JP2006128634A - Organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitting element with good luminescent properties and durability. <P>SOLUTION: An organic electroluminescent element has at least one layer of an organic layer containing a luminescent layer between a pair of electrodes. The organic electroluminescent element contains at least one kind of a metal complex having a ligand with five or more coordination atoms in the organic layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a light emitting device, particularly an organic electroluminescent device (EL device).

  Today, research and development on various display elements are active. Among them, organic electroluminescence (EL) elements are attracting attention as promising display elements because they can emit light with high luminance at a low voltage. Durability is an important characteristic of organic EL elements, and attempts to improve the durability of organic EL elements are being studied. As a means for improving durability, a light-emitting element using CuPc (copper phthalocyanine) in a hole injection layer is known (for example, see Patent Document 1 and Non-Patent Document 1), but the quantum efficiency is low, Further improvements were sought.

On the other hand, in recent organic EL device development, various studies on improving external quantum efficiency have been conducted. Among them, trisphenylpyridine iridium complex (see, for example, Patent Document 2), octaethylporphyrin platinum complex, etc. An element containing a phosphorescent material such as a platinum complex (see, for example, Patent Documents 3 and 4) achieves high efficiency and has attracted attention.
However, devices containing these phosphorescent materials are not satisfactory in terms of durability, and further improvements have been demanded. In addition, conventional platinum complexes (see, for example, Patent Documents 3 and 4) have a light emission color limited to orange to red, and emit light having a short wavelength of blue to green necessary for full color and multicolor display applications. There was a problem that could not be obtained.
Furthermore, there are reports on tridentate metal complex phosphorescent materials (for example, Patent Documents 5, 6, and 7 and Non-Patent Documents 2 and 3), but the durability is not satisfactory. There wasn't.
Recently, a hexadentate iridium complex-based phosphorescent material and a hexadentate aluminum complex-based host material have been disclosed (Patent Document 8), but the device durability is still unsatisfactory.
JP-A-57-51781 International Publication No. 00/070655 Pamphlet US Pat. No. 6,303,238 B1 US Pat. No. 6,653,564B1 International Publication No. 04/039781 Pamphlet International Publication No. 04/039914 Pamphlet JP 2002-363552 A International Publication No. 04/081017 Pamphlet "Applied Physics Letters", 15, 69, (1996). “Journal of the American Chemical Society, 2004, 126, 4958-4971. “Journal of the Chemical Society, Dalton Transactions,” 2002, 3234-3240.

  An object of the present invention is to provide a light emitting element having good light emitting characteristics and durability.

  The above object has been achieved by the following means.

<1> An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic layer contains at least one metal complex having a pentadentate or higher ligand. Organic electroluminescent element characterized.
<2> The metal ion in the metal complex is one selected from the group consisting of platinum ion, gold ion, iridium ion, rhenium ion, palladium ion, rhodium ion, ruthenium ion, tungsten ion, and copper ion. The organic electroluminescent element as described in <1>.
<3> The organic electroluminescent element as described in <1>, wherein the metal ion in the metal complex is one selected from the group of aluminum ion and gallium ion.
<4> The organic electroluminescent element as described in <1> or <2>, wherein the metal complex is a metal complex that emits phosphorescence and contains the metal complex in a light emitting layer.

<5> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (1).

(In General Formula (1), M ¹ represents a metal ion. L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ and L ¹⁷ are each independently a coordinating group that coordinates to M ^1. Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ and Y ¹⁵ each independently represents a single bond or a linking group, n ¹¹ represents 0 or 1, and n ¹² represents an integer of 0 to 4.)
<6> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (3).

(In the general formula (3), M ³ represents a metal ion. L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ and L ³⁷ are each independently a coordinating group which coordinates to M ^3. Y ³¹ , Y ³² , Y ³³ , Y ³⁴ and Y ³⁵ each independently represents a single bond or a linking group, n ³¹ represents 0 or 1, and n ³² represents an integer of 0 to 4.)
<7> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (4).

(In the general formula (4), M ⁴ represents a metal ion. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ and L ⁴⁷ each independently represent a coordinating group which coordinates to M ^4. Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represents a single bond or a linking group, and n ⁴¹ and n ⁴² each independently represents 0 or 1, but at least one of n ⁴¹ and n ⁴² is 1 N ⁴³ represents an integer of 0 to 4.)
<8> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (5).

(In general formula (5), M ⁵ represents a metal ion. L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ and L ⁵⁷ each independently represent a coordinating group which coordinates to M ^5. Y ⁵¹ , Y ⁵² and Y ⁵³ each independently represents a single bond or a linking group, and n ⁵¹ and n ⁵² each independently represents 0 or 1, but at least one of n ⁵¹ and n ⁵² is 1 N ⁵³ represents an integer of 0 to 4.)
<9> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (6).

(In the general formula (6), M ⁶ represents a metal ion. L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ each independently represent a coordinating group which coordinates to M ^6. Y ⁶¹ , Y ⁶² and Y ⁶³ each independently represents a single bond or a linking group.n ⁶¹ represents 0 or 1. n ⁶² represents an integer of 0 to 4.)
<10> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (7).

(In the general formula (7), M ⁷ represents a metal ion. L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ⁷⁶ and L ⁷⁷ each independently represent a coordinating group which coordinates to M ^7. Y ⁷¹ , Y ⁷² and Y ⁷³ each independently represents a single bond or a linking group, and n ⁷¹ and n ⁷² each independently represents 0 or 1, but at least one of n ⁷¹ and n ⁷² is 1 N ⁷³ represents an integer of 0 to 4.)
<11> The organic electroluminescent element according to any one of <1> to <4>, wherein the metal complex is a compound represented by the following general formula (2).

(In the general formula (2), M ² represents a metal ion. L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ and L ²⁷ are each independently a coordinating group which coordinates to M ^2. Y ²¹ , Y ²² , Y ²³ and Y ²⁴ each independently represents a single bond or a linking group, n ²¹ represents 0 or 1, and n ²² represents an integer of 0 to 4.
<12> n ²¹ is 1, and the organic electroluminescent device according to <11> where n ²² is equal to or an integer of 1 to 4.
<13> The organic electroluminescent element according to <11> or <12>, wherein at least one of Y ²² and Y ²³ represents a linking group.
<14> The compound represented by the general formula (2) is one selected from the group of compounds represented by the following general formulas (2-1) to (2-13) <11 The organic electroluminescent element according to any one of> to <13>.

(Formula (2-1) to formula (2-13) in, .Y ^21, Y ²³ and Y ²⁴ M ² is representative of the metal ions, .L ²³ which each independently represent a single bond or a linking group, L ²⁴ , L ²⁵ and L ²⁶ each independently represent a coordinating group which coordinates to M ² , A represents CR ^A , N or P, R ^A represents a hydrogen atom or a substituent, and Z represents N or .X showing a P represents O, S, and NR ^N1, .Q R ^N1 is representative of the .n ^x is 0 or 1 representing a hydrogen atom or a substituent ^{O, S, Se, NR N2} , CR C1 R ^C2 is represented, R ^N2 represents a substituent, R ^C1 and R ^C2 each independently represents a substituent, and G represents O or S.)

<15> The organic electroluminescent element according to any one of <1> to <14>, wherein the metal complex is contained in a hole injection layer and / or a hole transport layer.
<16> The organic electroluminescent element according to any one of <1> to <14>, wherein the metal complex is contained in an electron injection layer and / or an electron transport layer.
<17> The organic electroluminescent element according to any one of <1> to <14>, wherein the light emitting layer contains a host material, and the host material is a metal complex.
<18> The organic electroluminescent element according to any one of <1> to <14>, wherein the light emitting layer contains two or more host materials.
<19> The organic electroluminescent element according to any one of <1> to <14>, wherein the light emitting layer contains at least one kind of the metal complex and another light emitting compound.

