JP4460952B2 - Organic electroluminescent device and complex compound - Google Patents

Description

  The present invention relates to an organic electroluminescent element (light emitting element or EL element) that can emit light by converting electric energy into light. Moreover, it is related with the metal complex which can be used suitably for it.

  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.

  In recent years, application of organic EL elements to color displays and white light sources has been actively studied, but in order to develop high-performance color displays and white light sources, blue, green, and red light-emitting elements. It is necessary to improve the characteristics.

On the other hand, as a phosphorescent light emitting element emitting red light, an element using a platinum porphyrin complex having a cyclic tetradentate ligand as a light emitting material is known (for example, see Non-Patent Document 1 and Patent Document 1). Improvements have been sought due to low brightness.
In addition, platinum porphyrin complexes having a chain bipyridine-based or phenanthroline-based tetradentate ligand have been reported (see Non-Patent Document 2, Patent Document 2, and Patent Document 3), but light emission characteristics such as color purity. And durability were not compatible, and improvements were desired. In addition, there has been a demand for the development of green and blue light emitting materials with shorter wavelengths that are further excellent in light emission characteristics and durability.
US Pat. No. 6,303,231 B1 US Pat. No. 6,653,654 B1 International Publication No. 03 / 093283A1 Pamphlet Nature 395, 151 (1998) Chem. Eur. J. et al. , 9, No. 6,1264 (2003)

  An object of the present invention is to provide a light emitting device having good light emitting characteristics and durability. It is another object of the present invention to provide a metal complex that can be suitably used.

This 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, having at least one tridentate ligand in at least one layer between the pair of electrodes, and coordination An organic electroluminescence device comprising at least one metal complex in which a child is a chain ligand.
[2] The organic electroluminescence according to [1], wherein the metal ion in the metal complex is selected from the group of platinum ion, iridium ion, rhenium ion, palladium ion, rhodium ion, ruthenium ion, and copper ion element.
[3] The organic electroluminescent element as described in [1] or [2], wherein the metal complex does not have a carbon-metal bond.
[4] The organic electroluminescent element as described in any one of [1] to [3], wherein the metal complex is a metal complex that emits phosphorescence, and the metal complex is contained in the light emitting layer.
[5] The organic electroluminescent element as described in any one of [1] to [4], wherein the metal complex is a compound represented by the general formula (1).

(M ¹¹ represents a metal ion, and L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , and L ¹⁵ each represent a ligand that coordinates to M ^11. There is an additional atomic group between L ¹¹ and L ^14. L ¹⁵ does not combine with both L ¹¹ and L ¹⁴ to form a cyclic ligand, Y ¹¹ , Y ¹² and Y ¹³ are each a linking group, A bond between L ¹¹ and Y ¹² , Y ¹² and L ¹² , L ¹² and Y ¹¹ , Y ¹¹ and L ¹³ , L ¹³ and Y ¹³ , and Y ¹³ and L ¹⁴ represents a single bond or a double bond. Represents a single bond or a double bond, and n ¹¹ represents 0 to 4.)
[6] The organic electroluminescent element as described in any one of [1] to [5], wherein the metal complex is a compound represented by the general formula (2).

(M ²¹ represents a metal ion, Y ²¹ represents a linking group, a single bond, or a double bond. Y ²² and Y ²³ each represent a single bond or a linking group. Q ²¹ and Q ²² represent nitrogen-containing hetero groups, respectively. represents an atomic group forming a ring, the bond between the ring and Y ²¹ which are formed by binding and Q ²² between the ring and Y ²¹ formed by Q ²¹ represents a single bond or a double bond .X ²¹ , X ²² each represents an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, R ²¹ , R ²² , R ²³ , and R ²⁴ each represent a hydrogen atom or a substituent, and R ^21, R ²² , and R ²³ And R ²⁴ may combine with each other to form a ring, L ²⁵ represents a ligand coordinated to M ²¹ , and n ²¹ represents an integer of 0 to 4.)
[7] The metal complex is represented by the general formula (2), the ring formed by Q ²¹ and Q ²² is a pyridine ring, and Y ²¹ is a compound representing a linking group composed of one or more atoms. The organic electroluminescent element according to [6].
[8] The metal complex is represented by the general formula (2), the ring formed by Q ²¹ and Q ²² is a pyridine ring, Y ²¹ is a single bond or a double bond, X ²¹ and X ²² are sulfur atoms, Or it is a compound showing an unsubstituted nitrogen atom, The organic electroluminescent element as described in [6] characterized by the above-mentioned.
[9] The organic electroluminescent element as described in [6], wherein the metal complex is represented by the general formula (2), and the ring formed by Q ²¹ and Q ²² is a nitrogen-containing hetero 5-membered ring.
[10] The metal complex is represented by the general formula (2), and the ring formed by Q ²¹ and Q ²² is a nitrogen-containing 6-membered ring containing two or more nitrogen atoms. Organic electroluminescent device.
[11] The organic electroluminescent element as described in [1] or [2], wherein the metal complex is a compound represented by the general formula (9).

(M ^A1 represents a metal ion, Q ^A1 and Q ^A2 each represent an atomic group forming a nitrogen-containing heterocycle. RA1, R ^A2 , R ^A3 and R ^A4 each represents a hydrogen atom or a substituent, and R ^A1 And R ^A2 and R ^A3 and R ^A4 may be bonded to each other to form a ring, Y ^A2 and Y ^A3 each represent a linking group or a single bond, and Y ^A1 represents two bidentate ligands in parentheses. And L ^A5 represents a ligand coordinated to M ^A1 , and n ^A1 represents an integer of 0 to 4.)
[12] The organic electroluminescent element as described in [1] or [2], wherein the metal complex is a compound represented by the general formula (10).

(M ^B1 represents a metal ion, Y ^B1 represents a linking group. Y ^B2 and Y ^B3 each represent a linking group or a single bond. X ^B1 and X ^B2 represent an oxygen atom, a sulfur atom, a substituted or unsubstituted group, respectively. Represents a nitrogen atom, and n ^B1 and n ^B2 represent an integer of 0 to 1. R ^B1 , R ^B2 , R ^B3 , R ^B4 , R ^B5 , and R ^B6 each represents a hydrogen atom or a substituent, and R ^B1 and R ^{B B2} and R ^B3 and R ^B4 may be bonded to each other to form a ring, L ^B5 represents a ligand coordinated to M ^B1 , n ^B3 represents an integer of 0 to 4, provided that Y ^B1 It never is connected to the R ^B5 or R ^B6 is.)
[13] The organic electroluminescent element as described in any one of [1] to [4], wherein the metal complex is a compound represented by the general formula (8).

(M ⁸¹ represents a metal ion, and L ⁸¹ , L ⁸² , L ⁸³ , and L ⁸⁵ each represent a ligand that coordinates to M ^{81. An} atomic group further exists between L ⁸¹ and L ⁸³ to form a ring or It does not form a tetradentate or higher ligand, L ⁸⁵ does not connect to L ⁸¹ or L ⁸³ without a metal, Y ⁸¹ and Y ⁸² each represent a linking group, a single bond, or a double bond. It represents a bond .n ⁸¹ represents an integer of 0 to 3.)
[14] An aromatic carbocyclic or heterocyclic ring in which the metal complex is represented by the general formula (8) and L ⁸¹ , L ⁸² and L ⁸³ are coordinated to M ⁸¹ with a carbon atom, or coordinated to M ⁸¹ with a nitrogen atom It represents a nitrogen-containing heterocyclic ring, the organic electroluminescent device as described in [13], wherein at least one of L ^81, L ^82, L ⁸³ is a nitrogen-containing heterocycle.
[15]
The organic electroluminescent element according to [1] or [2], wherein the metal complex is represented by the general formula (X1).

(In the general formula ^(X1), M X1 .L is .Q ^X11 to Q ^X16 representing a metal ion represents a atomic group containing an atom coordinating to an atom or M ^X1 coordinating to M ^{X1 X11} ~L ^X14 Represents a single bond, a double bond or a linking group, that is, an atomic group consisting of Q ^X11 -L ^X11 -Q ^X12 -L ^X12 -Q ^X13 and Q ^X14 -L ^X13 -Q ^X15 -L ^X14 -Q ^X16 Each atomic group is a tridentate ligand. The bond between M ^X1 and Q ^{X11 to} Q ^X16 may be a coordinate bond or a covalent bond.)
[16]
The organic electroluminescent element as described in [15], wherein the metal complex represented by the general formula (X1) is represented by the general formula (X2).

(In the general formula (X2), M ^X2 is .Y ^X21 to Y ^X26 representing a metal ion represents a coordinating atom M ^X2, Q ^X21 ~Q ^X26 is an aromatic ring or aromatic with each Y ^X21 to Y ^X26 .L ^X21 ~L ^X24 representing an atom group forming a family heterocycle single bond, the bond between .M ^X2 and Y ^X21 to Y ^X26 representing a double bond or a linking group can be a covalent bond at each coordinate bond Good.)
[17]
The organic electroluminescent element as described in [15], wherein the metal complex represented by the general formula (X1) is represented by the general formula (X3).

(In the general formula (X3), M ^X3 represents a metal ion. Y ^X31 to Y ^X36 represent a carbon atom, a nitrogen atom or a phosphorus atom. L ^{X31 to} L ^X34 represent a single bond, a double bond or a linking group. (The bond between M ^X3 and Y ^X31 to Y ^X36 may be a coordinate bond or a covalent bond.)
[18] An organic electroluminescent device comprising at least one light emitting layer between a pair of electrodes, in addition to a hole transport layer and a light emitting layer, an exciton block layer, a hole injection layer, a hole block layer, and an electron transport It has at least 1 layer chosen from the group which consists of layers, The organic electroluminescent element as described in any one of [1]-[17] characterized by the above-mentioned.
[19] An organic electroluminescent device comprising at least one light emitting layer between a pair of electrodes, wherein the host material of the light emitting layer is an amine compound, a metal chelate oxinoid compound (compound having a metal-oxygen bond) (the metal is aluminum) , Zinc, or a transition metal), a polyarylene compound, a condensed aromatic carbocyclic compound, and a non-complex aromatic heterocyclic compound, wherein any one of [1] to [18] The organic electroluminescent element as described.
[20] An organic electroluminescent device comprising at least one electron transport layer between a pair of electrodes, wherein the electron transport material is a metal chelate oxinoid compound, a polyarylene compound, a condensed aromatic carbocyclic compound, and a non-complex aromatic The organic electroluminescence device according to any one of [1] to [19], which is selected from the group consisting of heterocyclic compounds.
[21] An organic electroluminescent device comprising at least one light emitting layer between a pair of electrodes, wherein the host material of the light emitting layer comprises at least two kinds of compounds. The organic electroluminescent element as described in any one.
[22] A compound represented by the general formula (11).

