JP4484833B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to a metal complex compound and an organic electroluminescent device containing the same.

So far, tetradentate platinum complexes such as phenylpyridine platinum complexes and phenoxypyridine platinum complexes (for example, Patent Document 1) and tetradentate platinum complexes such as octaethylporphyrin platinum complexes (for example, Patent Documents 2 and 3). An organic electroluminescent device (hereinafter, also referred to as “organic EL device”) containing a material such as the above has been disclosed, but further improvements have been demanded in terms of light emission characteristics such as shortening of the emission wavelength and durability. .
International Patent Publication No. 04/108857 Pamphlet US Pat. No. 6,303,238 B1 US Pat. No. 6,653,654 B1

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

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

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ each independently represents an atom selected from carbon, nitrogen, oxygen, sulfur and silicon. Bonds between atoms in a 5-membered ring formed from Z ₁ , Z ₂ , Z ₃ , Z ₄ and N atoms, and Z ₅ , Z ₆ , Z ₇ , Z ₈ and N atoms are single bonds or double bonds. To express. When Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ can be further substituted, they may have a substituent. A ₁ represents a divalent linking group. B ₁ and B ₂ each independently represents a single bond or a divalent linking group. X ₁ and X ₂ each represents a partial structure having an atom bonded to a platinum atom. However, X ₁ and X ₂ are not bonded to form a ring.
(2) The organic electroluminescence device as described in (1) above, wherein the general formula (I) is represented by the following general formula (II) or (III).
Formula (II)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , and B ₂ are the same as those in the general formula (I). Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ , Z ₁₇ , Z ₁₈ , Z ₁₉ , and Z ₂₀ are each independently an atom selected from carbon, nitrogen, oxygen, sulfur, and silicon. In the case where it can be further substituted, it may have a substituent. Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, or a single bond.
Formula (III)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , and B ₂ are the same as those in the general formula (I). Z ₃₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ , Z ₃₅ , Z ₃₆ , Z ₃₇ , and Z ₃₈ each independently represent an atom selected from carbon, nitrogen, oxygen, sulfur, and silicon, and can be further substituted In some cases, it may have a substituent. Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, or a single bond.
(3) The organic electroluminescent element as described in (2) above, wherein the general formula (II) is represented by the following general formula (IIA).
Formula (IIA)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , B ₂ , Y ₁ and Y ₂ are those of the general formula (II). It is synonymous. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom or a substituent.
(4) The organic electroluminescent element as described in (3) above, wherein the general formula (IIA) is represented by the following general formula (IIB).
Formula (IIB)

In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , Y ₁ , Y ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined in general formula (IIA).
(5) The organic electroluminescent element as described in (4) above, wherein the general formula (IIB) is represented by the following general formula (IIB1).
Formula (IIB1)

In the formula, A ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as those in formula (IIB). R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent.
(6) The organic electroluminescent element as described in (4) above, wherein the general formula (IIB) is represented by the following general formula (IIB2).
Formula (IIB2)

In the formula, A ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as those in formula (IIB). R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a substituent.
(7) The organic electroluminescent element as described in (2) above, wherein the general formula (III) is represented by the following general formula (IIIA).
Formula (IIIA)