<20> The organic electroluminescent element according to any one of <1> to <14>, wherein the light emitting layer contains at least two or more of the metal complexes.
<21> The organic electroluminescence device according to any one of <1> to <20>, wherein the metal complex has a lowest excited triplet energy level of 65 kcal / mol to 95 kcal / mol. .
<22> The organic electroluminescent element according to any one of <1> to <21>, wherein the metal complex is a host material, and the metal complex is contained in a light emitting layer.
<23> The organic electroluminescent element as described in <22>, wherein the luminescent material is a platinum complex of a tetradentate ligand.
<24> The organic electroluminescence device according to any one of <1> to <22>, wherein the emission maximum wavelength of the emission spectrum of the device is shorter than 450 nm.

  According to the present invention, it is possible to provide a light emitting element capable of emitting light with high efficiency and having excellent durability.

The organic electroluminescent element of the present invention has at least one organic layer including a light emitting layer between a pair of electrodes, and contains at least one metal complex having a pentadentate or higher ligand in the organic layer. Features.
By containing a metal complex that is multidentate in five or more positions in the organic layer between the pair of electrodes, there is an effect that stability against electric charges is improved and driving durability is remarkably improved as compared with conventional compounds. . Moreover, the quantum yield of light emission and the stability in an excited state are also improved, and when used as a light emitting material, the effects of improving the light emission efficiency and durability can be obtained.
Hereinafter, the structure and the like of the metal complex having a pentadentate or higher ligand in the present invention (hereinafter referred to as “the complex of the present invention”) will be described in detail.

The metal ion of the metal complex of the present invention is not particularly limited, but monovalent to tetravalent metal ions are preferable, monovalent to trivalent metal ions are more preferable, and divalent or trivalent metal ions are still more preferable.
Specific examples of metal ions include aluminum ions, cobalt ions, nickel ions, copper ions, gallium ions, ruthenium ions, rhodium ions, palladium ions, silver ions, cerium ions, europium ions, tungsten ions, rhenium ions, osmium ions, Examples include iridium ions, platinum ions, gold ions, lead ions, and zinc ions.

  When the complex of the present invention is used as a charge injection layer (hole injection layer, electron injection layer) material, charge blocking layer (hole blocking layer, electron blocking layer) material, exciton blocking layer material, and host material of a light emitting layer The metal ions are preferably aluminum ions, cobalt ions, nickel ions, copper ions, gallium ions, ruthenium ions, rhodium ions, palladium ions, iridium ions, platinum ions, gold ions, lead ions, aluminum ions, gallium ions, Rhodium ion, palladium ion, iridium ion, platinum ion, and gold ion are more preferable, and iridium ion, aluminum ion, and gallium ion are still more preferable.

When the complex of the present invention is used as a light emitting material, the metal ions are preferably platinum ions, gold ions, iridium ions, rhenium ions, palladium ions, rhodium ions, ruthenium ions, tungsten ions, copper ions, and more preferably platinum ions. Ion, iridium ion, and rhenium ion, more preferably platinum ion and iridium ion, and particularly preferably iridium ion.
There are no particular restrictions on the atoms coordinated to the metal ion, but oxygen atoms, nitrogen atoms, carbon atoms, sulfur atoms, phosphorus atoms, and halogen atoms are preferred, and oxygen atoms, nitrogen atoms, and carbon atoms are more preferred. An atom, a sulfur atom, a phosphorus atom, and a chlorine atom, more preferably an oxygen atom, a nitrogen atom, a carbon atom, and a phosphorus atom, and particularly preferably an oxygen atom, a nitrogen atom, and a carbon atom.

  The coordination group structure of the ligand is not particularly limited. For example, an aromatic hydrocarbon ring ligand (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably carbon number). 6 to 16, for example, benzene ligand, naphthalene ligand, anthracene ligand, phenanthracene ligand, etc.), heterocyclic ligand (preferably having 1 to 20 carbon atoms, More preferably, it is C1-C16, More preferably, it is C1-C12, Most preferably, it is an aromatic heterocyclic ligand. Thiophene ligand, pyridine ligand, pyrazine ligand, pyrimidine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole ligand Oxadiazole ligands, thiadiazole ligands, and condensed rings containing them (eg, indole ligands, quinoline ligands, isoquinoline ligands, quinoxaline ligands, purine ligands, carbazole coordination) And phenanthroline ligands, benzothiazole ligands, benzimidazole ligands, etc.) and their tautomers) etc. These heterocyclic ligands are heteroatoms or carbon atoms in the heterocycle. Any of these may be coordinated to the metal ion).

Alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like. ), An aryloxy ligand (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc. A heterocyclic oxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy ), A silyloxy ligand (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms). Particularly preferably 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.),

Carboxylato ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carboxylate, methylcarboxylate, phenylcarboxylate, naphthylcarboxylate, Pyridine carboquilate, quinolinecarboxylate, etc.), ether ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, dialkyl ethers). Ligand (dimethyl ether, diethyl ether, etc.), diaryl ether ligand (eg, diphenyl ether, etc.), furyl ligand, etc.),

Amino ligands (alkylamino ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methylamino, dimethylamino, diethylamino, etc.) An arylamino ligand (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms, such as phenylamino), a heterocycle Amino ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylamino, pyrazylamino, pyrimidylamino, quinolylamino, isoquinolylamino, quinoxalyl Amino, carbazolylamino, thienylamino, furylamino, thiazolylamino, oxazolylamino , Pyrazolylamino, triazolylamino, etc.), acylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example acetyl Amino, benzoylamino, etc.), alkoxycarbonylamino ligands (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 ligands (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino) ), Sulfonylamino ligands (preferably having 1 to 30 carbon atoms, more preferably charcoal) 1-20, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, trifluoromethanesulfonylamino, benzenesulfonylamino, etc. pentafluorobenzenesulfonyl amino and the like.)),

Carbonyl ligands (eg, ketone ligands, ester ligands, amide ligands, etc.), alkylthio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon numbers) 1 to 12, for example, methylthio, ethylthio, etc.), an arylthio ligand (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, For example, phenylthio etc.), a heterocyclic thio ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as 2-pyridylthio, 2 -Benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), thiocarbonyl ligands (eg thioketone coordination) A thioether ligand (for example, a dialkyl thioether ligand, a diaryl thioether ligand, a thiofuryl ligand, etc.), a group consisting of a combination of the above, and the like Is mentioned.

  As a coordinating group, an aromatic hydrocarbon ring ligand, an aromatic heterocyclic ligand (for example, furan ligand, thiophene ligand, pyridine ligand, pyrazine ligand, pyrimidine ligand) , Pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxadiazole ligand, thiadiazole ligand Ligands and condensed ring ligands containing them (for example, quinoline ligands, isoquinoline ligands, phenanthroline ligands, benzoxazole ligands, benzimidazole ligands, etc.) Mutants, etc.), alkyloxy ligands, aryloxy ligands, ether ligands, alkylthio ligands, arylthio ligands, alkylamino ligands, ants A ligand comprising a ruamino ligand, an acylamino ligand, a carboxylate ligand, and a combination thereof, more preferably an aromatic carbocyclic ligand, a pyridine ligand, or a pyrazine ligand. , Pyrimidine ligand, pyridazine ligand, thiophene ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole ligand, quinoline ligand , Isoquinoline ligand, benzimidazole ligand, alkyloxy ligand, aryloxy ligand, ether ligand, alkylthio ligand, arylthio ligand, alkylamino ligand, arylamino ligand , An acylamino ligand, a carboxylate ligand, and a group consisting of a combination thereof, more preferably an aromatic carbocyclic ligand, pyridi Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole ligand, quinoline Ligand, isoquinoline ligand, benzimidazole ligand, alkyloxy ligand, aryloxy ligand, alkylamino ligand, arylamino ligand, acylamino ligand, carboxylate ligand, And a group comprising a combination of these.

The above ligands may have a substituent if possible. As the substituent, those exemplified as the following substituent group A can be applied.
<Substituent group A> 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, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number). 2-10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably carbon number). 2-10, for example, propargyl, 3-pentynyl, etc.)

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. Group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, methylthio, ethylthio and the like can be mentioned. ), An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably carbon 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and 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). -30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, and examples include methanesulfinyl, benzenesulfinyl and the like.
), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine 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 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.)