(R ^C1 and R ^C2 each represent a hydrogen atom or a substituent, and R ^C3 , R ^C4 , R ^C5 and R ^C6 each represent a substituent. N ^C3 and n ^C6 represent 0 to 3, n ^C4 and n ^C5 represent represents an integer of 0 to 4, when having a plurality of ^{R C3, R C4, R C5} , R C6 , respectively, the plurality of ^{R C3, R C4, R C5} , R C6 may be the same or different , May be linked to form a ring.)
[23] A compound represented by the general formula (12).

（Ｒ ^C1 、Ｒ ^C2 はそれぞれ水素原子、アルキル基、アリール基、アミノ基又はアシル基を表し、Ｒ ^C3 、Ｒ ^C4 、Ｒ ^C5 、Ｒ ^C6 は置換基を表す。ｎ ^C3 、ｎ ^C6 は０〜３、ｎ ^C4 、ｎ ^C5 は０〜４の整数を表し、Ｒ ^C3 、Ｒ ^C4 、Ｒ ^C5 、Ｒ ^C6 をそれぞれ複数個有する場合、複数個のＲ ^C3 、Ｒ ^C4 、Ｒ ^C5 、Ｒ ^C6 は同じであっても異なってもよく、連結して環を形成してもよい。）
（２）
前記Ｒ ^C3 、Ｒ ^C4 、Ｒ ^C5 、Ｒ ^C6 はそれぞれアルキル基、アルケニル基、アルキニル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルホニル基、スルフィニル基、ウレイド基、リン酸アミド基、ヒドロキシ基、メルカプト基、ハロゲン原子、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基、シリル基、又はシリルオキシ基である、〔１〕に記載の有機電界発光素子。
（３）
前記置換基が、アルキル基、アリール基、アミノ基又はアシル基である、（１）又は（２）に記載の有機電界発光素子。
（４）
前記Ｒ^C1、Ｒ^C2が、それぞれ、アルキル基である、（１）〜（３）のいずれかに記載の有機電界発光素子。
（５）
一対の電極間に少なくとも一層の発光層を含む有機電界発光素子であって、正孔輸送層と発光層に加え、励起子ブロック層、正孔注入層、正孔ブロック層および電子輸送層からなる群から選ばれる少なくとも一つの層を有することを特徴とする（１）〜（４）のいずれかに記載の有機電界発光素子。
（６）
一対の電極間に少なくとも一層の発光層を含む有機電界発光素子であって、発光層のホスト材料がアミン化合物、金属キレートオキシノイド化合物（金属はアルミニウム、亜鉛、または遷移金属）、ポリアリーレン化合物、縮合芳香族炭素環化合物および非錯体芳香族ヘテロ環化合物からなる群から選ばれることを特徴とする（１）〜（５）のいずれか一項に記載の有機電界発光素子。
（７）
一対の電極間に少なくとも一層の電子輸送層を含む有機電界発光素子であって、電子輸送材料が、金属キレートオキシノイド化合物、ポリアリーレン化合物、縮合芳香族炭素環化合物および非錯体芳香族ヘテロ環化合物からなる群から選ばれることを特徴とする（１）〜（４）のいずれか一項に記載の有機電界発光素子。
（８）
一対の電極間に少なくとも一層の発光層を含む有機電界発光素子であって、発光層のホスト材料が少なくとも２種の化合物からなることを特徴とする（１）〜（５）のいずれか一項に記載の有機電界発光素子。
（９）
（１）〜（４）のいずれかに記載の前記一般式（１１）で表される発光材料。
（１０）
（１）〜（４）のいずれかに記載の前記一般式（１１）で表される化合物を含有する発光層。
（１１）
（１）〜（８）のいずれかに記載の有機電界発光素子を用いた表示素子。
（１２）
（１）〜（８）のいずれかに記載の有機電界発光素子を用いたディスプレイ。
（１３）
（１）〜（８）のいずれかに記載の有機電界発光素子を用いた照明光源。
なお、本発明は上記（１）〜（１３）に関するものであるが、その他の事項についても参考のために記載した。 (R ^D3 and R ^D4 each represent a hydrogen atom or a substituent, and R ^D1 and R ^D2 each represent a substituent. N ^D1 and n ^D2 each represent an integer of 0 to 4, and R ^D1 and R ^D2 each represent a plurality of R ^D1 and R ^D2. In the case of having one, a plurality of R ^D1 and R ^D2 may be the same or different, and may be connected to form a ring, Y ^D1 is a vinyl group substituted at the 1- or 2-position, a phenylene ring, Represents a pyridine ring, a pyrazine ring, a pyrimidine ring or a methylene group having 1 to 8 carbon atoms.)
[24] A compound represented by the general formula (X1).
[25] A compound represented by the general formula (X2).
[26] A compound represented by the general formula (X3).
The present invention relates to the following (1) to (13).
(1)
An organic electroluminescence device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one compound of the general formula ( 11 ) is contained in at least one layer between the pair of electrodes. An organic electroluminescent element characterized by the above.

(R ^C1 and R ^C2 each represent a hydrogen atom, an alkyl group, an aryl group, an amino group or an acyl group, and R ^C3 , R ^C4 , R ^C5 and R ^C6 each represent a substituent. N ^C3 and n ^C6 represent 0 to 0. 3, n ^C4, n ^C5 represents an integer of ^{0~4, R C3, R C4,} R C5, if the R ^C6 each having a plurality, a plurality of ^{R C3, R C4, R C5} , R C6 are the same Or may be linked to form a ring.
(2)
R ^C3 , R ^C4 , R ^C5 and R ^C6 are each an alkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxy Carbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, Phosphoramido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group, silyl group, or silyloxy group Yes, [1] The organic electroluminescence device according.
( 3 )
The organic electroluminescence device according to (1) or (2) , wherein the substituent is an alkyl group, an aryl group, an amino group, or an acyl group.
( 4 )
The organic electroluminescent element according to any one of (1) to (3), wherein each of R ^C1 and R ^C2 is an alkyl group.
( 5 )
An organic electroluminescent device comprising at least one light emitting layer between a pair of electrodes, comprising an exciton block layer, a hole injection layer, a hole block layer and an electron transport layer in addition to a hole transport layer and a light emitting layer It has at least 1 layer chosen from a group, The organic electroluminescent element in any one of (1 )-(4) characterized by the above-mentioned.
( 6 )
An organic electroluminescent element including at least one light emitting layer between a pair of electrodes, wherein a host material of the light emitting layer is an amine compound, a metal chelate oxinoid compound (a metal is aluminum, zinc, or a transition metal), a polyarylene compound, The organic electroluminescent device according to any one of (1 ) to (5) , which is selected from the group consisting of a condensed aromatic carbocyclic compound and a non-complex aromatic heterocyclic compound.
( 7 )
An organic electroluminescent device comprising at least one electron transport layer between a pair of electrodes, wherein the electron transport material is a metal chelate oxinoid compound, a polyarylene compound, a condensed aromatic carbocyclic compound, and a non-complex aromatic heterocyclic compound The organic electroluminescent element according to any one of (1) to (4) , wherein the organic electroluminescent element is selected from the group consisting of:
( 8 )
An organic electroluminescent device comprising at least one layer of the light-emitting layer between a pair of electrodes, the host material in the light-emitting layer is characterized in that it consists of at least two compounds (1) any one of - (5) The organic electroluminescent element of description.
( 9 )
(1 ) -The luminescent material represented by the said General formula (11 ) in any one of (4) .
( 10)
(1 ) The light emitting layer containing the compound represented by the said General formula (11 ) in any one of (4) .
( 11 )
The display element using the organic electroluminescent element in any one of (1 )-(8 ).
( 12 )
A display using the organic electroluminescent element according to any one of (1 ) to (8) .
( 13 )
(1 ) The illumination light source using the organic electroluminescent element in any one of (8) .
The present invention relates to the above (1) to (13) , but other matters are also described for reference.

The chain ligand in the present specification is a ligand that is not a cyclic ligand (for example, porphyrin, phthalocyanine, etc.). Taking the general formula (8) as an example, it means a ligand in which L ⁸¹ and L ⁸³ are not linked via Y ⁸¹ , L ⁸² , Y ⁸² and M ⁸¹ . Even if L ⁸¹ , Y ⁸¹ , L ⁸² , Y ⁸² , and L ⁸³ contain a ring structure (eg, benzene, pyridine, quinoline, etc.), L ⁸¹ and L ⁸³ are Y ⁸¹ , L ⁸² , Y ⁸² , M ^81. If they are not linked without intervening, the ligand is called a chain ligand. An atomic group may exist between L ⁸¹ and Y ⁸¹ , between Y ⁸¹ and L ⁸² , between L ⁸² and Y ⁸² , and between Y ⁸² and L ⁸³ to form a ring.

  The light emitting device of the present invention has high external quantum efficiency and maximum luminance, excellent light emission characteristics, and excellent durability. The light emitting device of the present invention can be suitably used in the fields of display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. The compounds of the present invention can also be applied to medical uses, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, color filter dyes, color conversion filters, and the like. is there. The novel complex of the present invention is suitable for producing an excellent light emitting device as described above.

  The organic electroluminescence device of the present invention (hereinafter sometimes referred to as the device of the present invention) may be at least one organic layer including a light emitting layer between a pair of electrodes (a layer made of only an organic compound). And an organic layer containing an inorganic compound), which includes a metal complex that emits phosphorescence in an arbitrary layer sandwiched between a pair of electrodes, and the metal The complex has a tridentate or higher ligand, and the ligand is a chain ligand.

The metal complex having a tridentate or higher chain ligand of the present invention (hereinafter sometimes referred to as the metal complex of the present invention) is a metal complex having a tridentate or higher and a lower eight or lower chain ligand. Preferred is a metal complex having a tetradentate or more and 8 or less chain ligand, more preferred is a metal complex having a tetradentate or more and 6 or less chain ligand, and more preferred is a tetradentate chain coordination. A metal complex having a child is particularly preferred.
The chain ligand in the present invention represents a central metal {for example, M ¹¹ in the case of the general formula (1). } Preferably has at least one nitrogen-containing heterocycle coordinated with nitrogen (for example, a pyridine ring, a quinoline ring, a pyrrole ring, etc.).

