group represented.
Partial structure group can be used for Q ^D is [QB61CC] is a partial structure group represented by [QB60CN].
A partial structure that can be used for L is a partial structure group represented by [L]. Two Q partial structure group [L] is the left side of Q is Q ^B, right Q represents Q ^C.

[Partial structure represented by Q ^A and Q ^D ]
Partial structure group QB60CN is shown below.
[QB60CN]:

The partial structure group QB61CC is shown below.
[QB61CC]:

[Q partial structure represented by ^B]
The partial structure group QT60CN is shown below.
[QT60CN]:

The partial structure group QT61CC is shown below.
[QT61CC]:

[Partial structure represented by ^{Q C]}
The partial structure group QT51CC is shown below.
[QT51CC]:

Partial structure group QT51CN is shown below.
[QT51CN]:

The partial structure group QT50CN is shown below.
[QT50CN]:

[Linking group L]
The partial structure group [L] of the linking group L is shown below.
[L]:

The compound represented by the general formula (I) has a combination of the above partial structures Q ^{A to} Q ^D (Q ^A , Q ^B , Q ^C , Q ^D ),
(QB60CN, QT60CN, QT51CC, QB61CC)
(QB60CN, QT60CN, QT51CN, QB61CC)
(QB60CN, QT61CC, QT50CN, QB61CC)
(QB60CN, QT61CC, QT51CC, QB60CN)
(QB60CN, QT61CC, QT51CN, QB60CN)
(QB61CC, QT60CN, QT50CN, QB61CC)
(QB61CC, QT60CN, QT51CC, QB60CN)
(QB61CC, QT60CN, QT51CN, QB60CN)
(QB61CC, QT61CC, QT50CN, QB60CN)
As such, it can be represented by any combination selected from four partial structures selected from each partial structure group, a group of linking groups L, and a divalent metal ion.

For example, compounds of general formula shown below as a compound represented by the general formula (I) Q ^A in the general formula (A) represents QB60CN-1, Q ^B represents QT61CC-1, Q ^C is QT51CN-3 the stands, Q ^D represents QB60CN-1, L represents L-1, M is meant to represent the platinum atom.

  Although the example of a specific compound is illustrated below, this invention is not limited to these.

The metal complex having the specific structure may be a low molecular compound, an oligomer compound, or a polymer compound, but is preferably a low molecular compound.
In the case of a polymer compound, the weight average molecular weight (polystyrene conversion) is preferably 2000 or more, more preferably 2000 to 1000000, and still more preferably 3000 to 100000. In the case of a polymer compound, the structure represented by each of the above general formulas may be included in the polymer main chain, or may be included in the polymer side chain. In the case of the polymer compound, it may be a homopolymer compound or a copolymer compound.
Although the specific example in case the metal complex which has the said specific structure is a polymer compound is shown below, it is not limited to these.

The compound represented by the general formula (I) can be synthesized by a known synthesis method. Specifically, it is obtained by reacting a compound serving as a ligand with a metal source in the presence or absence of a solvent, in the presence or absence of a base, at room temperature or below or under heating according to a known method. It is done.
As a known method, Journal of Organic Chemistry 53, 786, (1988), GR Newkome et al.), Page 789, left line 53 to right line 7, line 790, left line 18 line The method described in line 38, page 790, the method described in lines 19-30 of the right column, Chemische Berichte 113, 2749 (1980), H. Lexy et al.), The method described in page 2752, lines 26-35. Etc.

  Examples of the metal source include platinum chloride, platinum bromide, platinum acetylacetonate, potassium chloroplatinate, palladium chloride, sodium chloropalladate, copper acetate, copper acetylacetonate, dichloro (N, N, N ′, N '-Tetramethylenediamine) zinc, zinc acetate, etc. can be used.

  When using 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, a sulfone solvent, a sulfoxide solvent, water or the like is used. be able to. More specifically, acetonitrile, benzonitrile, acetic acid, ethanol, methoxyethanol, glycerol, water, and a mixed solvent thereof can be used.