  When it has a substituent, these substituents may be further substituted. Moreover, you may connect with substituents and may form a ring.

  The complex of the present invention is preferably a compound represented by the general formulas (1), (2), (3), (4), (5), (6) and (7).

(In General Formula (1), M ¹ represents a metal ion. L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ and L ¹⁷ are each independently a coordinating group that coordinates to M ^1. Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ and Y ¹⁵ each independently represents a single bond or a linking group, n ¹¹ represents 0 or 1, and n ¹² represents an integer of 0 to 4.)

(In the general formula (2), M ² represents a metal ion. L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ and L ²⁷ are each independently a coordinating group which coordinates to M ^2. Y ²¹ , Y ²² , Y ²³ and Y ²⁴ each independently represents a single bond or a linking group, n ²¹ represents 0 or 1, and n ²² represents an integer of 0 to 4.

In general formula (3), M ³ represents a metal ion. L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ and L ³⁷ each independently represent a coordinating group which coordinates to M ³ . Y ³¹ , Y ³² , Y ³³ , Y ³⁴ and Y ³⁵ each independently represents a single bond or a linking group. n ³¹ represents 0 or 1; n ³² represents an integer of 0 to 4.

(In the general formula (4), M ⁴ represents a metal ion. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ and L ⁴⁷ each independently represent a coordinating group which coordinates to M ^4. Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represents a single bond or a linking group, and n ⁴¹ and n ⁴² each independently represents 0 or 1, but at least one of n ⁴¹ and n ⁴² is 1 N ⁴³ represents an integer of 0 to 4.)

（一般式（５）中、Ｍ⁵は金属イオンを表す。Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³、Ｌ⁵⁴、Ｌ⁵⁵、Ｌ⁵⁶およびＬ⁵⁷はそれぞれ独立にＭ⁵に配位する配位基を表す。Ｙ⁵¹、Ｙ⁵²およびＹ⁵³はそれぞれ独立に単結合または連結基を表す。ｎ⁵¹、ｎ⁵²はそれぞれ独立に０または１を表すが、ｎ⁵¹とｎ⁵²の少なくともいずれか一方は１を表す。ｎ⁵³は０〜４の整数を表す。）

(In general formula (5), M ⁵ represents a metal ion. L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ and L ⁵⁷ each independently represent a coordinating group which coordinates to M ^5. Y ⁵¹ , Y ⁵² and Y ⁵³ each independently represents a single bond or a linking group, and n ⁵¹ and n ⁵² each independently represents 0 or 1, but at least one of n ⁵¹ and n ⁵² is 1 N ⁵³ represents an integer of 0 to 4.)

(In the general formula (6), M ⁶ represents a metal ion. L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ each independently represent a coordinating group which coordinates to M ^6. Y ⁶¹ , Y ⁶² and Y ⁶³ each independently represents a single bond or a linking group.n ⁶¹ represents 0 or 1. n ⁶² represents an integer of 0 to 4.)

(In the general formula (7), M ⁷ represents a metal ion. L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ⁷⁶ and L ⁷⁷ each independently represent a coordinating group which coordinates to M ^7. Y ⁷¹ , Y ⁷² and Y ⁷³ each independently represents a single bond or a linking group, and n ⁷¹ and n ⁷² each independently represents 0 or 1, but at least one of n ⁷¹ and n ⁷² is 1 N ⁷³ represents an integer of 0 to 4.)

Next, the compound represented by the general formula (1) will be described in detail.
The metal ion represented by M ¹ is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ and L ¹⁷ are synonymous with the coordinating groups of the complex of the present invention described above. L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , and L ¹⁷ are other L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , L ^{17, if possible.} Or Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , and Y ¹⁵ may be connected to each other.

^{Y 11, Y 12, Y 13} , Y 14 and is not particularly restricted but includes linking group represented by Y ^15, such as an alkylene group, an alkenylene group, an arylene group, a heterocyclic linking group, oxygen atom linking, sulfur atom linking And a linking group comprising a group, a silicon atom linking group, an imino linking group, a carbonyl linking group, and a combination thereof.

Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ are preferably a single bond, an alkylene group, an alkenylene group, an arylene group, a heterocyclic linking group, an imino linking group, an oxygen atom linking group, a sulfur atom linking group, and The linking group is a combination of these, and more preferably a single bond, an alkylene group, a nitrogen-containing aromatic heterocyclic linking group, an imino linking group, an oxygen atom linking group, or a linking group consisting of these combinations.
Specific examples of the linking group represented by Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ are shown below.

n ¹¹ represents 0 or 1, and is preferably 1. n ¹² represents an integer of 0 to 4, preferably 0 or 1, more preferably 0. When n ¹² is an integer of 2 to 4, a plurality of L ¹⁷ may be the same or different from each other. A plurality of L ¹⁷ may be linked to form a bidentate or more multidentate ligand.

  Of the compounds represented by the general formula (1), a compound represented by the following general formula (1-A) is preferable, and a compound represented by the following general formula (1-B) is more preferable.

In general formula (1-A), M ¹ , L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , and Y ¹⁵ are each represented by the general formula ( It is synonymous with those in 1), and the preferred range is also the same.

In the general formula (1-B), M ¹ , L ¹² , L ¹³ , L ¹⁵ , L ¹⁶ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ are the same as those in the general formula (1). The preferred range is also the same.

Next, the compound represented by the general formula (3) will be described in detail.
The metal ion represented by M ³ is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ and L ³⁷ are synonymous with the coordinating groups of the complex of the present invention described above. If possible, L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ are respectively L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ^37. Or Y ³¹ , Y ³² , Y ³³ , Y ³⁴ , Y ³⁵ may be connected to each other.

^{Y 31, Y 32, Y 33} , the linking group represented by Y ³⁴ and Y ³⁵ are not particularly limited, it can be applied those mentioned Y ¹¹ to Y ¹⁵ in formula (1).
n ³¹ represents 0 or 1, and is preferably 1. n ³² represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ³² is an integer of 2 to 4, the plurality of L ³⁷ may be the same or different from each other. A plurality of L ³⁷ may be linked to form a bidentate or more multidentate ligand.

  Among the compounds represented by the general formula (3), a compound represented by the following general formula (3-A) is preferable.

(In the general formula (3-A), M ³ , L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , Y ³¹ , Y ³² , Y ³³ , Y ³⁴ , Y ³⁵ are respectively the general formulas. (It is synonymous with those in (3), and the preferred range is also the same.)

Next, the compound represented by the general formula (4) will be described in detail.
The metal ion represented by M ⁴ has the same meaning as the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ and L ⁴⁷ are synonymous with the coordinating groups of the aforementioned complex of the present invention, and the preferred ranges are also the same. is there. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ^46, and L ⁴⁷ may be the other L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ^46, and L ^{47, if possible.} Or Y ⁴¹ , Y ⁴² and Y ⁴³ may be connected to each other.
n ⁴¹ and n ⁴² each independently represents 0 or 1, but at least one of n ⁴¹ and n ⁴² represents 1. n ⁴¹ is preferably 1, and n ⁴² is preferably 1. n ⁴³ represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ⁴³ is an integer of 2 to 4, the plurality of L ⁴⁷ may be the same or different from each other. A plurality of L ⁴⁷ may be linked to form a bidentate or more multidentate ligand.

Next, the compound represented by the general formula (5) will be described in detail.
The metal ion represented by M ⁵ is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ and L ⁵⁷ are synonymous with the coordinating groups of the aforementioned complex of the present invention, and the preferred ranges are also the same. is there. L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ^56, and L ⁵⁷ may be the other L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ^56, and L ^{57, if possible.} Or Y ⁵¹ , Y ⁵² and Y ⁵³ may be connected to each other.
n ⁵¹ and n ⁵² each independently represents 0 or 1, but at least one of n ⁵¹ and n ⁵² represents 1. n ⁵¹ is preferably 1, and n ⁵² is preferably 1. n ⁵³ represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ⁵³ is an integer of 2 to 4, the plurality of L ⁵⁷ may be the same or different from each other. Or it may have a bidentate or multidentate ligand linked to each other a plurality of L ^57.