  The metal complex of the present invention preferably has no carbon-metal bond. That is, in a metal complex, it means that there is no bond between a metal atom and a carbon atom. Specifically, having no carbon-metal bond is preferably the following bond. Metal-nitrogen bond, metal-oxygen bond, metal-sulfur bond, metal-phosphorus bond, metal-selenium bond are preferable, metal-nitrogen bond, metal-oxygen bond, metal-sulfur bond, metal-phosphorus bond are more preferable, More preferred are metal-nitrogen bonds, metal-oxygen bonds, and metal-sulfur bonds.

  The compound used in the present invention is not particularly limited as long as it emits phosphorescence (preferably emits phosphorescence at −30 ° C. or more, more preferably emits phosphorescence at −10 ° C. or more, more preferably 0 ° C. In the above, phosphorescence is emitted, particularly preferably phosphorescence is emitted at 10 ° C. or higher.) Although fluorescence may be emitted at the same time, the phosphorescence intensity at 20 ° C. is more than twice the fluorescence intensity. Compounds are preferred, compounds that are 10 times or more are more preferred, and compounds that are 100 times or more are more preferred.

  The phosphorescent material of the present invention is preferably a material having a phosphorescence quantum yield at 20 ° C. of 10% or more and a phosphorescence λmax (emission maximum value) of 400 nm or more and 700 nm or less, and a phosphorescence quantum yield at 20 ° C. Is more preferably 15% or more, and phosphorescence λmax is more preferably 400 nm or more and 575 nm or less, and a phosphorescence quantum yield at 20 ° C. is 20% or more and phosphorescence λmax is more preferably 400 nm or more and 560 nm or less.

  The metal complex of the present invention is contained in an arbitrary layer sandwiched between a pair of electrodes, but is preferably contained in a hole injection / transport layer and / or a light emitting layer, and more preferably contained in a light emitting layer. When the metal complex of the present invention is contained in the light emitting layer, the concentration of the phosphorescent compound in the light emitting layer is preferably 1% by mass to 30% by mass with respect to the mass of the light emitting layer, and 2% by mass. It is more preferably ˜20% by mass, and further preferably 3% by mass to 15% by mass.

  The preferable form of the metal complex having a tetradentate or higher ligand of the present invention is the general formula (1). Preferred forms of the general formula (1) are the general formula (2), the following general formula (5), the general formula (9), and the general formula (10).

  A preferred form of the general formula (2) is the following general formula (3).

Preferred forms of the general formula (9) are the following general formulas (6) and (7), and a preferred form of the following general formula (7) is the general formula (11).
A preferred form of the general formula (10) is the general formula (12).

The general formula (1) will be described. M ¹¹ represents a metal ion. Although it does not specifically limit as a metal ion, A bivalent or trivalent metal ion is preferable. As the divalent or trivalent metal ions, platinum ions, iridium ions, rhenium ions, palladium ions, rhodium ions, ruthenium ions, copper ions, europium ions, gadolinium ions, and terbium ions are preferable, and platinum ions, iridium ions, and europium ions. Ions are more preferable, platinum ions and iridium ions are more preferable, and platinum ions are particularly preferable.

L ¹¹ , L ¹² , L ¹³ and L ¹⁴ each represent a ligand coordinated to M ¹¹ . As an atom contained in L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ and coordinated to M ¹¹ , a nitrogen atom, an oxygen atom, a sulfur atom, and a carbon atom are preferable, and a nitrogen atom, an oxygen atom, and a carbon atom are included. More preferred.

The bond formed by M ¹¹ and L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ may be a covalent bond, an ionic bond, or a coordinate bond. The ligand composed of L ¹¹ , Y ¹² , L ¹² , Y ¹¹ , L ¹³ , Y ¹³ , and L ¹⁴ may be an anionic ligand (a ligand in which at least one anion binds to a metal). preferable. 1-3 are preferable, as for the number of anions in an anionic ligand, 1 and 2 are more preferable, and 2 is further more preferable.

L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ coordinated to M ¹¹ by a carbon atom are not particularly limited, but imino ligands, aromatic carbocyclic ligands (eg, benzene ligands, naphthalene ligands) , Anthracene ligand, phenanthracene ligand, etc.), heterocyclic ligand (eg thiophene ligand, pyridine ligand, pyrazine ligand, pyrimidine ligand, thiazole ligand, oxazole coordination) And pyrrole ligands, imidazole ligands, pyrazole ligands, and condensed rings containing them (for example, quinoline ligands, benzothiazole ligands, and the like, and tautomers thereof).

L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ coordinated to M ¹¹ by a nitrogen atom are not particularly limited, but nitrogen-containing heterocyclic ligands {eg, pyridine ligand, pyrazine ligand, pyrimidine coordination Ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxadiazole ligand, Thiadiazole ligands, condensed rings containing them (for example, quinoline ligands, benzoxazole ligands, benzimidazole ligands, etc.), and tautomers thereof (in the present invention, normal isomerism) The following examples are also defined as tautomers, for example, 5-membered heterocyclic ligand of compound (24), 5-membered heterocyclic ligand of compound (64), compound (145) 5-membered heterocycle coordination Are also defined as pyrrole tautomers, etc.}, amino ligands {alkylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms). Such as methylamino), arylamino ligands (such as phenylamino), acylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms). Particularly preferably having 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino ligand (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, especially Preferably having 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino ligands (preferably Or 7 to 20 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino and the like, and a sulfonylamino ligand (preferably carbon number). 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), imino ligands, etc.}. These ligands may be further substituted.

L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ coordinated to M ¹¹ by an oxygen atom are not particularly limited, but are alkoxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly Preferably it is C1-C10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy etc.), an aryloxy ligand (preferably C6-C30, more preferably C6-C6). 20, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), heterocyclic oxy ligands (preferably 1 to 30 carbon atoms, more preferably Is a C1-C20, particularly preferably C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. An acyloxy ligand (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), silyloxy ligand ( Preferably it has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, etc.), carbonyl ligands (for example ketones) Ligands, ester ligands, amide ligands, etc.), ether ligands (eg, dialkyl ether ligands, diaryl ether ligands, furyl ligands, etc.).

Is not particularly limited as ^{L 11, L 12, L 13} , L 14 to coordinating sulfur atom M ^11, alkylthio ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, in particular Preferably it is C1-C12, for example, methylthio, ethylthio etc. are mentioned), an arylthio ligand (preferably C6-C30, more preferably C6-C20, especially preferably C6-C6). 12 such as phenylthio), a heterocyclic thio 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, pyridylthio. , 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), thiocarbonyl ligands (for example, thioketone ligands) Etc. thioester ligand), a thioether ligands (e.g. dialkyl thioether ligands, diaryl thioether ligands, etc. thiofuryl ligand), and the like. These substituted ligands may be further substituted.

L ¹¹ and L ¹⁴ are aromatic carbocyclic ligands, alkyloxy ligands, aryloxy ligands, ether ligands, alkylthio ligands, arylthio ligands, alkylamino ligands, arylamino ligands. Ligands, acylamino ligands, nitrogen-containing heterocyclic ligands (eg pyridine ligands, pyrazine ligands, pyrimidine ligands, pyridazine ligands, triazine ligands, thiazole ligands, oxazole ligands) Ligands, pyrrole ligands, imidazole ligands, pyrazole ligands, triazole ligands, oxadiazole ligands, thiadiazole ligands, and condensed ligand bodies containing them (for example, quinoline ligands) Ligands, benzoxazole ligands, benzimidazole ligands, and the like, and tautomers thereof) are preferred, aromatic carbocyclic ligands, aryloxy ligands, Reelthio ligands, arylamino ligands, pyridine ligands, pyrazine ligands, imidazole ligands, and condensed ligand bodies containing them (for example, quinoline ligands, quinoxaline ligands, Benzimidazole ligands) and tautomers thereof are more preferable, aromatic carbocyclic ligands, aryloxy ligands, arylthio ligands, arylamino ligands are more preferable, and aromatic A carbocyclic ligand and an aryloxy ligand are particularly preferred.

L ¹² and L ¹³ are preferably ligands that form a coordinate bond with M ¹¹ . Examples of the ligand that forms a coordination bond with M ¹¹ include a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, a pyrrole ring, a triazole ring, and a condensed ring containing them (for example, Quinoline ring, benzoxazole ring, benzimidazole ring, indolenine ring, etc.) and tautomers thereof, and pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, and condensed ring containing them (for example, Quinoline ring, benzpyrrole, etc.) and tautomers thereof are more preferable, pyridine ring, pyrazine ring, pyrimidine ring, and condensed ring containing them (for example, quinoline ring, etc.) are more preferable, pyridine ring And a condensed ring containing a pyridine ring (such as a quinoline ring) is particularly preferable.

L ¹⁵ represents a ligand coordinated to M ¹¹ . L ¹⁵ is preferably a 1-4-dentate ligand, and more preferably a 1-4-dentate anionic ligand. Although it does not specifically limit as an anionic ligand of 1-4 tetradentate, The monoanionic property 2 containing a halogen ligand, a 1, 3- diketone ligand (for example, acetylacetone ligand etc.), and a pyridine ligand. Formed with a bidentate ligand (eg, picolinic acid ligand, 2- (2-hydroxyphenyl) -pyridine ligand, etc.), L ¹¹ , Y ¹² , L ¹² , Y ¹¹ , L ¹³ , Y ¹³ , L ¹⁴ The tetradentate ligand is preferably a 1,3-diketone ligand (such as an acetylacetone ligand), a monoanionic bidentate ligand containing a pyridine ligand (such as a picolinic acid ligand, 2- (2-hydroxyphenyl) -pyridine ligands, etc.), L ¹¹ , Y ¹² , L ¹² , Y ¹¹ , L ¹³ , Y ¹³ , L ¹⁴ and more preferably tetradentate ligands. , 3-diketone ligand (eg acetylacetone ligand), Monoanionic bidentate ligands containing lysine ligands (eg, picolinic acid ligands, 2- (2-hydroxyphenyl) -pyridine ligands, etc.) are more preferred, and 1,3-diketone ligands Particularly preferred are (eg acetylacetone ligands). The number of coordination sites and the number of ligands do not exceed the coordination number of the metal. L ¹⁵ does not combine with both L ¹¹ and L ¹⁴ to form a cyclic ligand.