  When a base is used, various bases of inorganic compounds or organic compounds can be used. For example, sodium methoxide, t-butoxy potassium, triethylamine, potassium carbonate and the like can be used.

The reaction temperature of the reaction varies depending on the activity of the reaction, and can be performed in the range of −30 ° C. to 400 ° C. Preferably, it is 0 degreeC-350 degreeC, and 25 degreeC-250 degreeC is more preferable. In addition, when heating, the method of heating with a microwave other than a normal heating means can also be used.
The reaction time varies depending on the activity of the reaction raw materials, and can usually be carried out in the range of 1 minute to 60 hours. Preferably, it is 30 minutes to 24 hours, and more preferably 1 hour to 5 hours.

  In addition, additives that promote the reaction (silver trifluoromethanesulfonate, pyridine, triethylamine, etc.) may be added. The reaction may be performed in the presence of an inert gas (nitrogen gas, argon gas, etc.).

  It is preferable to use a material having at least one deuterium atom for the organic layer. The durability can be further improved by using a material having at least one deuterium atom.

  The material having at least one deuterium atom may be contained in any organic layer, but the hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, exciton blocking layer, charge It is preferably contained in one or more of the block layers, more preferably contained in one or more of the light emitting layer, exciton blocking layer, and charge blocking layer, and contained in the light emitting layer. More preferably, it is preferably contained as a host material in the light emitting layer.

  The material having at least one deuterium atom may be an organic material, an inorganic material, or both, but is preferably an organic material.

An organic material having at least one deuterium atom is a ratio of a deuterium atom to a hydrogen atom at a position where a hydrogen atom or deuterium atom in the organic material can be bonded (number of deuterium atoms: number of hydrogen atoms). ) In the range of 100: 0 to 1:99. Here, the position at which a hydrogen atom or deuterium atom can be bonded may be in any range from at least one specific position to the entire position in one molecule. In other words, the said ratio is synonymous with the ratio (deuteration rate) which a deuterium atom occupies in the sum total of the position where a hydrogen atom or a deuterium atom can couple | bond together.
Therefore, the state of the above ratio can be realized by simultaneously using a compound containing deuterium at the position and a compound not containing deuterium at an appropriate ratio.

  The composition range of deuterium atoms and hydrogen atoms is preferably 100: 0 to 5:95, more preferably 100: 0 to 50:50, and particularly preferably 100: 0 to 80:20.

  Examples of the organic material having at least one deuterium atom include, but are not limited to, compounds described in International Publication No. 02-47440 pamphlet.

  Preferable organic materials having at least one deuterium atom are materials containing nitrogen atoms. Among materials containing a nitrogen atom, a material containing a tertiary amine skeleton, a carbazole skeleton or an indole skeleton is preferred, a material containing a carbazole skeleton or an indole skeleton is more preferred, and a material containing a carbazole skeleton is particularly preferred.

  Examples of the material having at least one deuterium atom and containing a carbazole skeleton or an indole skeleton include the following.

  Next, each element constituting the organic EL element will be described.

<Organic layer>
The organic layer includes at least a light emitting layer and may be composed of a single layer or a plurality of layers. When composed of a plurality of layers, as the organic layer other than the light emitting layer, as described above, a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, etc. Each layer is mentioned.

-Formation of organic layer-
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 may be a single layer or may be formed of two or more layers. In the case of two or more layers, each layer may emit light with different emission colors.

The light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material.
Here, the host material is a material other than the light emitting material among the materials constituting the light emitting layer, and functions to disperse the light emitting material and hold it in the layer, and receive holes from the anode, the hole transport layer, and the like. Function, function to receive electrons from cathode, electron transport layer, etc., function to transport holes and / or electrons, function to provide recombination field of holes and electrons, and emit energy of excitons generated by recombination It means a material having at least one of a function of transferring to a material and a function of transporting holes and / or electrons to a light emitting material.

  The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, 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.

  Examples of host materials 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, those having an arylsilane skeleton, and holes described below. Examples thereof include the materials exemplified in the sections of the injection layer, the hole transport layer, the electron injection layer, and the electron transport layer.