Next, the compound represented by the general formula (6) will be described in detail.
The metal ion represented by M ⁶ is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ are synonymous with the coordinating groups of the complex of the present invention, and the preferred ranges are also the same. is there. L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ^66, and L ⁶⁷ may be added to other L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ^66, and L ^{67, if possible} Or Y ⁶¹ , Y ⁶² and Y ⁶³ may be connected to each other.
n ⁶¹ represents 0 or 1, and n ⁶¹ is preferably 1. n ⁶² represents an integer of 0 to 4, preferably 0 or 1, more preferably 0. When n ⁶² is an integer of 2 to 4, the plurality of L ⁶⁷ may be the same or different from each other. A plurality of L ⁶⁷ may be linked to form a bidentate or more multidentate ligand.

Next, the compound represented by the general formula (7) will be described in detail.
The metal ion represented by M ⁷ is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ⁷⁶ and L ⁷⁷ are synonymous with the coordinating groups of the complex of the present invention, and the preferred ranges are also the same. is there. L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ^76, and L ⁷⁷ may be the other L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ^76, and L ^{77, if possible.} Or Y ⁷¹ , Y ⁷² and Y ⁷³ may be connected to each other.
n ⁷¹ and n ⁷² each independently represents 0 or 1, but at least one of n ⁷¹ and n ⁷² represents 1. n ⁷¹ is preferably 1, and n ⁷² is preferably 1. n ⁷³ represents an integer of 0 to 4, preferably 0 or 1, more preferably 0. When n ⁷³ is an integer of 2 to 4, the plurality of L ⁷⁷ may be the same or different from each other. A plurality of L ⁷⁷ may be linked to form a bidentate or more multidentate ligand.

Next, the compound represented by the general formula (2) will be described in detail.
The metal ion represented by M ² is synonymous with the metal ion of the complex of the present invention described above, and the preferred range is also the same.
The coordinating groups represented by L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ and L ²⁷ are synonymous with the coordinating groups of the aforementioned complex of the present invention, and the preferred ranges are also the same. is there. L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ , and L ²⁷ are each other L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ , L ^{27, if possible.} Or Y ²¹ , Y ²² , Y ²³ , and Y ²⁴ may be connected to each other.

Y ^21, Y ^22, Y ²³ and although Y is not particularly restricted but includes linking group represented by ^24, it can be applied those mentioned Y ¹¹ to Y ¹⁵ in formula (1).
n ²¹ represents 0 or 1, and is preferably 1. n ²² represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ²² is an integer of 2 to 4, the plurality of L ²⁷ may be the same or different from each other. Or it may have a bidentate or multidentate ligand coupled multiple L ²⁷ together.

  Of the compounds represented by the general formula (2), a compound represented by the following general formula (2-A) is preferable.

In the general formula (2-A), M ² , L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ , Y ²¹ , Y ²² , Y ²³ , and Y ²⁴ are respectively in the general formula (2). They are synonymous with them, and preferred ranges are also the same.

  Of the compounds represented by the general formula (2-A), compounds represented by the following general formulas (2-1) to (2-13) are preferable.

(Formula (2-1) to formula (2-13) in, .Y ^21, Y ²³ and Y ²⁴ M ² is representative of the metal ions, .L ²³ which each independently represent a single bond or a linking group, L ²⁴ , L ²⁵ and L ²⁶ each independently represent a coordinating group which coordinates to M ² , A represents CR ^A , N or P, R ^A represents a hydrogen atom or a substituent, and Z represents N or .X showing a P represents O, S, and NR ^N1, .Q R ^N1 is representative of the .n ^x is 0 or 1 representing a hydrogen atom or a substituent ^{O, S, Se, NR N2} , CR C1 R ^C2 is represented, R ^N2 represents a substituent, R ^C1 and R ^C2 each independently represents a substituent, and G represents O or S.)

Next, general formulas (2-1) to (2-13) will be described in detail.
M ² , Y ²¹ , Y ²³ , Y ²⁴ , L ²³ , L ²⁴ , L ²⁵ and L ²⁶ have the same meanings as those in formula (2), and preferred ranges are also the same.
A represents CR ^A , N or P. R ^A represents a hydrogen atom or a substituent, and as the substituent, those exemplified as the substituent group A can be applied. The substituent is preferably an alkyl group, an aryl group, a fluorine atom, an alkoxy group, an amino group, or a cyano group. A is preferably CR ^A or N, and more preferably CR ^A.
Z represents N or P, preferably N.
X represents O, S, NR ^N1 . R ^N1 represents a hydrogen atom or a substituent. As the substituent represented by R ^N1 , those listed as the following substituent group B can be applied.
<Substituent group B> 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, cyclopropyl, cyclopentyl, cyclohexyl, etc.).

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 acyl 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 acetyl, benzoyl, formyl, pivaloyl, and 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, and examples thereof include mesyl and tosyl).

Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl and furyl. , Thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, especially Preferably it is C3-C24, for example, trimethylsilyl, a triphenylsilyl, etc.), a silyloxy group (Preferably C3-C40, More preferably C3-C30, Most preferably C3-C3 24, for example, trimethylsilyloxy, triphenylsilyloxy, etc. It is.)

The substituent represented by R ^N1 is preferably an alkyl group or a sulfonyl group. X is preferably an oxygen atom or a sulfur atom.
n ^x represents 0 or 1. If M ² represents a platinum ion, a gold ion, iridium ion, a rhenium ion, a palladium ion, a rhodium ion, n ^x is preferably 0, if M ² represents an aluminum ion, a gallium ion, n ^x is preferably 1.
G represents O or S. G is preferably O.
Q represents O, S, Se, NR ^N2 , or CR ^C1 R ^C2 . As RN2, those ^exemplified as the substituent group B can be applied. The substituent represented by R ^N2 is preferably an alkyl group, an aryl group, or a heterocyclic group. As R ^C1 and R ^C2 , those ^exemplified as the substituent group A can be applied. R ^C1 and R ^C2 are preferably an alkyl group, an aryl group, or a heterocyclic group. Q is preferably O, S, NR ^N2 or CR ^C1 R ^C2 , more preferably O, S or NR ^N2 , and further preferably NR ^N2 .

  The complex of the present invention has 5 or more ligands, preferably 5 to 10 ligands, more preferably 5 to 8 seats, more preferably 5 or 6 seats. 6 seats are particularly preferred. By using a complex having a ligand in the range of 5 to 10 seats, the complex stability is increased, thereby improving drive durability and storage stability with time. Further, the phosphorescence quantum yield is increased, and as a result, the light emission efficiency is also increased. Furthermore, complexes having a pentadentate or higher ligand tend to have a short phosphorescence lifetime, which increases the luminance and efficiency when driven at high currents. In addition, since the phosphorescence lifetime is shortened, the time during which the excitonic state is unstable is shortened, and thus durability is also improved.

  The complex of the present invention may be a low molecular compound, and an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 1000000, and still more preferably 3000 to 100000. Yes.) In the case of a polymer compound, the complex portion may be contained in the polymer main chain, or may be contained in the polymer side chain. In the case of a polymer compound, it may be a homopolymer compound or a copolymer. The complex of the present invention is preferably a low molecular compound.

  Next, although the compound example of the complex of this invention is shown, this invention is not limited to this.

The complex of the present invention can be synthesized by using the method described in “Journal of Chemical Society, 5008, (1952)”, the synthesis method described later, and the like.
For example, a ligand or a dissociated product thereof and a metal compound are mixed with 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, In the presence of a base (eg, inorganic or organic bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate). Or in the absence of a base, at room temperature or lower, or by heating (in addition to normal heating, a method of heating with microwaves is also effective).

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

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

  In the complex of the present invention, the ligand forming the partial structure of the target complex is preferably 0.1 equivalent to 20 equivalents, more preferably 0.3 equivalent to 10 equivalents, more preferably, relative to the metal compound. Can be synthesized by adding 0.5 to 6 equivalents. Examples of the metal compound include metal halides (for example, platinum chloride), metal acetates (for example, palladium acetate), metal acetylacetonates (for example, europium acetylacetonate), or hydrates thereof. can give.