式中、Ａ ₁ は、−Ｃ（Ｒ ₂₅ ）（Ｒ ₂₆ ）−、−Ｃ（Ｒ ₂₇ ）（Ｒ ₂₈ ）Ｃ（Ｒ ₂₉ ）（Ｒ ₃₀ ）−、−Ｓｉ（Ｒ ₃₁ ）（Ｒ ₃₂ ）−、−Ｎ（Ｒ ₃₅ ）−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ ₂ −、−ＣＯ−（Ｒ ₂₅ 、Ｒ ₂₆ 、Ｒ ₂₇ 、Ｒ ₂₈ 、Ｒ ₂₉ 、Ｒ ₃₀ 、Ｒ ₃₁ 、及びＲ ₃₂ はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アリール基、ハロゲン原子、アルキルチオ基、アリールチオ基、アルキルオキシ基、又はアリールオキシ基を表し、Ｒ ₃₅ は水素原子、アルキル基、シクロアルキル基、又はアリール基を表す。）から選択される基を表す。Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、Ｒ ₅ 、Ｒ ₆ 、Ｒ ₇ 、及びＲ ₈ は各々独立に水素原子、アルキル基、アリール基、ハロゲン原子又はシアノ基を表し、Ｒ ₁₁ 、Ｒ ₁₂ 、Ｒ ₁₃ 及びＲ ₁₄ は、各々独立に水素原子、アルキル基又はアリール基を表す。
（１１）Ｒ _２ 及びＲ _６ がともに水素原子であることを特徴とする上記（１０）に記載の有機電界発光素子。
（１２）Ａ _１ が−Ｃ（Ｒ ₂₅ ）（Ｒ ₂₆ ）−又は−Ｃ（Ｒ ₂₇ ）（Ｒ ₂₈ ）Ｃ（Ｒ ₂₉ ）（Ｒ ₃₀ ）−（Ｒ ₂₅ 、Ｒ ₂₆ 、Ｒ ₂₇ 、Ｒ ₂₈ 、Ｒ ₂₉ 及びＲ ₃₀ はそれぞれ独立に水素原子、アルキル基、又はアリール基を表す。）であることを特徴とする上記（１０）又は（１１）に記載の有機電界発光素子。
（１３）前記Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、Ｒ ₅ 、Ｒ ₆ 、Ｒ ₇ 、及びＲ ₈ が、各々独立に水素原子、又はアルキル基、又はハロゲン原子を表し、Ｒ ₁₁ 、Ｒ ₁₂ 、Ｒ ₁₃ 及びＲ ₁₄ が、各々独立に水素原子、又はアルキル基を表すことを特徴とする上記（１０）〜（１２）のいずれか一項に記載の有機電界発光素子。
（１４）下記一般式（ＩＩＢ１）で表される化合物。
一般式（ＩＩＢ１）

式中、Ａ ₁ は、−Ｃ（Ｒ ₂₅ ）（Ｒ ₂₆ ）−、−Ｃ（Ｒ ₂₇ ）（Ｒ ₂₈ ）Ｃ（Ｒ ₂₉ ）（Ｒ ₃₀ ）−、−Ｓｉ（Ｒ ₃₁ ）（Ｒ ₃₂ ）−、−Ｎ（Ｒ ₃₅ ）−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ ₂ −、−ＣＯ−（Ｒ ₂₅ 、Ｒ ₂₆ 、Ｒ ₂₇ 、Ｒ ₂₈ 、Ｒ ₂₉ 、Ｒ ₃₀ 、Ｒ ₃₁ 、及びＲ ₃₂ はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アリール基、ハロゲン原子、アルキルチオ基、アリールチオ基、アルキルオキシ基、又はアリールオキシ基を表し、Ｒ ₃₅ は水素原子、アルキル基、シクロアルキル基、又はアリール基を表す。）から選択される基を表す。Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、Ｒ ₅ 、Ｒ ₆ 、Ｒ ₇ 、及びＲ ₈ は各々独立に水素原子、アルキル基、アリール基、ハロゲン原子又はシアノ基を表し、Ｒ ₁₁ 、Ｒ ₁₂ 、Ｒ ₁₃ 及びＲ ₁₄ は、各々独立に水素原子、アルキル基又はアリール基を表す。
（１５）前記Ａ ₁ が、−Ｃ（Ｒ ₂₅ ）（Ｒ ₂₆ ）−又は−Ｃ（Ｒ ₂₇ ）（Ｒ ₂₈ ）Ｃ（Ｒ ₂₉ ）（Ｒ ₃₀ ）−（Ｒ ₂₅ 、Ｒ ₂₆ 、Ｒ ₂₇ 、Ｒ ₂₈ 、Ｒ ₂₉ 及びＲ ₃₀ はそれぞれ独立に水素原子、アルキル基又はアリール基を表す。）であることを特徴とする上記（１４）に記載の化合物。
（１６）前記Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、Ｒ ₅ 、Ｒ ₆ 、Ｒ ₇ 、及びＲ ₈ が、各々独立に水素原子、又はアルキル基、又はハロゲン原子を表し、Ｒ ₁₁ 、Ｒ ₁₂ 、Ｒ ₁₃ 及びＲ ₁₄ が、各々独立に水素原子、又はアルキル基を表すことを特徴とする上記（１４）又は（１５）に記載の化合物。
（１７）上記（１４）〜（１６）のいずれか一項に記載の化合物を含む発光材料。
（１８）上記（１４）〜（１６）のいずれか一項に記載の化合物を含む発光層。
（１９）上記（１０）〜（１３）のいずれか一項に記載の有機電界発光素子を用いた表示素子。
（２０）上記（１０）〜（１３）のいずれか一項に記載の有機電界発光素子を用いたディスプレイ。
（２１）上記（１０）〜（１３）のいずれか一項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（１０）〜（２１）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記載した。 In the formula, Z ₁ , Z ₂ , Z ₃ , Z ₅ , Z ₆ , Z ₇ , A ₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ , Z ₃₆ , Z ₃₇ , Z ₃₈ , Y ₁ and Y ₂ are general formulas. It is synonymous with those of (III) .
( 8 ) The organic electroluminescent element as described in any one of (3) to (6) above, wherein both R ₂ and R ₆ are hydrogen atoms .
( 9 ) In the general formulas (I) to (IIIA), A ₁ is —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-, -Si (R ₃₁ ) (R ₃₂ )-, -N (R ₃₅ )-, -O-, -S-, -SO-, -SO _2- , -CO- (R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₅ each independently represents a hydrogen atom or a substituent.) (1) to (8) above The organic electroluminescent element as described in any one.
(10) An organic electroluminescence device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the organic compound layer contains at least one compound represented by the following general formula (IIB1). An organic electroluminescent element.
Formula (IIB1)