Y ¹¹ , Y ¹² and Y ¹³ each represent a linking group, a single bond or a double bond. The linking group is not particularly limited, but for example, a carbonyl linking group, a thiocarbonyl linking group, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, an oxygen atom linking group, a nitrogen atom linking group, a silicon atom linking group, and Examples thereof include a linking group composed of these combinations. The bonds between L ¹¹ and Y ¹² , Y ¹² and L ¹² , L ¹² and Y ¹¹ , Y ¹¹ and L ¹³ , L ¹³ and Y ¹³ , and Y ¹³ and L ¹⁴ represent a single bond or a double bond.

Y ¹¹ , Y ¹² and Y ¹³ are each preferably a single bond, a double bond, a carbonyl linking group, an alkylene linking group or an alkenylene group, and Y ¹¹ is more preferably a single bond or an alkylene group, further preferably an alkylene group. Y ¹² and Y ¹³ are more preferably a single bond or an alkenylene group, and even more preferably a single bond.

Ring formed by Y ¹² , L ¹¹ , L ¹² , M ¹¹ , Ring formed by Y ¹¹ , L ¹² , L ¹³ , M ¹¹ , Ring formed by Y ¹³ , L ¹³ , L ¹⁴ , M ¹¹ Are preferably 4 to 10 ring members, more preferably 5 to 7 ring members, and still more preferably 5 or 6 ring members.

n ¹¹ represents the 0-4. When M ¹¹ is a metal having a coordination number of 4, n ¹¹ is 0. When M ¹¹ is a metal having a coordination number of 6, n ¹¹ is preferably 1, 2, and more preferably 1. When M ¹¹ is coordination number 6 and n ¹¹ is 1, L ¹⁵ represents a bidentate ligand, and when M ¹¹ is coordination number 6 and n ¹¹ is 2, L ¹⁵ represents a monodentate ligand. When M ¹¹ is a metal having a coordination number of 8, n ¹¹ is preferably 1 to 4, more preferably 1 or 2, and more preferably 1. When M ¹¹ is coordination number 8 and n ¹¹ is 1, L ¹⁵ represents a tetradentate ligand, and when n ¹¹ is 2, L ¹⁵ represents a bidentate ligand. When n ¹¹ is plural, the plural L ¹⁵ may be the same or different.

The general formula (2) will be described. M ²¹ has the same meaning as M ¹¹ , and the preferred range is also the same.

Q ²¹ and Q ²² each represent an atomic group forming a nitrogen-containing heterocycle (a ring containing nitrogen coordinated to M ²¹ ). The nitrogen-containing heterocycle formed by Q ²¹ and Q ²² is not particularly limited. For example, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, thiazole ring, oxazole ring, pyrrole ring, triazole ring, and Examples of the condensed ring include quinoline ring, benzoxazole ring, benzimidazole ring, and indolenine ring, and tautomers thereof.

The nitrogen-containing heterocycle formed by Q ²¹ and Q ²² is preferably a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrazole ring, imidazole ring, oxazole ring, pyrrole ring, benzazole ring, and A condensed ring containing them (for example, quinoline ring, benzoxazole ring, benzimidazole ring, etc.) and tautomers thereof, more preferably pyridine ring, pyrazine ring, pyrimidine ring, imidazole ring, pyrrole ring, And a condensed ring containing them (for example, quinoline ring and the like) and tautomers thereof, more preferably a pyridine ring and a condensed ring thereof (for example, quinoline ring), A pyridine ring is preferred.

X ²¹ and X ²² are each preferably an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom, more preferably an oxygen atom, a sulfur atom, or a substituted nitrogen atom, still more preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom. preferable.

Y ²¹ has the same meaning as Y ¹¹ , and the preferred range is also the same.

Y ²² and Y ²³ each represent a single bond or a linking group, and preferably a single bond. The linking group is not particularly limited, and includes, for example, a carbonyl linking group, a thiocarbonyl linking group, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, an oxygen atom linking group, a nitrogen atom linking group, and a combination thereof. Examples thereof include a linking group.

  The linking group is preferably a carbonyl linking group, an alkylene linking group, or an alkenylene linking group, more preferably a carbonyl linking group or an alkenylene linking group, and even more preferably a carbonyl linking group.

R ²¹ , R ²² , R ²³ and R ²⁴ each represent a hydrogen atom or a substituent. Although it does not specifically limit as a substituent, For example, it is an alkyl group (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, 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, it has 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, Particularly preferably, it has 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl. Preferably it has 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, and an amino group (preferably). Has 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms. Examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino. ),

An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, 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 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like. ), A heterocyclic oxy 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 pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like.) An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably carbon number) -12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms). For example, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyl And oxycarbonyl).

An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), an acylamino group (preferably having a carbon number) 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably carbon atoms). 7 to 20, particularly preferably 7 to 12 carbon atoms, for example phenyloxycarbonylamino ), Sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc. A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, Famoyl etc.),

A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like), alkylthio. A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolyl E, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, mesyl, tosyl, etc.), sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzene And ureido groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples thereof include ureido, methylureido, and phenylureido. ),

A phosphoric acid 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); Hydroxy group, mercapto group, halogen atom (eg 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 ring A 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, furyl and thienyl. , Piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl , An 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, such as trimethylsilyl and triphenylsilyl). ), A silyloxy 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 trimethylsilyloxy and triphenylsilyloxy). Is mentioned. These substituents may be further substituted.

R ²¹ , R ²² , R ²³ , and R ²⁴ are each an alkyl group, an aryl group, R ²¹ and R ^22, or R ²³ and R ²⁴ are combined to form a ring structure (for example, a benzo condensed ring, a pyridine condensed ring, etc.). And a group in which R ²¹ and R ²² or R ²³ and R ²⁴ are combined to form a ring structure (for example, a benzo-fused ring, a pyridine-fused ring, etc.) is more preferred.

L ²⁵ has the same meaning as L ¹⁵ described above, and the preferred range is also the same.

n ²¹ has the same meaning as n ¹¹ , and the preferred range is also the same.

In formula (2), when the ring formed by Q ²¹ and Q ²² is a pyridine ring, Y ²¹ is a metal complex representing a linking group, or the ring formed by Q ²¹ and Q ²² is a pyridine ring, ²¹ is a single bond or a double bond, and X ²¹ and X ²² are a sulfur atom, a substituted or unsubstituted nitrogen atom, or a ring formed by Q ²¹ and Q ²² is a nitrogen-containing hetero 5-membered A metal complex representing a ring or a nitrogen-containing 6-membered ring containing two or more nitrogen atoms is preferable.

The general formula (3) will be described. M ³¹ has the same meaning as M ¹¹ , and the preferred range is also the same.

Z ³¹ , Z ³² , Z ³³ , Z ³⁴ , Z ³⁵ and Z ³⁶ each represent a substituted or unsubstituted carbon atom or a nitrogen atom, and a substituted or unsubstituted carbon atom is more preferred. Examples of the substituent on the carbon include the groups described above for R ²¹ , Z ³¹ and Z ³² , Z ³² and Z ³³ , Z ³³ and Z ³⁴ , Z ³⁴ and Z ³⁵ , Z ³⁵ and Z ^36. May be bonded via a linking group to form a condensed ring (for example, benzo condensed ring, pyridine condensed ring, etc.). Z ³¹ and T ³¹ , Z ³⁶ and T ³⁸ are bonded via a linking group, and A ring (for example, a benzo condensed ring, a pyridine condensed ring, etc.) may be formed.

  As the substituent on the carbon, an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group forming a condensed ring (for example, a benzo condensed ring, a pyridine condensed ring, etc.) or a halogen atom is preferable. A group that forms a group or a condensed ring (for example, a benzo-condensed ring, a pyridine-condensed ring, etc.) is more preferable, a group that forms an aryl group or a condensed ring (for example, a benzo-condensed ring, a pyridine-condensed ring, etc.) is more preferable A group that forms a benzo-fused ring, a pyridine-fused ring, etc.) is particularly preferred.

T ³¹ , T ³² , T ³³ , T ³⁴ , T ³⁵ , T ³⁶ , T ³⁷ , and T ³⁸ represent a substituted or unsubstituted carbon atom and a nitrogen atom, respectively, and a substituted or unsubstituted carbon atom is more preferable. Examples of the substituent on the carbon include the groups described for R ²¹ , and T ³¹ and T ³² , T ³² and T ³³ , T ³³ and T ³⁴ , T ³⁵ and T ³⁶ , T ³⁶ and T ^37. T ³⁷ and T ³⁸ may be bonded via a linking group to form a condensed ring (for example, a benzo-condensed ring).

  The substituent on the carbon is preferably an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group that forms a condensed ring (for example, a benzo condensed ring, a pyridine condensed ring, etc.), or a halogen atom. A group that forms (for example, a benzo-fused ring, a pyridine-fused ring, etc.) and a halogen atom are more preferred, an aryl group and a halogen atom are more preferred, and an aryl group is particularly preferred.

X ³¹ and X ³² have the same meanings as X ²¹ and X ²² , respectively, and preferred ranges are also the same.

The general formula (5) will be described. M ⁵¹ has the same meaning as M ¹¹ , and the preferred range is also the same.

Q ⁵¹ and Q ⁵² are synonymous with Q ²¹ and Q ²² , respectively, and preferred ranges are also the same.

Q ⁵³ and Q ⁵⁴ each represent a group forming a nitrogen-containing heterocycle (a ring containing a nitrogen coordinated to M ⁵¹ ). The nitrogen-containing heterocycle formed by Q ⁵³ and Q ⁵⁴ is not particularly limited, but a tautomer of a pyrrole derivative, a tautomer of an imidazole derivative (for example, a hetero 5-membered ring ligand of compound (29), etc.) ), A tautomer of a thiazole derivative (such as a hetero 5-membered ring ligand of the compound (30)), a tautomer of a oxazole derivative (such as a hetero 5-membered ring ligand of the compound (31)), and the like. Preferably, tautomers of pyrrole derivatives, tautomers of imidazole derivatives, tautomers of thiazole derivatives are more preferable, tautomers of pyrrole derivatives, tautomers of imidazole derivatives are more preferable, pyrrole derivatives The tautomers are particularly preferred.