  Next, a typical method for synthesizing the complex of the present invention will be described using synthesis of a hexadentate ligand as an example.

The hexadentate ligand (compounds 14-17 in the above scheme) can be synthesized by linking different tridentate ligands.
For example, 1,3-bis- (2-pyridyl) benzene derivative (3) having a linking site on a benzene ring is obtained by converting 1,3-dibromobenzene derivative (1) and 2- (trialkylstannyl) pyridine. By using a Stille coupling reaction as a starting material and deprotecting the methyl group (using the method described in Journal of Organic Chemistry, 741, 11, (1946), heating in pyridine hydrochloride, etc.) Can be synthesized.

  The 1,3-bis (2-pyridyl) benzene derivative (8) having a linking site on the pyridine ring is subjected to a Suzuki coupling reaction with 2-bromopyridine using 3-hydroxyphenylboric acid as a starting material. , By reacting with trifluoromethanesulfonic anhydride in the presence of a base, converting the hydroxyl group to triflate (6), conducting a coupling reaction with bispinacol borane (method described in Journal of Organic Chemistry, 60, 7508 (1995)), After obtaining 3- (2-pyridyl) phenylboric acid derivative (7), it can be further synthesized by carrying out Suzuki coupling reaction with 2-bromo-3-hydroxypyridine.

  The 2,6-biphenylpyridine derivative (11) having a linking site on the benzene ring is obtained by lithiating the α-position on the pyridine ring with 2-phenylpyridine (9) using dimethylaminoethanol / n-butyllithium. It can be synthesized by reacting with carbon tetrabromide to give 2-bromo-6-phenylpyridine (10) and then performing a Suzuki coupling reaction with 4-hydroxyphenylboric acid.

Tridentate ligands having different kinds and numbers of substituents and different substitution positions of the substituents can be synthesized by using the above method.
The hexadentate ligand (14) reacts with the tridentate ligand (11) and a haloalcohol (such as 8-bromooctanol) in the presence of a base (potassium carbonate, sodium carbonate, pyridine, triethylamine, etc.). The compound (12) can be synthesized by bromination with phosphorous tribromide and a coupling reaction (an ether bond introduction reaction in the presence of a base) with a tridentate ligand (3). .

  By using a corresponding tridentate ligand as a starting material in the same manner, a hexadentate ligand (15 to 17) in which the tridentate ligand is linked at two positions can also be synthesized.

[Light emitting element]
Next, a light emitting device containing the complex of the present invention will be described.
The light-emitting element of the present invention is an element in which at least one organic compound layer including a light-emitting layer is formed between a pair of electrodes of an anode and a cathode. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, and an electron injection An organic compound layer such as a layer or an electron transport layer, a protective layer, or the like may be provided, and each of these layers may have another function. At least one of the organic compound layers contains the complex of the present invention. Various materials can be used for forming each layer.
The complex of the present invention may be used alone or in combination of two or more.

In the light emitting device of the present invention, the metal complex of the present invention is preferably used as a charge transport material, and an embodiment in which it is contained in a hole injection layer and / or a hole transport layer is preferable.
By including it in the hole injection layer and / or the hole transport layer, driving voltage is lowered, durability is improved,
There is a tendency that effects such as improvement in luminous efficiency are easily exhibited.
Moreover, the aspect contained in an electron injection layer and / or an electron carrying layer is also a preferable aspect.
By including it in the electron injection layer and / or the electron transport layer, effects such as a decrease in driving voltage, an improvement in durability, and an improvement in light emission efficiency tend to be manifested.

The light emitting device of the present invention can use a normal light emitting system, a driving method, a usage form, and the like except that it is a device using the complex of the present invention.
An embodiment in which the complex of the present invention is used as a light emitting material, a hole injection material / hole transport material, or an electron injection material / electron transport material is preferable. When used as a light emitting material, the emission wavelength is not particularly limited, and may be ultraviolet light emission or infrared light emission, and may be fluorescent light emission or phosphorescence light emission.

  The light-emitting element of the present invention can improve the light extraction efficiency by various known methods. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.

The external quantum efficiency of the light emitting device of the present invention is preferably 5% or more, more preferably 10% or more, and further preferably 13% or more.
The maximum value of the external quantum efficiency when numeric external quantum efficiency of the device is driven at 20 ° C., or around 100~300cd / m ² when the device is driven at 20 ° C. (preferably 200~300cd / m ²⁾ The value of external quantum efficiency at can be used.
The value of the external quantum efficiency in the present invention is the maximum value of the external quantum efficiency when the device is driven at 20 ° C.
In the present invention, using a source measure unit type 2400 manufactured by Toyo Technica, a DC constant voltage is applied to the EL element to emit light, and the luminance is measured using a luminance meter BM-8 manufactured by Topcon Corporation, and is 200 cd / m ^2. The external quantum efficiency at can be calculated.
Specifically, the external quantum efficiency of the device is calculated from the result and the luminous efficiency curve obtained by measuring the emission luminance, emission spectrum, and current density. That is, the number of input electrons can be calculated using the current density value. The emission luminance was converted to the number of photons emitted by integral calculation using the emission spectrum and the relative visibility curve (spectrum). From these, the external quantum efficiency (%) is calculated by “(number of photons emitted / number of electrons input to the device) × 100”.

The emission spectrum can be measured using a multi-channel analyzer PMA-11 manufactured by Hamamatsu Photonics.
The light emission maximum wavelength of the light emission spectrum of the light emitting device of the present invention is preferably shorter than 450 nm from the viewpoint of obtaining a blue phosphorescent light emitting device with high color purity, and more preferably 410 nm to 450 nm.

Further, the internal quantum efficiency of the light emitting device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by “internal quantum efficiency = external quantum efficiency / light extraction efficiency”.
In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

  The light-emitting element of the present invention is a so-called top emission method that takes out light emission from the anode side (described in JP-A-2003-208109, 2003-248441, 2003-257651, 2003-282261, etc.). There may be.

  The driving durability of the light emitting device of the present invention is, for example, by using a source measure unit 2400 type manufactured by Toyo Technica, etc., applying a direct current voltage to the organic EL device to emit light, and the luminance is measured by a luminance meter BM- It can be evaluated by measuring the time until the initial luminance is halved (luminance half time).

  The organic electroluminescent device of the present invention may contain a blue fluorescent light emitting compound, or a multicolor light emitting device using a blue light emitting device containing a blue fluorescent compound and a light emitting device other than the blue light emitting device at the same time. A full-color light emitting device may be manufactured.

A host material can be used for the light-emitting element of the present invention, and the host material is preferably contained in the light-emitting layer.
As host materials, in addition to the complex of the present invention, arylamine derivatives (triphenylamine derivatives, benzidine derivatives, etc.), aromatic hydrocarbon compounds (triphenylbenzene derivatives, triphenylene derivatives, phenanthrene derivatives, naphthalene derivatives, tetraphenylene derivatives, etc.) ), Aromatic nitrogen-containing heterocyclic compounds (pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, pyrazole derivatives, imidazole derivatives, oxazole derivatives, pyrrole derivatives, etc.), metal complexes other than the complex of the present invention (zinc complex, aluminum complex) And gallium complex).

  In the light-emitting element of the present invention, a layer containing a compound having an ionization potential of 5.9 eV or more (more preferably 6.0 eV or more) is preferably used between the cathode and the light-emitting layer, and an electron transport having an ionization potential of 5.9 eV or more is used. More preferably, layers are used.