  As the host material, compounds described in paragraphs 0113 to 0161 of JP-A No. 2002-1000047 and compounds described in paragraphs of 0087 to 0098 of JP-A No. 2004-214179 can be suitably used.

  The glass transition point of the host material is preferably 100 ° C. or higher and 500 ° C. or lower, more preferably 110 ° C. or higher and 300 ° C. or lower, and further preferably 120 ° C. or higher and 250 ° C. or lower.

  The fluorescence wavelength of the host material in the film state is preferably in the range of 400 nm to 650 nm, more preferably in the range of 420 nm to 600 nm, and still more preferably in the range of 440 nm to 550 nm.

  The concentration of the host material in the light emitting layer is not particularly limited, but is preferably the main component (the component having the largest content) in the light emitting layer, more preferably 50% by mass or more and 99.9% by mass or less, 70 mass% or more and 99.8 mass% or less are more preferable, 80 mass% or more and 99.7 mass% or less are especially preferable, and 90 mass% or more and 99.5 mass% or less are the most preferable.

The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and may be used alone or in combination of two or more.
As the light emitting material, a metal complex having the specific structure can be used. Further, as other light emitting materials, the following fluorescent light emitting materials and / or phosphorescent light emitting materials can be used.
Fluorescent materials generally include benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene. Bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, condensed polycyclic aromatic compounds (such as anthracene, phenanthroline, pyrene, perylene, rubrene, or pentacene), 8- Various metal complexes represented by quinolinol metal complexes, pyromethene complexes and rare earth complexes, polythiophene, polyphenylene, polyphenylene vinylene and other poly Over compounds, organic silane, and the like, and their derivatives.

In general, examples of phosphorescent materials include complexes containing transition metal atoms or lanthanoid atoms.
For example, the transition metal atom is not particularly limited, but preferably includes ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum, and more preferably rhenium, iridium. And platinum, more preferably iridium and platinum.
Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .
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.

  Preferable specific examples of the phosphorescent material include the following. It is particularly preferable to use the following compound and the compound represented by the general formula (I) in combination as a light emitting material.

  In general, the light emitting material is preferably in a range of 0.1% by mass or more and 60% by mass or less, more preferably in a range of 0.2% by mass or more and 50% by mass or less, with respect to the total compound mass forming the light emitting layer. The range of 0.3% by mass or more and 40% by mass or less is more preferable, and the range of 0.5% by mass or more and 30% by mass or less is most preferable.

  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.

  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 In addition, a layer containing various metal complexes represented by an Ir complex having phenylazole or phenylazine as a ligand is 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 500 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 organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- Aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10- phenanthroline derivatives such as phenanthroline (abbreviated 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.

<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 doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). 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.

  There is no restriction | limiting in particular as a formation position of an anode, According to the use and objective of a light emitting element, it can select suitably. Is preferably formed 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 using a laser, or by 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 Electrode 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 usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

  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 publications 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.

There is no restriction | limiting in particular in the cathode formation position, You may form in the whole on an organic layer, and may be formed in the part.
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.

<Protective layer>
The entire organic EL 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.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and 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 A copolymer obtained by copolymerization of a copolymer having a cyclic structure in the copolymer main chain. Copolymer, 1% by weight of the water absorbing water absorption material, 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. 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.

<Board>
The electrode and the organic layer can be formed on a substrate.
The substrate is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. Specific examples 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 applied barrier coats, 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 substrate structure 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 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.

<Sealing container>
The organic EL device of the present invention may seal the entire device using a sealing container.
Moreover, you may enclose a water | moisture-content absorber or an inert liquid in the space between a sealing container and an organic EL 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.

<Driving method>
The organic EL device of the present invention obtains light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. be able to.
Regarding the driving method of the organic EL device of the present invention, each of JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in the publications, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, and the like can be applied.

<Application>
The organic EL element of the present invention can be suitably used for 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.