Y ⁵¹ has the same meaning as the Y ^11, and the preferred range is also the same.

L ⁵⁵ has the same meaning as the L ^15, and the preferred range is also the same.

n ⁵¹ has the same meaning as n ¹¹ , and the preferred range is also the same.

W ⁵¹ and W ⁵² each represent a substituted or unsubstituted carbon atom or a nitrogen atom, preferably an unsubstituted carbon atom or a nitrogen atom, and more preferably an unsubstituted carbon atom.

The general formula (9) will be described. M ^A1 , Q ^A1 , Q ^A2 , Y ^A1 , Y ^A2 , Y ^A3 , R ^A1 , R ^A2 , R ^A3 , R ^A4 , L ^A5 , n ^A1 are M ²¹ , Q ²¹ , Q in the general formula (2). ²² , Y ²¹ , Y ²² , Y ²³ , R ²¹ , R ²² , R ²³ , R ²⁴ , L ²⁵ , n ²¹ , and the preferred range is also the same.

The general formula (6) will be described. M ⁶¹ has the same meaning as M ¹¹ , and the preferred range is also the same.

Q ⁶¹ and Q ⁶² each represent a group forming a ring. The ring formed by Q ⁶¹ and Q ⁶² is not particularly limited, and examples thereof include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a thiophene ring, an isothiazole ring, a furan ring, an isoxazole ring, and a condensed ring thereof. A ring.

The ring formed by Q ⁶¹ and Q ⁶² is preferably a benzene ring, a pyridine ring, a thiophene ring, a thiazole ring, or a condensed ring thereof, and more preferably a benzene ring, a pyridine ring, or a condensed ring thereof. More preferred are benzene rings and condensed rings thereof.

Y ⁶¹ has the same meaning as Y ¹¹ , and the preferred range is also the same.

Y ⁶² and Y ⁶³ each represent a linking group or a single bond. The linking group is not particularly limited, and includes, for example, a carbonyl linking group, a thiocarbonyl linking group, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, an oxygen atom linking group, a nitrogen atom linking group, and combinations thereof. Examples thereof include a linking group.

Y ⁶² and Y ⁶³ are each preferably a single bond, a carbonyl linking group, an alkylene linking group or an alkenylene group, more preferably a single bond or an alkenylene group, and even more preferably a single bond.

L ⁶⁵ has the same meaning as L ¹⁵ described above, and the preferred range is also the same.

n ⁶¹ has the same meaning as n ¹¹ , and the preferred range is also the same.

Z ⁶¹ , Z ⁶² , Z ⁶³ , Z ⁶⁴ , Z ⁶⁵ , Z ⁶⁶ , Z ⁶⁷ and Z ⁶⁸ each represent a substituted or unsubstituted carbon atom or a nitrogen atom, and a substituted or unsubstituted carbon atom is preferred. Examples of the substituent on the carbon include the groups described above for R ²¹ , Z ⁶¹ and Z ⁶² , Z ⁶² and Z ⁶³ , Z ⁶³ and Z ⁶⁴ , Z ⁶⁵ and Z ⁶⁶ , Z ⁶⁶ and Z ^67. Z ⁶⁷ and Z ⁶⁸ may be bonded via a linking group to form a condensed ring (for example, a benzo condensed ring, a pyridine condensed ring, etc.). The ring formed by Q ⁶¹ and Q ⁶² may be bonded to Z ⁶¹ and Z ⁶⁸ via a linking group to form a ring.

  As the substituent on the carbon, an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group forming a condensed ring (for example, a benzo condensed ring, a pyridine condensed ring, etc.) or a halogen atom is preferable. A group that forms a group or a condensed ring (for example, a benzo-condensed ring, a pyridine-condensed ring, etc.) is more preferable, a group that forms an aryl group or a condensed ring (for example, a benzo-condensed ring, a pyridine-condensed ring, etc.) is more preferable A group that forms a benzo-fused ring, a pyridine-fused ring, etc.) is particularly preferred.

The general formula (7) will be described. M ⁷¹ has the same meaning as the M ^11, and the preferred range is also the same.

Y ⁷¹ , Y ⁷² , and Y ⁷³ have the same meanings as Y ⁶² , and preferred ranges are also the same.

L ⁷⁵ has the same meaning as L ¹⁵ described above, and the preferred range is also the same.

n ⁷¹ has the same meaning as the n ^11, and the preferred range is also the same.

Z ⁷¹ , Z ⁷² , Z ⁷³ , Z ⁷⁴ , Z ⁷⁵ and Z ⁷⁶ each represent a substituted or unsubstituted carbon atom or a nitrogen atom, and a substituted or unsubstituted carbon atom is preferred. Examples of the substituent on carbon include the groups described for R ²¹ . Z ⁷¹ and Z ⁷² , Z ⁷³ and Z ⁷⁴ may be bonded via a linking group to form a ring (for example, a benzene ring or a pyridine ring).
R ^{71 to} R ⁷⁴ are synonymous with the substituents of R ^{21 to} R ^{24 in} the general formula (2), and the preferred range is also the same.

The general formula (11) will be described.
R ^C1 and R ^C2 each represent a hydrogen atom or a substituent, and the substituent represents the alkyl group or aryl group described as the substituent for R ²¹ to R ^{24 in} the general formula (2). The substituents represented by R ^C3 , R ^C4 , R ^C5 and R ^C6 are also synonymous with the substituents of R ²¹ to R ^{24 in} the general formula (2). n ^C3, n ^C6 is 0 to 3, n ^C4, n ^C5 represents an integer of ^{0~4, R C3, R C4,} R C5, if the R ^C6 each having a plurality, a plurality of R ^C3, R ^C4 , R ^C5 and R ^C6 may be the same or different and may be linked to form a ring. R ^C3 , R ^C4 , R ^C5 and R ^C6 are preferably an alkyl group, an aryl group, a heteroaryl group and a halogen atom.

Next, the general formula (10) will be described.
M ^B1 , Y ^B2 , Y ^B3 , R ^B1 , R ^B2 , R ^B3 , R ^B4 , L ^B5 , n ^B3 , X ^B1 , X ^B2 are M ²¹ , Y ²² , Y ²³ , R in the general formula (2). ²¹ , R ²² , R ²³ , R ²⁴ , L ²⁵ , n ²¹ , X ²¹ , X ²² are synonymous and preferred ranges are also the same. Y ^B1 represents a linking group, wherein it is general formula similar to the Y ²¹ (2), preferably a vinyl group substituted at the 1- and 2-positions, a phenylene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring or 2 carbon atoms 8 represents a methylene group. R ^B5 and R ^B6 represent a hydrogen atom or a substituent, and the substituent represents the alkyl group, aryl group, or heterocyclic group described as the substituent of R ²¹ to R ^{24 in} the general formula (2). However, Y ^B1 is not linked to R ^B5 or R ^B6 . n ^B1 and n ^B2 each represents an integer of 0 to 1.

Next, the general formula (12) will be described.
The substituents represented by R ^D1 , R ^D2 , R ^D3 and R ^D4 are the same as the substituents represented by R ^B5 and R ^{B6 in} the general formula (10), and the preferred ranges are also the same. n ^D1 and n ^D2 represent an integer of 0 to 4. Y ^D1 represents a vinyl group, a phenylene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or a methylene group having 1 to 8 carbon atoms substituted at the 1 and 2 positions.

  A preferred form of the metal complex having a tridentate ligand of the present invention is the general formula (8).

The general formula (8) will be described. M ⁸¹ has the same meaning as M ¹¹ , and the preferred range is also the same.

L ⁸¹ , L ⁸² , and L ⁸³ are synonymous with L ¹¹ , L ¹² , and L ¹⁴ , respectively, and preferred ranges are also the same.

Y ⁸¹ and Y ⁸² have the same meanings as Y ¹¹ and Y ¹² , respectively, and preferred ranges are also the same.

L ⁸⁵ represents a ligand coordinated to M ⁸¹ . L ⁸⁵ is preferably a 1 to 3 ligand, more preferably a 1 to 3 anionic ligand. No particular limitation is imposed on the anionic ligand 1-3 seat, tridentate ligand formed by halogen ^{ligand, L 81, Y 81, L} 82, Y 82, L 83 is preferably, L ⁸¹ , Y ⁸¹ , L ⁸² , Y ⁸² and L ⁸³ are more preferable. Never L ⁸⁵ is connected to the L ^81, L ⁸³ without passing through the metal. The number of coordination sites and the number of ligands do not exceed the coordination number of the metal.

n ⁸¹ represents 0 to 5. When M ⁸¹ is a metal having a coordination number of 4, n ⁸¹ is 1 and L ⁸⁵ represents a monodentate ligand. When M ⁸¹ is a metal having a coordination number of 6, n ⁸¹ is preferably 1 to 3, more preferably 1, 3 and even more preferably 1. When M ⁸¹ is coordination number 6 and n ⁸¹ is 1, L ⁸⁵ represents a tridentate ligand, and when M ⁸¹ is coordination number 6 and n ⁸¹ is 2, L ⁸⁵ is one monodentate ligand and bidentate. ligand one of the stands, when L ⁸⁵ of n ⁸¹ in M ⁸¹ is coordination number of 6 3 represents a monodentate ligand. When M ⁸¹ is a metal having a coordination number of 8, n ⁸¹ is preferably 1 to 5, more preferably 1 or 2, and more preferably 1. When M ⁸¹ is coordination number 8 and n ⁸¹ is 1, L ⁸⁵ represents a pentadentate ligand, and when n ⁸¹ is 2, L ⁸⁵ represents one tridentate ligand and one bidentate ligand. , N ⁸¹ is 3, L ⁸⁵ represents one tridentate ligand and two monodentate ligands, or two bidentate ligands and one monodentate ligand, and when n ⁸¹ is 4, L ⁸⁵ Represents one bidentate ligand and three monodentate ligands, and when n ⁸¹ is 5, L ⁸⁵ represents five monodentate ligands. When ⁿ⁸¹ is plural, the plural ^L85s may be the same or different.