The method for forming the organic layer of the light-emitting element containing the compound of the present invention is not particularly limited, but resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spray coating method, dip coating method, Impregnation method, roll coat method, gravure coat method, reverse coat method, roll brush method, air knife coat method, curtain coat method, spin coat method, flow coat method, bar coat method, micro gravure coat method, air doctor coat, blade Coating methods, squeeze coating methods, transfer roll coating methods, kiss coating methods, cast coating methods, extrusion coating methods, wire bar coating methods, screen coating methods, etc.), inkjet methods, printing methods, transfer methods, etc. are used, Resistance heating vapor deposition and coating in terms of characteristics and manufacturing Packaging method, a transfer method is preferable. The organic compound layer containing the complex of the present invention is formed on the substrate by any of the above forming methods, but the thickness is not particularly limited. Preferably it is 10 nm or more, More preferably, it is 50 nm-5 micrometers.

<Base material>
The substrate used in the light-emitting device of the present invention is not particularly limited, but inorganic materials such as zirconia-stabilized yttrium and glass, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polycarbonate, and polyethersulfone. High molecular weight materials such as polyarylate, allyl diglycol carbonate, polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), Teflon (registered trademark), polytetrafluoroethylene-polyethylene copolymer good.

<Anode>
The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more.
Specific examples of anode materials include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and these metals and conductive metals. Mixtures or laminates with oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, and laminates of these with ITO, preferably It is a conductive metal oxide, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used.
Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), a coating of a dispersion of indium tin oxide, etc. A film is formed by this method.
The anode can be subjected to cleaning or other treatments to lower the drive voltage of the element or increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

<Cathode>
The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, stability, etc., between the negative electrode and the adjacent layer such as the electron injection layer, electron transport layer, light emitting layer, etc. Selected in consideration of As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples include an alkali metal (for example, Li, Na, K, etc.) and its fluoride. Or oxides, alkaline earth metals (eg Mg, Ca, etc.) and fluorides or oxides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or their mixed metals, lithium-aluminum alloys or their mixtures Examples thereof include metals, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, preferably materials having a work function of 4 eV or less, more preferably aluminum, lithium-aluminum alloys or mixed metals thereof. , Magnesium-silver alloys or mixed metals thereof. The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide is preferable. The film thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm.
For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a coating method, and a transfer method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

<Organic compound layer>
The organic compound layer of the light-emitting element of the present invention contains at least the metal complex having a pentadentate or higher ligand, but may be contained in one layer or in multiple layers.
The content of the metal complex in the organic compound layer is not particularly limited, but from the viewpoint of lowering driving voltage, improving durability, and improving luminous efficiency, 1 to 100 with respect to the total solid mass. It is preferable that it is mass%, 10-70 mass% is more preferable, and 20-50 mass% is especially preferable.

(Light emitting layer)
The material of the light emitting layer is a function that can inject holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, Any structure can be used as long as it can form a layer having a function of moving injected electric charge and a function of emitting light by providing a recombination field of holes and electrons. In addition to the metal complex having a child, other compounds such as benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perinone, oxadiazole, aldazine , Pyraridine, cyclopentadiene, bisstyrylanthracene, quinacridone Pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol metal complexes and rare earth complexes, polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, organic silanes, Examples include iridium trisphenylpyridine complexes, transition metal complexes represented by platinum porphyrin complexes, and derivatives thereof.

  The light emitting layer preferably contains at least one metal complex having a pentadentate or higher ligand and another light emitting compound in terms of durability improvement and light emission efficiency. As said other luminescent compound, the said other compound and a well-known luminescent compound can be selected as needed.

  Examples of the known luminescent compound include a fluorescent luminescent compound, a phosphorescent luminescent compound, the host material, and the like. From the viewpoint of luminescent efficiency, a phosphorescent luminescent compound is preferable.

The phosphorescent compound is not particularly limited, but is preferably a transition metal complex, more preferably an iridium complex, a platinum complex, a rhenium complex, a ruthenium complex, a palladium complex, a rhodium complex, or a rare earth complex, and an iridium complex or a platinum complex. Further preferred.
JP2002-235076, JP2002-170684, JP2003-123982, JP2003-133074, US6303238 B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234 A2, WO 01/41512 A1, WO 02/02714 A2, WO 02/15645 A1, WO 02/44189 A1, JP 2001-247859, Japanese Patent Application 2000-33561, JP 2002-117978, EP 12111257, JP 2002 26495, JP 2002-234894, JP 2001-247659, JP 2001-298470, JP 2002-173675, JP 2002-203678, JP 2002-203679, special Phosphorescent compounds described in patent documents such 2003-157066 can also be preferably used.
In the case of a light-emitting element using a metal complex having a pentadentate or higher ligand as a host material, the lowest excited triplet energy level (T 1 level) of the metal complex of the present invention is 65 kcal / mol. (272.35 kJ / mol) or more and 95 kcal / mol (398.05 J / mol) or less is preferable, more preferably 67 kcal / mol (280.73 kJ / mol) or more and 95 kcal / mol (398.05 J / mol) or less. More preferably 69 kcal / mol (289.11 kJ / mol) or more and 95 kcal / mol (398.05 J / mol) or less, particularly preferably 71 kcal / mol (297.49 kJ / mol) or more and 95 kcal / mol ( 398.05 J / mol) or less. The above range is particularly preferable from the viewpoint of obtaining a phosphorescent light emitting element having high luminous efficiency and high brightness, and further preferred from the viewpoint of obtaining a blue phosphorescent light emitting element having high color purity.

  Fluorescent compounds include benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bis Stylylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, condensed polycyclic aromatic compounds (anthracene, phenanthroline, pyrene, perylene, rubrene, pentacene, etc.), 8-quinolinol metal Complexes, various metal complexes represented by pyromethene complexes and rare earth complexes, polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, Machine silane, and derivatives thereof.

The host material in the light emitting layer may be one kind, but preferably contains two or more kinds.
The host material is preferably a complex. As the complex, in addition to the complex of the present invention, a metal complex having a ligand having at least one nitrogen atom, oxygen atom or sulfur atom coordinated to a metal is preferable. . The metal ion in the metal complex is not particularly limited, but is preferably beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, tin ion, more preferably beryllium ion, aluminum ion, gallium ion, zinc. An ion, more preferably an aluminum ion, a gallium ion, or a zinc ion.
In the case of a light emitting device in which the metal complex of the present invention is a host material and contains the metal complex in a light emitting layer, the light emitting material is a tetradentate platinum complex from the viewpoint of light emitting efficiency and durability of the device. It is preferable. Examples of the platinum complex of the tetradentate ligand include platinum complexes described in WO 04/108857 pamphlet.

There are various known ligands contained in the metal complex. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Examples include ligands described in Yersin's 1987 issue, “Organometallic Chemistry: Fundamentals and Applications”, Hankabo Publishing Company, Akio Yamamoto, 1982 issue, and the like.
The ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and a monodentate ligand. Or a bidentate or higher ligand, preferably a bidentate ligand such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylazole ligand (hydroxyphenyl) Benzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably carbon 1-10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligands Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl Oxy, 4-biphenyloxy, etc.), heteroaryloxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyl. Oxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), alkylthio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.), arylthio ligand (preferably having 6 to 30 carbon atoms, more preferred) Has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), heteroarylthio ligand (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms). Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, siloxy ligand (preferably carbon number). 1 to 30, more preferably 3 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, and examples thereof include a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group. Is a nitrogen-containing heterocyclic ligand, aryloxy ligand, heteroaryloxy group, siloxy ligand, and more preferably Includes a nitrogen-containing heterocyclic ligand, an aryloxy ligand, and a siloxy ligand.
Specific examples of such a metal complex include the following materials.

  In addition to the above, Exemplified Compounds (H2 to H34) described in JP-A No. 2002-305083, Exemplified Compounds (1-1) to (1-67) described in JP-A No. 2004-221106, JP-A No. 2004-221068 The metal complexes described in the exemplified compounds (H-1) to (H-51) described in the publication can also be suitably used.

As content of the metal complex which has the said pentadentate or more ligand in a light emitting layer, it is 0.01-50 mass% with respect to the total solid content mass from luminous efficiency and durability viewpoint. Preferably, 0.1-20 mass% is more preferable, and 1-10 mass% is especially preferable.
The content of the host material in the light emitting layer is preferably 10 to 80% by weight, more preferably 20 to 70% by weight, based on the total solid content, from the viewpoints of driving voltage, light emission efficiency, and durability. 30 to 60% by mass is particularly preferable.