  Hereinafter, the present invention will be described in detail based on examples, but the embodiment of the present invention is not limited thereto.

[Examples 1-1 to 1-20]
[Production of Organic EL Element (Examples 1-1 to 1-20)]
A glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomatek Co., Ltd., surface resistance: 10 Ω / □) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. On the transparent anode (ITO film), the following organic layer 1, organic layer 2, organic layer 3, and organic layer 4 were sequentially deposited by vacuum deposition.
The vapor deposition rate in this example is 0.2 nm / second unless otherwise specified. The deposition rate was measured using a crystal resonator film forming controller CRTM-9000 manufactured by ULVAC.
The film thickness described below is also calculated from a calibration curve created based on the numerical value of CRTM-9000 and the film thickness measured with a Dektak stylus type film thickness meter.

<Organic layer 1> Hole injection material (HI) described in Table 1: film thickness 10 nm
<Organic layer 2> Hole transport material (HT) described in Table 1: film thickness 10 nm
<Organic layer 3> Co-evaporation of host material (H) (95% by mass) described in Table 1 and luminescent material (EM) (5% by mass) described in Table 1: film thickness 50 nm
<Organic layer 4> Electron transport material (ET) described in Table 1: film thickness 40 nm

  Finally, 0.1 nm of lithium fluoride and 100 nm of metal aluminum were deposited in this order to form a cathode. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it using a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) The organic EL elements of Examples 1-1 to 1-22 were obtained.

[Production of Organic EL Element (Comparative Example 1-1)]
A glass substrate having an ITO film of 0.5 mm thickness and 2.5 cm square (manufactured by Geomatek Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, ultrasonically cleaned in 2-propanol, and then treated with UV-ozone for 30 minutes. Went. On the transparent anode (ITO film), the following organic layer 1, organic layer 2, organic layer 3, and organic layer 4 were sequentially deposited by vacuum deposition.

<Organic layer 1> HI-4: film thickness 10 nm
<Organic layer 2> HT-1: film thickness 10 nm
<Organic layer 3> Co-deposition of H-8 (95% by mass) and the following compound (5% by mass) described in JP-A-2008-37848: film thickness 50 nm
<Organic layer 4> ET-1: film thickness 40 nm

  Finally, 0.1 nm of lithium fluoride and 100 nm of metal aluminum were deposited in this order to form a cathode. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it using a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) The organic EL element of Comparative Example 1-1 was obtained.

[Production of Organic EL Element (Comparative Example 1-2)]
In Comparative Example 1-1, Comparative Example was conducted in the same manner as Comparative Example 1-1 except that the following compound described in JP-A-2006-261623 was used instead of the compound described in JP-A-2008-37848. A 1-2 organic EL device was prepared.

[Evaluation]
(Measurement of drive voltage with drive time)
The organic EL elements of Examples 1-1 to 1-20, Comparative Example 1-1, and Comparative Example 1-2 were set in an OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd. Was driven under the condition of initial luminance of 1000 cd / m ² , the initial voltage and the voltage after 20 hours were measured, and the difference in drive voltage was determined.

  The evaluation results of the organic EL elements of Comparative Example 1-1, Comparative Example 1-2, and Examples 1-1 to 1-20 are shown in the following table. In the table below, the drive voltage difference between Comparative Example 1-2 and Examples 1-1 to 1-20 is 100 (drive voltage after 20 hours)-(initial voltage) of Comparative Example 1-1. It is a numerical value expressed as a relative value.

[Examples 2-1 to 2-3]
[Production of Organic EL Element (Example 2-1)]
A glass substrate having an ITO film of 0.5 mm thickness and 2.5 cm square (manufactured by Geomatek Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, ultrasonically cleaned in 2-propanol, and then treated with UV-ozone for 30 minutes. Went. On the transparent anode (ITO film), the following organic layer 1, organic layer 2, organic layer 3, and organic layer 4 were sequentially deposited by vacuum deposition.