A preferable form of the general formula (8) is an aromatic carbocyclic or heterocyclic ring in which L ⁸¹ , L ⁸² and L ^{83 in the} general formula (8) are carbon atoms and coordinate to M ⁸¹ , or a nitrogen atom and M ⁸¹ Represents a nitrogen-containing heterocycle that is coordinated to each other, and at least one of L ⁸¹ , L ⁸² , and L ⁸³ is a nitrogen-containing heterocycle. Aromatic carbocycles, heterocycles and nitrogen-containing heterocycles coordinated by nitrogen atoms coordinate with these carbon atoms are ligands and nitrogen atoms coordinated with carbon atoms to M ¹¹ described in the general formula (1). Examples of coordination are given, and the preferred range is also the same. Y ⁸¹ and Y ⁸² preferably represent a single bond or a methylene group.
Other preferable forms of the general formula (8) are the following general formula (13) and the following general formula (14).

The general formula (13) will be described. M ⁹¹ has the same meaning as M ⁸¹ , and the preferred range is also the same.

Q ⁹¹ and Q ⁹² represent a group that forms a nitrogen-containing heterocycle (a ring containing nitrogen coordinated to M ⁹¹ ). Although Q ⁹¹ is not particularly restricted but includes nitrogen-containing heterocyclic ring formed by, Q ^92, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, an imidazole Examples thereof include a ring, a triazole ring, and a condensed ring containing them (for example, a quinoline ring, a benzoxazole ring, a benzimidazole ring, an indolenine ring, and the like) and tautomers thereof.

Q ^91, nitrogen-containing heterocyclic ring formed by Q ⁹² is preferably a pyridine ring, a pyrazole ring, a thiazole ring, an imidazole ring, a pyrrole ring, a condensed ring body thereof (for example, quinoline ring, benzothiazole ring, Benzimidazole ring, indolenine ring, etc.) and tautomers thereof, more preferably pyridine ring, pyrrole ring, and condensed ring containing them (for example, quinoline ring, etc.), and these A tautomer, more preferably a pyridine ring, and a condensed ring containing them (for example, a quinoline ring), particularly preferably a pyridine ring.

Q ⁹³ represents a group forming a (ring containing coordinating nitrogen M ⁹¹⁾ nitrogen-containing heterocyclic ring. No particular limitation is imposed on the nitrogen-containing heterocyclic ring formed by Q ^93, a pyrrole ring, an imidazole ring, tautomers of the triazole ring, and a condensed ring body thereof (for example, benzopyrrole, etc.) are preferred, a pyrrole ring And tautomers of condensed rings containing a pyrrole ring (for example, benzpyrrole) are more preferable.

W ⁹¹ and W ⁹² are synonymous with W ⁵¹ and W ⁵² , respectively, and preferred ranges are also the same.

L ⁹⁵ has the same meaning as the L ^85, and the preferred range is also the same.

n ⁹¹ has the same meaning as the n ^81, and the preferred range is also the same.

The general formula (14) will be described. M ¹⁰¹ has the same meaning as M ⁸¹ , and the preferred range is also the same.

Q ¹⁰² has the same meaning as the Q ^21, and the preferred range is also the same.

Q ¹⁰¹ has the same meaning as Q ⁹¹ , and the preferred range is also the same.

Q ¹⁰³ represents a group that forms an aromatic ring. The aromatic ring formed by Q ¹⁰³ is not particularly limited, but a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, and a condensed ring containing them (for example, a naphthalene ring) are preferable. The condensed ring containing (for example, naphthalene ring etc.) is more preferable, and a benzene ring is particularly preferable.

Y ¹⁰¹ and Y ¹⁰² each have the same meaning as Y ²² described above, and the preferred range is also the same.

L ¹⁰⁵ has the same meaning as the L ^85, and their preferable ranges are also the same.

n ¹⁰¹ has the same meaning as the n ^81, and the preferred range is also the same.

X ¹⁰¹ has the same meaning as X ²¹ , and the preferred range is also the same.

  The compound of the present invention may be a low molecular compound, and is an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 1000000, still more preferably 3000 to 100000. Yes.) In the case of a polymer compound, the structure represented by the general formula (1) may be included in the polymer main chain, or may be included in the polymer side chain. In the case of a polymer compound, it may be a homopolymer compound or a copolymer. The compound of the present invention is preferably a low molecular compound.

  Another embodiment of the metal complex having a tridentate ligand of the present invention is a metal complex represented by the general formula (X1). Of the metal complexes represented by the general formula (X1), a metal complex represented by the general formula (X2) is preferable, and a metal complex represented by the general formula (X3) is more preferable.

The general formula (X1) will be described.
M ^X1 represents a metal ion. The metal ion is not particularly limited, but a monovalent to trivalent metal ion is preferable, a divalent or trivalent metal ion is more preferable, and a trivalent metal ion is more preferable. Specifically, platinum ion, iridium ion, rhenium ion, palladium ion, rhodium ion, ruthenium ion, copper ion, europium ion, gadolinium ion, terbium ion are preferable, platinum ion, iridium ion, europium ion are more preferable, platinum ion Further, iridium ions are more preferable, and iridium ions are particularly preferable.
Q ^X11 to Q ^X16 represents an atomic group containing an atom coordinating to an atom or M ^X1 coordinating to M ^X1. When Q ^{X11 to} Q ^X16 represent an atom coordinated to M ^X1 , specific atoms include a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, and preferably nitrogen. An atom, an oxygen atom, a sulfur atom, and a phosphorus atom, more preferably a nitrogen atom and an oxygen atom.
When Q ^{X11 to} Q ^X16 represent an atomic group including an atom coordinated to M ^X1 , examples of those coordinated by a carbon atom include an imino group, an aromatic hydrocarbon ring group (benzene, naphthalene, etc.), hetero Examples thereof include ring groups (thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole and the like) and condensed rings containing them, and tautomers thereof.

  Examples of those coordinated by a nitrogen atom include nitrogen-containing heterocyclic groups (pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, etc.), amino groups (preferably alkylamino groups (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, such as methylamino), arylamino groups (eg phenylamino), etc.), acylamino groups (preferably Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2 carbon atoms). To 30, more preferably 2 to 20 carbon atoms, particularly preferably A prime number of 2 to 12, for example, methoxycarbonylamino, etc.), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, and particularly preferably having 7 to 12 carbon atoms). Yes, for example, phenyloxycarbonylamino, etc.), a sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino) , Benzenesulfonylamino, etc.), and imino groups. These groups may be further substituted.

  As the one coordinated by an oxygen atom, an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2- Ethylhexyloxy, etc.), aryloxy groups (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 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 pyridyloxy and pyrazyloxy). , Pyrimidyloxy, quinolyloxy, etc.), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, such as acetoxy and benzoyloxy), silyloxy groups (preferably 3-40 carbon atoms, more preferably 3-30 carbon atoms, especially Preferably it has 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, etc.), carbonyl group (for example, ketone group, ester group, amide group, etc.), ether group (for example, dialkyl ether group, diaryl ether). Group, furyl group, etc.).

  The thing coordinated with a sulfur atom is an alkylthio 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 methylthio, ethylthio and the like. ), 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, particularly preferably 1-12, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like. ), Thiocarbonyl groups (for example, thioketone groups, thioester groups, etc.), thioether groups (for example, dialkylthioethers). Group, diaryl thioether, etc. thiofuryl group).

  Examples of those coordinated by a phosphorus atom include a dialkylphosphino group, a diarylphosphino group, a trialkylphosphine, a triarylphosphine, and a phosphinin group. These groups may be further substituted.

As an atomic group represented by Q ^{X11 to} Q ^X16 , an aromatic hydrocarbon ring group coordinated with carbon, an aromatic heterocyclic group coordinated with carbon, and a nitrogen-containing aromatic heterocyclic group coordinated with nitrogen An alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a dialkylphosphino group, more preferably an aromatic hydrocarbon ring group coordinated with carbon, an aromatic heterocyclic group coordinated with carbon, and nitrogen. It is a nitrogen-containing aromatic heterocyclic group to be coordinated.

L ^{X11 to} L ^X14 represent a single bond, a double bond or a linking group. Although it does not specifically limit as a coupling group, The coupling group which consists of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom is preferable, Although a specific example is shown below, it is not limited to these.

These linking groups may be further substituted, and as the substituent, those exemplified as the substituents represented by R ^{21 to} R ²⁴ in the general formula (2) can be applied, and the preferred ranges are also the same. L ^{X11 to} L ^X14 are preferably a single bond, a dimethylmethylene group, or a dimethylsilylene group.

The metal complex represented by the general formula (X1) is more preferably a metal complex represented by the general formula (X2). Next, the general formula (X2) will be described.
M ^X2 has the same meaning as M ^X1 in formula (X1), and the preferred range is also the same. Y ^X21 to Y ^X26 represent an atom coordinating to M ^X2. The bond between Y ^{X21 to} Y ^X26 and M ^X2 may be a coordinate bond or a covalent bond. Y ^{X21 to} Y ^X26 include a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a silicon atom, preferably a carbon atom and a nitrogen atom. Q ^X21 to Q ^X26 represents an atomic group forming an aromatic hydrocarbon ring or aromatic heterocyclic ring each include Y ^X21 to Y ^X26. The aromatic hydrocarbon ring and aromatic heterocycle formed in this case are benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring. , Thiazole ring, oxadiazole ring, thiadiazole ring, thiophene ring, furan ring, preferably benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, imidazole ring, triazole ring, more preferably benzene. A ring, a pyridine ring, a pyrazine ring, a pyrazole ring and a triazole ring, and particularly preferably a benzene ring and a pyridine ring. These may further have a condensed ring or a substituent.

L ^{X21 to} L ^X24 are synonymous with L ^{X11 to} L ^X14 in the general formula (X1), and preferred ranges thereof are also the same.

The metal complex represented by the general formula (X1) is more preferably a metal complex represented by the general formula (X3). Next, the general formula (X3) will be described.
M ^X3 has the same meaning as M ^X1 in formula (X1), and the preferred range is also the same. Y ^{X31 to} Y ^X36 each represent an atom coordinated to M ^X3 . The bond between Y ^{X31 to} Y ^X36 and M ^X3 may be a coordinate bond or a covalent bond. Y ^{X31 to} Y ^X36 include a carbon atom, a nitrogen atom and a phosphorus atom, and preferably a carbon atom and a nitrogen atom. L ^{X31 to} L ^X34 are synonymous with L ^{X11 to} L ^X14 in the general formula (X1), and preferred ranges thereof are also the same.