Although the film thickness of a light emitting layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm.
The method for forming the light emitting layer is not particularly limited, and methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method, ink jet method, printing method, LB method, and transfer method are used. Of these, resistance heating vapor deposition and coating are preferred.

  The light emitting layer may be formed of a single compound or a plurality of compounds. Further, the light emitting layer may be one or plural, and each layer may emit light with different emission colors, for example, white light may be emitted. White light may be emitted from a single light emitting layer. When there are a plurality of light emitting layers, each light emitting layer may be formed of a single material or a plurality of compounds.

(Hole injection layer, hole transport layer)
The material of the hole injection layer and the hole transport layer may be any one having a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Good. Specific examples thereof include the complex of the present invention, carbazole, triazole, oxazole, oxadiazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, Stilbene, silazane, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, polythiophenes, etc. Examples thereof include conductive polymer oligomers, organic silanes, carbon (films), metal complexes represented by the general formula (1) of the present invention, and derivatives thereof. The film thickness of the hole injection layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 nm, more preferably 1 nm to 100 nm, and still more preferably 1 nm to 10 nm. The thickness of the hole transport layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 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.

As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection transport material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, or a transfer method is used. It is done. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.
The content of the metal complex having a pentadentate or higher ligand in the hole injection layer and / or the hole transport layer is from the viewpoint of driving voltage, durability, and luminous efficiency, with respect to the total solid mass. 10 to 80% by mass, preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.

(Electron injection layer, electron transport layer)
The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Specific examples include triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, and distyrylpyrazine in addition to the complex of the present invention. , Aromatic metal tetracarboxylic anhydrides such as naphthalene and perylene, metal complexes of phthalocyanine, 8-quinolinol, metal phthalocyanines, metal complexes having benzoxazole and benzothiazole as ligands, organic silanes, etc. Is mentioned. Although the film thickness of an electron injection layer and an electron carrying layer is not specifically limited, The thing of the range of 1 nm-5 micrometers is preferable normally, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 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.
As a method for forming the electron injection layer and the electron transport layer, a vacuum vapor deposition method, an LB method, a method in which the electron injection transport material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, a transfer method, and the like are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.
The content of the metal complex having a pentadentate or higher ligand in the electron injection layer and / or the electron transport layer is 10% relative to the total solid mass from the viewpoint of driving voltage, durability, and light emission efficiency. It is preferable that it is -80 mass%, 20-60 mass% is more preferable, 30-50 mass% is especially preferable.

<Protective layer>
As a material for the protective layer, any material may be used as long as it has a function of preventing substances 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 , TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ , CaF ₂ , nitrides such as SiN _x , SiO _x N _y , polyethylene, polypropylene, polymethyl methacrylate A monomer mixture comprising polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerization, fluorine-containing copolymer having a cyclic structure in the main chain Polymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.
There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, and transfer method can be applied.

  Hereinafter, although the present invention is explained using an example, the present invention is not limited to these.

[Comparative Example 1]
A glass plate having a thickness of 0.7 mm is cut into a 2.5 cm square as a base material, introduced into a vacuum chamber, and an ITO target having a SnO ₂ content of 10% by weight is used for DC magnetron sputtering (conditions : ITO thin film (thickness 0.2 μm) as a transparent electrode was formed at a substrate temperature of 100 ° C. and an oxygen pressure of 1 × 10 ⁻³ Pa). The surface resistance of the ITO thin film was 10Ω / □.

  Next, the substrate on which the transparent electrode was formed was placed in a cleaning container and subjected to IPA cleaning, and then UV-ozone treatment was performed for 30 minutes. The surface of the transparent electrode was spin-coated with a poly (ethylenedioxythiophene) / polystyrenesulfonic acid aqueous dispersion (manufactured by BAYER, Baytron P: solid content 1.3%), and then vacuumed at 150 ° C. for 2 hours. A hole injection layer having a thickness of 100 nm was formed by drying.

Next, polyvinylcarbazole (Mw = 63000, manufactured by Aldrich) and Ir (ppy) ₃ as a hole transporting and host material and Ir (ppy) ₃ were dissolved in dichloroethane at a weight ratio of 40: 1 to prepare a coating solution.

This coating solution was deoxygenated by a vacuum line. After the deoxygenation treatment, the entire vacuum line was replaced with nitrogen gas and stored.
The coating solution subjected to the deoxygenation treatment was applied onto the hole injection layer using a spin coater, and dried at room temperature to form a light emitting layer having a thickness of 50 nm.

On this light emitting layer, Balq ₂ was vapor-deposited by 10 nm at a rate of 0.5 nm / second, and further, Alq ₃ compound was vapor-deposited thereon by 30 nm at a rate of 0.5 nm / second.

Further, a patterned mask (a mask having a light emitting area of 2 mm × 2 mm) is placed on the light emitting layer, and lithium fluoride is deposited by 1 nm at a rate of 0.1 nm / second in a vapor deposition apparatus, and then aluminum is 1.2 nm. A back electrode was formed by vapor deposition at a rate of 400 nm / sec.
Aluminum lead wires were respectively connected from the transparent electrode (functioning as an anode) and the back electrode to form a laminated structure.

The obtained laminated structure was put in a glove box substituted with nitrogen gas, and sealed with a glass sealing container using an ultraviolet curable adhesive (manufactured by Nagase Ciba, XNR5493).
Thus, an organic electroluminescent element of Comparative Example 1 was produced.

Using the light emitting device, evaluation was performed by the following method.
Using a source measure unit type 2400 manufactured by Toyo Technica, a direct current voltage was applied to the organic EL element to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. Green light emission (519 nm) was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 6%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 60 hours.

[Comparative Example 2]
A light emitting device was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to the following complex R-1 (tridentate ligand + tridentate ligand). Evaluation was performed in the same manner as in Comparative Example 1. Green light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 6%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 80 hours.

[Example 1]
The light emitting device of Example 1 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to Complex K-9 of the present invention. It was evaluated with.
Green light emission (526 nm) was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 12%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 180 hours.

[Example 2]
The light emitting device of Example 2 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to Complex K-19 of the present invention. It was evaluated with.
Blue light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 7%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 170 hours.

[Example 3]
The light emitting device of Example 3 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to Complex K-43 of the present invention. It was evaluated with.
Blue light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 5%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 200 hours.

[Example 4]
The light emitting device of Example 4 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to Complex K-55 of the present invention. It was evaluated with.
Blue light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 6%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 210 hours.

[Example 5]
The light emitting device of Example 5 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to the complex K-331 of the present invention. It was evaluated with.
Green light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 10%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 160 hours.

[Example 6]
The light emitting device of Example 6 was produced in the same manner as in Comparative Example 1 except that Ir (ppy) ₃ in the light emitting layer in Comparative Example 1 was changed to Complex K-366 of the present invention. It was evaluated with.
Blue light emission was observed, and the external quantum efficiency (η ₁₀₀₀ ) at 1000 cd / m ² was 11%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the results of luminance was measured time (luminance half-life) until the 500 cd / m ^2, it was about 180 hours.

  The light emitting device of Example 1 to Example 6 (5-dentate or higher ligand) with respect to Comparative Example 1 (bidentate ligand) and Comparative Example 2 (tridentate ligand + tridentate ligand) Is excellent in terms of luminous efficiency and driving durability.

[Comparative Example 3]
The cleaned ITO substrate was placed in a vapor deposition apparatus in the same manner as in Comparative Example 1, NPD was vapor deposited at a thickness of 50 nm, CBP and Ir (ppy) ₃ were vapor deposited at a mass ratio of 10: 1 thereon, and further Balq ₂ was further deposited thereon. Was deposited to 10 nm, and Alq ₃ was further deposited to 30 nm thereon. A patterned mask (with a light emission area of 4 mm × 5 mm) was placed on the obtained organic thin film, lithium fluoride was deposited by 3 nm, and then aluminum was deposited by 60 nm to produce an organic EL device of Comparative Example 3. When a direct current constant voltage was applied to the obtained organic EL device, green light emission (λmax = 514 nm) was observed, and the external quantum efficiency was 6.4%.