<Organic layer 1> HI-4: film thickness 10 nm
<Organic layer 2> HT-1: film thickness 10 nm
<Organic layer 3> Co-evaporation of H-8 (90% by mass), Ir (ppy) ₃ (5% by mass), and compound (5) (5% by mass) of the present invention: film thickness 50 nm
<Organic layer 4> ET-1: film thickness 40 nm

  Finally, 0.1 nm of lithium fluoride and 100 nm of metal aluminum were deposited in this order to form a cathode. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it using a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) The organic EL element of Example 2-1 was obtained.

[Production of Organic EL Element (Example 2-2)]
In Example 2-1, the organic EL device of Example 2-2 was produced in the same manner as in Example 2-1, except that the compound (7) of the present invention was used instead of the compound (5) of the present invention. did.

[Production of Organic EL Element (Example 2-3)]
In Example 2-1, an organic EL device of Example 2-3 was produced in the same manner as Example 2-1, except that compound (8) of the present invention was used instead of compound (5) of the present invention. did.

[Production of Organic EL Element (Comparative Example 2-1)]
In Comparative Example 1-1, the organic EL device of Comparative Example 2-1 was used in the same manner as Comparative Example 1-1 except that Ir (ppy) ₃ was used instead of the compound described in JP-A-2008-37848. Was made.

[Evaluation]
(Measurement of drive voltage with drive time)
The organic electroluminescent elements of Examples 2-1 to 2-3 and Comparative Example 2-1 were set in the OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd., and the initial luminance was 1000 cd / in constant current mode. Driving was performed under the condition of m ² , the initial voltage and the voltage after 20 hours were measured, and the difference in driving voltage was determined.

  The evaluation results of the organic EL elements of Examples 2-1 to 2-3 and Comparative Example 2-1 are shown in the following table. In the table below, the drive voltage difference of Examples 2-1 to 2-3 is a numerical value represented by a relative value with (drive voltage after 20 hours)-(initial voltage) of Comparative Example 2-1 being 100. It is.

  From the above examples, by using the compound of the present invention, an organic EL device with little voltage increase with time can be obtained. When driven at high luminance, a light-emitting element with excellent power consumption can be manufactured.

Claims (11)

An organic electroluminescent device having an organic layer including at least a light emitting layer between a pair of electrodes, wherein the organic electroluminescent device contains a compound represented by the following general formula (I) in at least one of the organic layers element.

In which X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁶ , Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ¹⁴ and X ¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³ are represent 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. M represents a divalent metal ion. MZ ¹ , MZ ² , MZ ³ and MZ ⁴ represent a coordination bond or a covalent bond. L ¹ represents a divalent linking group. The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

In the formula, X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁶ , Z ¹¹ , Z ¹² , and Z ¹⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ³⁴ and X ³⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. Ring Q ¹³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The bond between ring Q ¹³ and Pt, Pt—Z ¹¹ , Pt—Z ¹² , and Pt—Z ¹⁴ represent a coordination bond or a covalent bond. L ² represents a divalent linking group. The organic electroluminescent element according to claim 2, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-a).

In the formula, X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁶ , Z ³¹ , Z ³² , and Z ³⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁷⁴ and X ⁷⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , X ⁷¹ , X ⁷² , X ⁷³ , X ⁷⁴ , and X ⁷⁵ are each independently substituted if further replaceable It may have a group. Ring Q ³³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. A broken line expressing a bond between the ring Q ³³ and Pt represents a coordinate ^{bond, Pt-Z 31, Pt-} Z 32, and Pt-Z ^34, represents a coordination or covalent bonds. L ⁴ represents a divalent linking group. The organic electroluminescent element according to claim 3, wherein the compound represented by the general formula (II-a) is a compound represented by the following general formula (II-a-1).

In the formula, X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , and X ¹¹⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹¹⁴ and X ¹¹⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁰¹ , X ¹⁰² , X ¹⁰³ , X ¹⁰⁴ , X ¹⁰⁵ , X ¹⁰⁶ , X ¹⁰⁷ , X ¹⁰⁸ , X ¹¹¹ , X ¹¹² , X ¹¹³ , X ¹¹⁴ , and X ¹¹⁵ are each independently replaced if further replaceable It may have a group. Ring Q ⁵³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. The solid line representing the bond between ring Q ⁵¹ , ring Q ⁵² , ring Q ⁵³ , and ring Q ⁵⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁶ represents a divalent linking group. The organic electroluminescent device according to claim 2, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-b).