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

(Method for synthesizing metal complex of the present invention)
The metal complexes of the present invention (compounds represented by the general formulas (1) to (14) and the general formulas (X1) to (X3)) can be synthesized by various methods.
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 sulfoxide solvent, water, etc., or in the absence of a solvent, in the presence of a base (inorganic and organic bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below, or by heating (in addition to normal heating, a method of heating with a microwave is also effective).

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

  The reaction temperature for synthesizing the metal 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.

  In the metal complex of the present invention, the general formulas (1) to (14) and the general formulas (X1) to (X3) are selected by appropriately selecting a ligand that forms the partial structure of the target complex. The compound represented by can be synthesized. For example, when synthesizing the compound represented by the general formula (3), a 6,6′-bis (2-hydroxyphenyl) -2,2′-bipyridyl ligand or a derivative thereof (for example, 2,9-bis (2-hydroxyphenyl) -1,10-phenanthroline ligand, 2,9-bis (2-hydroxyphenyl) -4,7-diphenyl-1,10-phenanthroline ligand, 6,6′-bis ( 2-hydroxy-5-tert-butylphenyl) -2,2′-bipyridyl ligand and the like are preferably 0.1 equivalents to 10 equivalents, more preferably 0.3 equivalents to 6 equivalents with respect to the metal compound. It can be synthesized by adding an equivalent amount, more preferably 0.5 equivalent to 4 equivalents. In the method for synthesizing the compound represented by the general formula (3), each of the reaction solvent, the reaction time, and the reaction temperature is the same as the matters described in the method for synthesizing the metal complex of the present invention.

  Derivatives of 6,6'-bis (2-hydroxyphenyl) -2,2'-bipyridyl ligand can be synthesized using various known methods. For example, a 2,2′-bipyridyl derivative (such as 1,10-phenanthroline) and an anisole derivative (such as 4-fluoroanisole) are reacted by the method described in Journal of Organic Chemistry, 741, 11, (1946). Can be synthesized. In addition, halogenated 2,2′-bipyridyl derivatives (eg, 2,9-dibromo-1,10-phenanthroline) and 2-methoxyphenylboronic acid derivatives (eg, 2-methoxy-5-fluorophenylboron) After the Suzuki coupling reaction using an acid or the like as a starting material, the methyl group is deprotected (the method described in Journal of Organic Chemistry, 741, 11, (1946), the method of heating in pyridine hydrochloride, etc. Can be synthesized. In addition, 2,2′-bipyridylboronic acid derivatives (eg, 6,6′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolyl) -2,2′-bipyridyl) and halogens After the Suzuki coupling reaction using a modified anisole derivative (such as 2-bromoanisole) as a starting material, the methyl group is deprotected (the method described in Journal of Organic Chemistry, 741, 11, (1946), Alternatively, it can also be synthesized by using a method such as heating in pyridine hydrochloride.

The light emitting element containing the metal complex of the present invention will be described. The light emitting device of the present invention is not particularly limited as long as it is a device using the metal complex of the present invention, such as a system, a driving method, and a usage form. An organic EL (electroluminescence) element can be mentioned as a typical light emitting element.
The light emitting device of the present invention is an organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, and in addition to a hole transport layer and a light emitting layer, an exciton block layer, a hole injection layer, It is preferable to have at least one layer selected from a hole blocking layer or an electron transporting layer.

  In the light emitting device 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 layer having an ionization potential of 5.9 eV or more is used. Is more preferable.

  The method for forming the organic layer of the light emitting device containing the metal complex 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 method, squeeze coating method, transfer roll coating method, kiss coating method, cast coating method, extrusion coating method, wire bar coating method, screen coating method, etc.), inkjet method, printing method, transfer method, etc. are used Resistance heating vapor deposition, Ingu method, a transfer method is preferable.

  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 include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal 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 conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint 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 (such as a sol-gel method), a dispersion of indium tin oxide A film is formed by a method such as coating.
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.

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.

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 compound can be used as long as it can form a layer having a function of transferring injected charges and a function of emitting light by providing a recombination field of holes and electrons. Oxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, Thiadiazolopyridine, cyclopentadi , 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, iridium trisphenylpyridine complexes, and platinum Examples include transition metal complexes represented by porphyrin complexes and derivatives thereof.
The host material of the light emitting layer is preferably an amine compound (for example, a triarylamine compound), a metal chelate oxinoid compound (a compound having a metal-oxygen bond) (a metal is aluminum, zinc, a transition metal, or a ligand is 8). -Hydroxyquinoline derivatives, 2- (2-pyridino) phenol derivatives, etc.), polyarylene compounds (such as hexaphenylbenzene derivatives), condensed aromatic carbocyclic compounds or non-complex aromatic nitrogen-containing heterocyclic compounds (such as carbazole derivatives) In addition, the host material of the light emitting layer may be a mixture of at least two kinds of compounds.
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 may be formed of a plurality of compounds.

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 include carbazole, triazole, oxazole, oxadiazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic group Tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic Examples include silane, carbon films, compounds of the present invention, and derivatives thereof. The film thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are 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.
The material for the hole injection layer is preferably copper phthalocyanine or a starburst amine compound.
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 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. The material for the electron transport layer is preferably a metal chelate oxinoid compound, a polyarylene compound, a condensed aromatic carbocyclic compound or a non-complex aromatic heterocyclic compound. Specific examples include fragrances such as triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene, and perylene. Various metal complexes represented by metal complexes of cyclic tetracarboxylic anhydride, phthalocyanine, 8-quinolinol, metal phthalocyanine, benzoxazole and benzothiazole as ligands, organic silanes, and derivatives thereof Can be 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.

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 and TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ , and CaF ₂ , SiN _x , SiO _x N _y Such as nitride, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene And a copolymer obtained by copolymerizing a monomer mixture containing at least one comonomer, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0 .1% or less of moisture-proof substances 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.

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
In this example, examples using compounds (1), (15), (65) and (88) shall be read as reference examples.
Synthesis of compound (1) Add 10 ml of benzonitrile to 0.16 g of 6,6′-bis (2-hydroxyphenyl) -2,2′-bipyridyl and 0.16 g of PtCl _2, and heat to reflux for 3 hours in a nitrogen atmosphere. It was. The reaction solution was cooled to room temperature, methanol was added for precipitation, and suction filtration was performed. The obtained solid was purified by silica gel column chromatography (developing solvent chloroform) to obtain 0.06 g of Compound (1). The structure of the compound (1) was confirmed by mass spectrum measurement. When a chloroform solution containing the compound (1) was irradiated with UV light in a nitrogen atmosphere, reddish orange light emission (λ _max = 624 nm) was obtained.

  The 6,6'-bis (2-hydroxyphenyl) -2,2'-bipyridyl used above as a starting material can be synthesized by the method described in Journal of Organic Chemistry, 741, 11, (1946). It can also be synthesized by the following scheme.

Synthesis of 6,6′-bis (2-methoxyphenyl) -2,2′-bipyridyl 1.15 g of 6,6′-dibromo-2,2′-bipyridine, 1.45 g of 2-methoxyphenylboronic acid, PPh _{3 To} 0.167 g, potassium carbonate 2.2 g, and Pd (OAc) ₂ 36 mg were added 10 ml of dimethoxyethane and 10 ml of water, and the mixture was heated to reflux for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, 20 ml of chloroform and 20 ml of water were added for liquid separation, and the organic layer was concentrated. Purification by silica gel column chromatography (developing solvent chloroform) gave 0.9 g of 6,6′-bis (2-methoxyphenyl) -2,2′-bipyridyl.
Synthesis of 6,6′-bis (2-hydroxyphenyl) -2,2′-bipyridyl 0.3 g of 6,6′-bis (2-methoxyphenyl) -2,2′-bipyridyl ligand, pyridine hydrochloride 10 g of the salt was heated at 160 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the mixture was cooled to room temperature, 20 ml of chloroform and 20 ml of water were added for liquid separation, and the organic layer was concentrated. Purification by silica gel column chromatography (developing solvent chloroform) gave 6,6′-bis (2-hydroxyphenyl) -2,2′-bipyridyl (0.2 g).

  A synthesis scheme of the compound (79) synthesized in the same manner and the compound (88) is shown.

The λmax of emission in dichloroethane of the compound (79) was 512 nm, and the λmax of emission in dichloroethane of the compound (88) was 620 nm.
Further, when the compound represented by the general formula (11) or the compound represented by the general formula (12) is substituted with an alkyl group, an aryl group, a heteroaryl group or a halogen atom, the compound can be synthesized by the above synthesis method. .
Synthesis of exemplary compound 58

Synthesis of Intermediate (2) 5 g (0.636 mol) of lithium hydride was suspended in a mixed solvent of 125 mL of toluene and 50 mL of N, N, N, N-tetramethylethylenediamine under a nitrogen atmosphere. To this, 4.33 g (0.106 mol) of dry acetonitrile was added and stirred at room temperature for 40 minutes. To the resulting suspension, 25 g (0.106 mol) of 2,6-dibromopyridine was added and heated, and the mixture was heated to reflux for 5 hours. The resulting yellow suspension was cooled to room temperature and slowly added dropwise into ice-cooled dilute hydrochloric acid. The organic layer was separated and extracted with chloroform, washed 3 times with water and once with saturated brine, and then dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain an orange-yellow (2) crude product. It was. After purification by silica gel column chromatography (chloroform), recrystallization from ethanol gave 6.1 g (yield 33%) of pure (2) as a yellow powder.

Synthesis of Intermediate (3) 4 g (11.33 mmol) of (2) was added to a mixed solution of 100 mL of concentrated hydrochloric acid and 100 mL of ethanol, and heated to reflux for 3 hours. After cooling to room temperature, neutralization was performed with an aqueous solution of sodium hydroxide while cooling with ice. The mixture was extracted with chloroform, washed 3 times with water and once with saturated brine, and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a pale yellow (3) crude product. After purification by silica gel column chromatography (chloroform), recrystallization from dichloromethane-hexane gave 2.5 g (yield 67%) of pure (3) as colorless needle crystals.