[Example 7]
A light emitting device of Example 7 was produced in the same manner as in Comparative Example 3 except that Complex K-31 of the present invention was used instead of NPD in Comparative Example 3. When evaluated in the same manner as in Comparative Example 3, green light emission (λmax = 514 nm) was observed, and the external quantum efficiency was 8%. Further, the time until the luminance reached 500 cd / m ² (luminance half time) was three times that of the device of Comparative Example 3 after continuous light emission at an initial luminance of 1000 cd / m ² .

  Comparison between Comparative Example 3 and Example 7 shows that the element using the complex of the present invention for the hole transport layer is excellent in terms of light emission efficiency and driving durability.

[Example 8]
A light emitting device of Example 7 was produced in the same manner as Comparative Example 3 except that Complex K-127 of the present invention was used instead of CBP in Comparative Example 3. When evaluated in the same manner as in Comparative Example 3, green light emission (λmax = 511 nm) was observed, and the external quantum efficiency was 11%. Also by continuous emission at an initial luminance 1000 cd / m ^2, the time until the brightness becomes 500 cd / m ² (luminance half-life) was twice device of Comparative Example 3.

  A comparison between Comparative Example 3 and Example 8 shows that an element using the complex of the present invention as a host material is excellent in terms of light emission efficiency and driving durability.

Claims (24)

An organic electroluminescence device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic layer contains at least one metal complex having a pentadentate or higher ligand. Organic electroluminescent device. The metal ion in the metal complex is one selected from the group consisting of platinum ion, gold ion, iridium ion, rhenium ion, palladium ion, rhodium ion, ruthenium ion, tungsten ion, and copper ion. Item 2. The organic electroluminescent device according to Item 1. 2. The organic electroluminescence device according to claim 1, wherein the metal ion in the metal complex is one selected from the group of aluminum ion and gallium ion. 3. The organic electroluminescent device according to claim 1, wherein the metal complex is a metal complex that emits phosphorescence, and the metal complex is contained in a light emitting layer. The organic electroluminescent element according to claim 1, wherein the metal complex is a compound represented by the following general formula (1).

(In General Formula (1), M ¹ represents a metal ion. L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ and L ¹⁷ are each independently a coordinating group that coordinates to M ^1. Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ and Y ¹⁵ each independently represents a single bond or a linking group, n ¹¹ represents 0 or 1, and n ¹² represents an integer of 0 to 4.) The organic electroluminescent element according to any one of claims 1 to 4, wherein the metal complex is a compound represented by the following general formula (3).

(In the general formula (3), M ³ represents a metal ion. L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ and L ³⁷ are each independently a coordinating group which coordinates to M ^3. Y ³¹ , Y ³² , Y ³³ , Y ³⁴ and Y ³⁵ each independently represents a single bond or a linking group, n ³¹ represents 0 or 1, and n ³² represents an integer of 0 to 4.) The organic electroluminescent element according to any one of claims 1 to 4, wherein the metal complex is a compound represented by the following general formula (4).

(In the general formula (4), M ⁴ represents a metal ion. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ and L ⁴⁷ each independently represent a coordinating group which coordinates to M ^4. Y ⁴¹ , Y ⁴² and Y ⁴³ each independently represents a single bond or a linking group, and n ⁴¹ and n ⁴² each independently represents 0 or 1, but at least one of n ⁴¹ and n ⁴² is 1 N ⁴³ represents an integer of 0 to 4.) The organic electroluminescent element according to any one of claims 1 to 4, wherein the metal complex is a compound represented by the following general formula (5).

(In general formula (5), M ⁵ represents a metal ion. L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ and L ⁵⁷ each independently represent a coordinating group which coordinates to M ^5. Y ⁵¹ , Y ⁵² and Y ⁵³ each independently represents a single bond or a linking group, and n ⁵¹ and n ⁵² each independently represents 0 or 1, but at least one of n ⁵¹ and n ⁵² is 1 N ⁵³ represents an integer of 0 to 4.) The organic electroluminescent element according to any one of claims 1 to 4, wherein the metal complex is a compound represented by the following general formula (6).

(In the general formula (6), M ⁶ represents a metal ion. L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ each independently represent a coordinating group which coordinates to M ^6. Y ⁶¹ , Y ⁶² and Y ⁶³ each independently represents a single bond or a linking group.n ⁶¹ represents 0 or 1. n ⁶² represents an integer of 0 to 4.) The organic electroluminescent element according to claim 1, wherein the metal complex is a compound represented by the following general formula (7).

(In the general formula (7), M ⁷ represents a metal ion. L ⁷¹ , L ⁷² , L ⁷³ , L ⁷⁴ , L ⁷⁵ , L ⁷⁶ and L ⁷⁷ each independently represent a coordinating group which coordinates to M ^7. Y ⁷¹ , Y ⁷² and Y ⁷³ each independently represents a single bond or a linking group, and n ⁷¹ and n ⁷² each independently represents 0 or 1, but at least one of n ⁷¹ and n ⁷² is 1 N ⁷³ represents an integer of 0 to 4.) The organic electroluminescent element according to claim 1, wherein the metal complex is a compound represented by the following general formula (2).

(In the general formula (2), M ² represents a metal ion. L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , L ²⁶ and L ²⁷ are each independently a coordinating group which coordinates to M ^2. Y ²¹ , Y ²² , Y ²³ and Y ²⁴ each independently represents a single bond or a linking group, n ²¹ represents 0 or 1, and n ²² represents an integer of 0 to 4. The organic electroluminescent device according to claim 11, wherein n ²¹ is 1 and n ²² is an integer of 1 to 4. The organic electroluminescent element according to claim 11 or 12, wherein at least one of Y ²² and Y ²³ represents a linking group. The compound represented by the general formula (2) is one selected from the group of compounds represented by the following general formulas (2-1) to (2-13). Organic electroluminescent element of any one of these.

(Formula (2-1) to formula (2-13) in, .Y ^21, Y ²³ and Y ²⁴ M ² is representative of the metal ions, .L ²³ which each independently represent a single bond or a linking group, L ²⁴ , L ²⁵ and L ²⁶ each independently represent a coordinating group which coordinates to M ² , A represents CR ^A , N or P, R ^A represents a hydrogen atom or a substituent, and Z represents N or .X showing a P represents O, S, and NR ^N1, .Q R ^N1 is representative of the .n ^x is 0 or 1 representing a hydrogen atom or a substituent ^{O, S, Se, NR N2} , CR C1 R ^C2 is represented, R ^N2 represents a substituent, R ^C1 and R ^C2 each independently represents a substituent, and G represents O or S.) The organic electroluminescent element according to any one of claims 1 to 14, wherein the metal complex is contained in a hole injection layer and / or a hole transport layer. The organic electroluminescent element according to claim 1, wherein the metal complex is contained in an electron injection layer and / or an electron transport layer. The organic light emitting device according to claim 1, wherein the light emitting layer contains a host material, and the host material is a metal complex. The organic electroluminescent element according to claim 1, wherein the light emitting layer contains two or more kinds of host materials. The organic electroluminescent element according to claim 1, wherein the light emitting layer contains at least one kind of the metal complex and another light emitting compound. The organic electroluminescent element according to claim 1, wherein at least two kinds of the metal complexes are contained in the light emitting layer. 21. The organic electroluminescent element according to claim 1, wherein the lowest excited triplet energy level of the metal complex is 65 kcal / mol or more and 95 kcal / mol or less. The organic electroluminescent element according to any one of claims 1 to 21, wherein the metal complex is a host material, and the metal complex is contained in a light emitting layer. The organic electroluminescent element according to claim 22, wherein the light emitting material is a platinum complex of a tetradentate ligand. The organic electroluminescence device according to any one of claims 1 to 22, wherein the emission maximum wavelength of the emission spectrum of the device is shorter than 450 nm.