In the formula, A ₁ represents —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si (R ₃₁ ) (R ₃₂ ) _{-, - N (R 35)} -, - O -, - S -, - SO -, - SO 2 -, - CO- (R 25, R 26, R 27, R 28, R 29, R 30, R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, or an aryloxy group, and R ₃₅ represents a hydrogen atom or an alkyl group. Represents a cycloalkyl group or an aryl group). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a cyano group, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an alkyl group or an aryl group.
(11) The organic electroluminescent element as described in (10) above, wherein both R ₂ and R ₆ are hydrogen atoms.
(12) A ₁ is -C (R ₂₅ ) (R ₂₆ )-or -C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-(R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ each independently represents a hydrogen atom, an alkyl group, or an aryl group.) The organic electroluminescent device as described in (10) or (11) above,
(13) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and R ₁₁ , R _12. R < _13> and R < ₁₄ > respectively independently represent a hydrogen atom or an alkyl group, The organic electroluminescent element as described in any one of said (10)-(12) characterized by the above-mentioned.
(14) A compound represented by the following general formula (IIB1).
Formula (IIB1)

In the formula, A ₁ represents —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si (R ₃₁ ) (R ₃₂ ) _{-, - N (R 35)} -, - O -, - S -, - SO -, - SO 2 -, - CO- (R 25, R 26, R 27, R 28, R 29, R 30, R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, or an aryloxy group, and R ₃₅ represents a hydrogen atom or an alkyl group. Represents a cycloalkyl group or an aryl group). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a cyano group, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an alkyl group or an aryl group.
(15) A ₁ is -C (R ₂₅ ) (R ₂₆ )-or -C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-(R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ each independently represents a hydrogen atom, an alkyl group or an aryl group.) The compound as described in (14) above,
(16) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an alkyl group, The compound according to (14) or (15) above,
(17) A luminescent material comprising the compound according to any one of (14) to (16) above.
(18) A light emitting layer containing the compound according to any one of (14) to (16).
(19) A display device using the organic electroluminescent device according to any one of (10) to (13).
(20) A display using the organic electroluminescent element according to any one of (10) to (13).
(21) An illumination light source using the organic electroluminescent element according to any one of (10) to (13).
The present invention relates to the above (10) to (21) , but other matters are also described for reference.

  An organic electroluminescence device comprising a platinum complex compound having a specific structure according to the present invention in an organic compound layer is excellent in emission characteristics (emission wavelength, luminance, quantum yield, driving voltage, etc.) and durability. Moreover, since this platinum complex compound is a complex containing an organic ligand, it is excellent in vapor deposition property.

  In the present specification, general formulas (I), (II), (III), (IIA), (IIB), (IIB1), (IIB2) and (IIIA) (general formulas (I) to (IIIA) Are used synonymously with the “compound of the present invention”. Moreover, the organic electroluminescent element which has the organic compound layer containing the compound of this invention is used synonymously with "the (light-emitting) element of this invention." In this specification, the substituent group A is defined as follows.

(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, etc.), cycloalkyl groups (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl). ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl. ), Alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferred) Has 2 to 10 carbon atoms, such as propargyl, 3-pentynyl, etc.), an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms). For example, phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), an amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms). For example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably Has 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy An aryloxy group (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-naphthyl). Oxy, etc.)

Heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl 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 acetyl, benzoyl, formyl, pivaloyl), an alkoxycarbonyl group (preferably Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably 7 carbon atoms). To 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 1 carbon atoms. Such as phenyloxycarbonyl), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferred. Ku is a C7-12, e.g., phenyloxycarbonylamino and the like.),

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.), a sulfamoyl group ( Preferably it is C0-30, More preferably, it is C0-20, Most preferably, it is C0-12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc. are mentioned. ), 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.) An alkylthio group (preferably having 1 to 30 carbon atoms) Preferably it is C1-C20, Most preferably, it is C1-C12, for example, methylthio, ethylthio etc. are mentioned, for example, An arylthio group (Preferably C6-C30, More preferably C6-C20, Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenylthio.), A heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms) For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably having 1 to 12 carbon atoms, such as mesyl and tosyl), sulfinyl group (preferably carbon 1-30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methane sulfinyl, and the like benzenesulfinyl.),

Ureido 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 ureido, methylureido, phenylureido), phosphoric acid amide 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 diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, more preferably fluorine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino Group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, Examples of the telo atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, Azepinyl group, etc.), silyl groups (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, and particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.). Can be mentioned. These substituents may be further substituted.

The general formula (I) will be described. Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ each independently represents an atom selected from carbon, nitrogen, oxygen, sulfur and silicon. The bond between atoms in a 5-membered ring formed from Z ₁ , Z ₂ , Z ₃ , Z ₄ and N atoms, and Z ₅ , Z ₆ , Z ₇ , Z ₈ and N atoms is not particularly limited. Any combination of a bond and a double bond may be used. Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are preferably carbon or nitrogen atoms.

In the general formula (I), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ have a substituent selected from the substituent group A when they can be further substituted. It may be. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group A heterocyclic group and a silyl group, more preferably an alkyl group, a cycloalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, and a heterocyclic group, and these groups are an alkyl group, an alkoxy group, and an alkoxy group. Substituted with an amino group It is preferable.

In the general formula (I), A ₁ represents a divalent linking group. Although it does not specifically limit as a bivalent coupling group, The bivalent coupling group containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a germanium atom, or a phosphorus atom is especially preferable, and the following coupling group group A More preferred groups are particularly preferred.
Linking group A

In the linking group A, R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ (R _{25 to} R ₃₆ ) are each Independently represents a hydrogen atom or a substituent. When R _{25 to} R ₃₆ represent a substituent, the substituent has the same meaning as the substituent selected from the substituent group A. When R _{25 to} R ₃₆ can be substituted, they may further have a substituent, R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ , R ₂₉ and R ₃₀ , R ₂₇ and R ₂₉ , R ₂₇ and R ₃₀ , R ₂₈ and R ₃₀ , R ₂₈ and R ₂₉ , R ₃₁ and R ₃₂ or R ₃₃ and R ₃₄ may be bonded to each other to form a ring.

A ₁ is preferably a hydrogen atom or a substituent selected from the linking group A, of which —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) _{(R 30) -, - Si} (R 31) (R 32) -, - N (R 35) -, - O -, - S -, - SO -, - SO 2 - or -CO- is preferable, - _{C (R 25) (R 26} ) -, - C (R 27) (R 28) C (R 29) (R 30) -, - Si (R 31) (R 32) -, - O-, or - S- is more preferable, and -C (R ₂₅ ) (R ₂₆ )-or -C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-is more preferable.

In C (R ₂₅ ) (R ₂₆ ) —, R ₂₅ and R ₂₆ are preferably a hydrogen atom or a substituent selected from the following substituent group B.

(Substituent group B)
Substituent group B is an alkyl group, cycloalkyl group, aryl group, halogen atom, amino group, alkylthio group, arylthio group, alkyloxy group, aryloxy group, hydroxy group, mercapto group, more preferably an alkyl group, A cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, and an aryloxy group are preferable, and an alkyl group and an aryl group are more preferable.

In the —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are preferably a hydrogen atom or a substituent selected from the substituent group B. is there.

In the —Si (R ₃₁ ) (R ₃₂ ) —, R ₃₁ and R ₃₂ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —Ge (R ₃₃ ) (R ₃₄ ) —, R ₃₃ and R ₃₄ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —N (R ₃₅ ) —, R ₃₅ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

In the above -P (R ₃₆ )-, R ₃₆ has the same _{meaning as} the preferred range of R ₃₅ .