Synthesis of Intermediate (4) Under a nitrogen atmosphere, 700 mg (2.13 mmol) of (3) and 674 mg (4.26 mmol) of 2,6-difluorophenylboronic acid were dissolved in 10 mL of 1,2-dimethoxyethane. . To this, 112 mg (0.43 mmol) of triphenylphosphine was added, and 15 mL (11.52 mmol) of an aqueous solution of 1.6 g of potassium carbonate was further added. Next, 24 mg (0.11 mmol) of palladium acetate was added and heated to reflux for 4 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate and washed twice with water and once with saturated brine. The extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product of brown oil (4). Recrystallization from chloroform / hexane gave pure (4) as a pale yellow powder in 500 mg (yield 60%).

Synthesis of Exemplified Compound 58 In a nitrogen atmosphere, 150 mg (0.38 mmol) of (4) and 101 mg (0.38 mmol) of platinum chloride were added to 15 mL of benzonitrile and heated at 180 ° C. for 2 hours. Upon cooling to room temperature, orange-red needle crystals were precipitated. The needle crystals were separated by filtration, purified by silica gel column chromatography (chloroform), and recrystallized from chloroform to obtain 110 mg (yield 49%) of pure exemplified compound 58 as orange-red needle crystals.

Comparative Example 1
The cleaned ITO substrate is put into a vapor deposition apparatus, and TPD (N, N-diphenyl-N, N-di (m-tolyl) -benzidine) is vapor-deposited to 50 nm. On top of this, PtOEP (octaethylporphyrin platinum complex) and compound A was co-evaporated at a ratio of 1 to 17 (mass ratio) by 36 nm, and Compound A was evaporated thereon by 36 nm. A patterned mask (a mask with a light emission area of 4 mm × 5 mm) was placed on the organic thin film, and 3 nm of lithium fluoride was deposited in a deposition apparatus, and 400 nm of aluminum was deposited thereon. Using a source measure unit 2400 type (trade name) manufactured by Toyo Technica, a DC constant voltage was applied to the EL element to emit light, and the luminance was measured using a luminance meter BM-8 (trade name) manufactured by Topcon Corporation. As a result, the external quantum efficiency of 1.1% at 200 cd / m ^2, emission of maximum luminance 390cd / m ² was obtained.

Example 1
The cleaned ITO substrate is put in a vapor deposition apparatus, and TPD (N, N-diphenyl-N, N-di (m-tolyl) -benzidine) is vapor-deposited by 50 nm, on which the compound (1) and the compound A of the present invention are deposited. Was co-evaporated at a ratio of 1 to 17 (mass ratio) at 36 nm, and Compound B was evaporated thereon at 36 nm. A patterned mask (a mask with a light emission area of 4 mm × 5 mm) was placed on the organic thin film, and 3 nm of lithium fluoride was deposited in a deposition apparatus, and 400 nm of aluminum was deposited thereon. Using a source measure unit 2400 type (trade name) manufactured by Toyo Technica, a DC constant voltage was applied to the EL element to emit light, and the luminance was measured using a luminance meter BM-8 (trade name) manufactured by Topcon Corporation. As a result, the external quantum efficiency of 2.8% at 200 cd / m ^2, emission of maximum luminance 1090cd / m ² was obtained.

Example 2
The cleaned ITO substrate is put in a vapor deposition apparatus, and TPD (N, N-diphenyl-N, N-di (m-tolyl) -benzidine) is vapor-deposited by 50 nm, on which the compound (1) and the compound A of the present invention are deposited. Was co-evaporated at a ratio of 1 to 2 (mass ratio) by 36 nm, and Compound B was evaporated thereon by 36 nm. A patterned mask (a mask with a light emission area of 4 mm × 5 mm) was placed on the organic thin film, and 3 nm of lithium fluoride was deposited in a deposition apparatus, and 400 nm of aluminum was deposited thereon. Using a source measure unit 2400 type (trade name) manufactured by Toyo Technica, a DC constant voltage was applied to the EL element to emit light, and the luminance was measured using a luminance meter BM-8 (trade name) manufactured by Topcon Corporation. As a result, the external quantum efficiency of 4.4% at 200 cd / m ^2, emission of maximum luminance 3820cd / m ² was obtained.

Comparative Example 2
An EL device was fabricated by the method described in Example 8 of US Pat. No. 6,653,654 B1 (US6.653654B1) (device No-101).

Comparative Example 3
The cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD was vapor deposited to a thickness of 50 nm to form a hole transport layer. On top of this, Bepp ₂ as a host and compound (65) as a light emitting material were co-evaporated to a film thickness of 40 nm at 0.4 nm / second and 0.02 nm / second, respectively, to form a light emitting layer. On top of that, a patterned mask (a mask with a light emitting area of 2 mm × 2 mm) is placed on the organic thin film, and after 1.5 nm of lithium fluoride is deposited in a deposition apparatus, 200 nm of aluminum is deposited, and then a desiccant is applied. The insert element was sealed to prepare an EL element (element No-102). The light emitting material was changed to compound (1) by the same operation as described above, and an EL device was produced (device No-103).

Example 3
A light emitting layer was formed in the same manner as in Comparative Example 3 except that the thickness of the host was 36 nm. On top of this, 36 nm of Compound B was deposited as an electron transport layer. A patterned mask (a mask with a light emission area of 2 mm x 2 mm) is placed on the organic thin film, 5 nm of lithium fluoride is deposited in the deposition apparatus, 500 nm of aluminum is then deposited, and then a desiccant is added to seal the device. Then, an EL element was produced (element No-104). An EL device was produced by changing the host material to Compound A in the same manner as above (device No-105).

Example 4
The cleaned ITO substrate was put into a vapor deposition apparatus, copper phthalocyanine was vapor-deposited to 10 nm, and α-NPD was vapor-deposited to 20 nm thereon to form a hole transport layer. On top of this, compound A as a host and compound (1) as a light emitting material were co-evaporated to a thickness of 30 nm at 0.4 nm / second and 0.02 nm / second, respectively, to form a light emitting layer. On top of that, 10 nm of BAlq was vapor-deposited as a hole blocking layer, and 40 nm of Alq was vapor-deposited as an electron transport layer. A patterned mask (a mask with a light emission area of 2 mm x 2 mm) is placed on the organic thin film, 5 nm of lithium fluoride is deposited in the deposition apparatus, 500 nm of aluminum is then deposited, and then a desiccant is added to seal the device. Then, an EL element was produced (element No-201). The light emitting material and the host material were changed as shown in Table 2 by the same operation as described above, and EL elements were produced (element Nos. 202 to 206).

Next, each element was evaluated as follows.
Using a source measure unit 2400 (trade name) manufactured by Toyo Technica on an organic thin film, a constant DC current was applied to the EL element, the comparative example and the element of the present invention were caused to emit light, and the luminance was measured by Topcon's luminance meter BM- 8 (trade name), the emission wavelength was measured using a spectrum analyzer PMA-11 (trade name) manufactured by Hamamatsu Photonics, and the luminous efficiency was determined. Next, durability was evaluated. First, the device was driven at 1 mA / 4 mm ² and the initial luminance was measured. Next, the luminance after the element was driven at a low current of 1 mA / 4 mm ² for ²⁰⁰ h was measured, and the luminance maintenance ratio was determined by comparing with the initial luminance. The results are shown in Tables 1 and 2.

  As compared with the comparative example, it can be seen that the element of the present invention in which the electron transport layer is introduced has an improved luminance maintenance ratio and excellent element durability. Further, by changing the host material to a non-complex aromatic heterocyclic compound such as Compound A, device durability is further improved.

  In addition, device durability is further improved by using copper phthalocyanine (CuPc) as the hole injection layer and BAlq as the hole blocking layer, and the compound of the present invention can emit red or green light with good color purity. It turns out that it is. In addition, even shorter wave emission is possible.

Claims (13)

An organic electroluminescence device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein at least one compound of the general formula ( 11 ) is contained in at least one layer between the pair of electrodes. An organic electroluminescent element characterized by the above.

(R ^C1 and R ^C2 each represent a hydrogen atom, an alkyl group, an aryl group, an amino group or an acyl group, and R ^C3 , R ^C4 , R ^C5 and R ^C6 each represent a substituent. N ^C3 and n ^C6 represent 0 to 0. 3, n ^C4, n ^C5 represents an integer of ^{0~4, R C3, R C4,} R C5, if the R ^C6 each having a plurality, a plurality of ^{R C3, R C4, R C5} , R C6 are the same Or may be linked to form a ring. R ^C3 , R ^C4 , R ^C5 and R ^C6 are each an alkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxy Carbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, Phosphoramido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group, silyl group, or silyloxy group there, claim The organic electroluminescence device according to. Wherein the substituent is selected from an alkyl group, an aryl group, an amino group or an acyl group, an organic electroluminescent device according to claim 1 or 2. The organic electroluminescent element according to claim ¹ , wherein R ^C1 and R ^C2 are each an alkyl group. An organic electroluminescent device comprising at least one light emitting layer between a pair of electrodes, comprising an exciton block layer, a hole injection layer, a hole block layer and an electron transport layer in addition to a hole transport layer and a light emitting layer the organic electroluminescence device according to any one of claims 1-4, characterized in that it comprises at least one layer selected from the group. An organic electroluminescent element including at least one light emitting layer between a pair of electrodes, wherein a host material of the light emitting layer is an amine compound, a metal chelate oxinoid compound (a metal is aluminum, zinc, or a transition metal), a polyarylene compound, The organic electroluminescent device according to any one of claims 1 to 5 , wherein the organic electroluminescent device is selected from the group consisting of a condensed aromatic carbocyclic compound and a non-complex aromatic heterocyclic compound. An organic electroluminescent device comprising at least one electron transport layer between a pair of electrodes, wherein the electron transport material is a metal chelate oxinoid compound, a polyarylene compound, a condensed aromatic carbocyclic compound, and a non-complex aromatic heterocyclic compound the organic electroluminescent element according to any one of claims 1-4, characterized in that it is selected from the group consisting of. An organic electroluminescent device comprising at least one layer of the light-emitting layer between a pair of electrodes, according to any one of claims 1-5 in which the host material of the luminescent layer is characterized in that it consists of at least two compounds Organic electroluminescent element. The luminescent material represented by the said General formula (11 ) in any one of Claims 1-4 . The light emitting layer containing the compound represented by the said General formula (11 ) in any one of Claims 1-4 . The display element using the organic electroluminescent element in any one of Claims 1-8 . The display using the organic electroluminescent element in any one of Claims 1-8 . The illumination light source using the organic electroluminescent element in any one of Claims 1-8 .