In the formula, X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , X ⁹⁵ , Z ⁴¹ , Z ⁴² , and Z Each of ⁴⁴ independently represents a carbon atom, a nitrogen atom or a phosphorus atom. X ⁸¹ , X ⁸² , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , X ⁸⁸ , X ⁹¹ , X ⁹² , X ⁹³ , X ⁹⁴ , and X ⁹⁵ are each independently replaced if further replaceable It may have a group. A solid line expressing a bond between the ring Q ³³ and Pt represents a covalent ^{bond, Pt-Z 41, Pt-} Z 42, and Pt-Z ^44, represents a coordination or covalent bonds. L ⁵ represents a divalent linking group. The organic electroluminescent device according to claim 5, wherein the compound represented by the general formula (II-b) is a compound represented by the following general formula (II-b-1).

In which X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each independently a carbon atom, Represents a nitrogen atom or a phosphorus atom. X ¹²¹ , X ¹²² , X ¹²³ , X ¹²⁴ , X ¹²⁵ , X ¹²⁶ , X ¹²⁷ , X ¹²⁸ , X ¹³¹ , X ¹³² , X ¹³³ , X ¹³⁴ , and X ¹³⁵ are each replaced independently It may have a group. The solid line representing the bond between ring Q ⁶¹ , ring Q ⁶² , ring Q ⁶³ , and ring Q ⁶⁴ and Pt represents a covalent bond, and the broken line represents a coordination bond. L ⁷ represents a divalent linking group. The organic electroluminescence device according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (III).

In the formula, X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁶ , Z ²¹ , Z ²² , and Z ²⁴ are Each independently represents a carbon atom, a nitrogen atom or a phosphorus atom, and X ⁵⁴ and X ⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. Ring Q ²³ represents a 5-membered ring, bonds between atoms forming a 5-membered ring is a single bond or a double bond. Coupling ring Q ²³ and Pt represents a covalent ^{bond, Pt-Z 21, Pt-} Z 22, and Pt-Z ^24, represents a coordination or covalent bonds. L ³ represents a divalent linking group. The organic electroluminescent element according to claim 7, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (III-a).

In the formula, X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , and X ¹⁵⁶ are each independently a carbon atom, nitrogen atom or Represents a phosphorus atom, and X ¹⁵⁴ and X ¹⁵⁵ each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. X ¹⁴¹ , X ¹⁴² , X ¹⁴³ , X ¹⁴⁴ , X ¹⁴⁵ , X ¹⁴⁶ , X ¹⁴⁷ , X ¹⁴⁸ , X ¹⁵¹ , X ¹⁵² , X ¹⁵³ , X ¹⁵⁴ , and X ¹⁵⁵ are each independently replaced if possible It may have a group. Ring Q ⁷³ represents a 5-membered ring, and the bond between the atoms forming the 5-membered ring is a single bond or a double bond. A solid line representing a bond between ring Q ⁷¹ , ring Q ⁷² , ring Q ⁷³ , and ring Q ⁷⁴ and Pt represents a covalent bond, and a broken line represents a coordination bond. L ⁸ represents a divalent linking group.   General formula (I), general formula (II), general formula (II-a), general formula (II-a-1), general formula (II-b), general formula (II-b-1), general formula The organic electroluminescent device according to any one of claims 1 to 8, wherein the light emitting layer contains at least one of compounds represented by (III) and general formula (III-a).   The organic electroluminescent element according to any one of claims 1 to 9, wherein a material having at least one deuterium atom is contained in at least one of the organic layers.   The organic electroluminescent element according to claim 10, wherein the material having at least one deuterium atom is a material containing either a carbazole skeleton or an indole skeleton having at least one deuterium atom.