In the general formula (I), B ₁ and B ₂ each independently represents a single bond or a divalent linking group. The linking group is not particularly limited, but is preferably a single bond or a divalent linking group containing a carbon atom, nitrogen atom, oxygen atom, sulfur atom, silicon atom, germanium atom or phosphorus atom. A group selected from the group A is more preferable, and a single bond, —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si ( R ₃₁ ) (R ₃₂ )-, -N (R ₃₅ )-, -O-, -S-, or -CO- is more preferred, and a single bond, -C (R ₂₅ ) (R ₂₆ )-or -O -Is particularly preferred. B ₁ is —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si (R ₃₁ ) (R ₃₂ ) —, —Ge In the case of representing (R ₃₃ ) (R ₃₄ ) —, —N (R ₃₅ ) — and P (R ₃₆ ) —, the preferred range is the same as the preferred range described for A ₁ above.

In general formula (I), X < ₁ >, X < ₂ > represents the partial structure which has an atom couple | bonded with a platinum atom. The X ₁ partial structure includes a group bonded by a carbon atom, a group bonded by a nitrogen atom, a group bonded by a silicon atom, a group bonded by a phosphorus atom, a group bonded by an oxygen atom, and a group bonded by a sulfur atom. A group bonded by a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom is more preferable, and a group bonded by a carbon atom or an oxygen atom is particularly preferable. However, X ₁ and X ₂ are not bonded to form a ring.

  Examples of the group bonded by the carbon atom include a substituted or unsubstituted aryl group bonded by a carbon atom, a substituted or unsubstituted 5-membered heteroaryl group bonded by a carbon atom, and a substituted or unsubstituted bond bonded by a carbon atom. Preferred is a 6-membered heteroaryl group, a substituted or unsubstituted aryl group bonded at a carbon atom, a substituted or unsubstituted nitrogen-containing 5-membered heteroaryl group bonded at a carbon atom, a nitrogen-containing 6-membered bonded at a carbon atom A ring heteroaryl group is more preferred, and a substituted aryl group bonded with a carbon atom is particularly preferred.

  The group bonded by the oxygen atom is preferably a substituted or unsubstituted hydroxyl group or a substituted or unsubstituted carboxyl group, and more preferably a substituted or unsubstituted carboxyl group.

  The group bonded with the nitrogen atom is preferably a substituted amino group, a nitrogen-containing five-membered heteroaryl group bonded with a nitrogen atom, more preferably a nitrogen-containing five-membered heteroaryl group bonded with a nitrogen atom, a substituted carbazole, Substituted pyrrole, substituted indole and the like are particularly preferred.

  The group bonded by the phosphorus atom is preferably a substituted phosphino group. As the group bonded by a silicon atom, a substituted silyl group is preferable. As the group bonded with a sulfur atom, a thiol group or a substituted thiol group is preferable.

The general formula (I) is preferably represented by the general formula (II) or (III).
Hereinafter, the general formula (II) will be described. In the general formula (II), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , and B ₂ are the same as those in the general formula (I). It is. Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ , Z ₁₇ , Z ₁₈ , Z ₁₉ , and Z ₂₀ (Z _{11 to} Z ₂₀ ) are each independently carbon, nitrogen, oxygen, sulfur, It represents an atom selected from silicon, preferably a carbon or nitrogen atom, more preferably a carbon atom, and still more preferably all of Z _{11 to} Z ₂₀ are carbon atoms ((unsubstituted) benzene ring). Z _{11 to} Z ₂₀ may further have a substituent when substitutable. Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, or a single bond, preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. When Y ₁ and Y ₂ represent a substituted nitrogen atom, examples of the substituent are preferably a substituent selected from Substituent Group A, more preferably an alkyl group, a cycloalkyl group, and an aryl group, and a carbon number of 1 An alkyl group having 7 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms (1 to 2 ring members) is more preferable.

Next, general formula (III) is demonstrated. In the general formula (III), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , and B ₂ are the same as those in the general formula (I). It is. Z ₃₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ , Z ₃₅ , Z ₃₆ , Z ₃₇ , and Z ₃₈ (Z _{31 to} Z ₃₈ ) are each independently an atom selected from carbon, nitrogen, oxygen, sulfur, and silicon. Represents a carbon, nitrogen or sulfur atom, more preferably a carbon or nitrogen atom. Z _{31 to} Z ₃₈ may further have a substituent when substitutable, and examples of the substituent are substituents selected from the substituent group A. Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, or a single bond, and have the same meanings as Y ₁ and Y ₂ in formula (II).

The general formula (II) is preferably represented by the general formula (IIA).
Hereinafter, general formula (IIA) is demonstrated. In the general formula (IIA), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , B ₁ , B ₂ , Y ₁ and Y ₂ represent the general formula (II ). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ (R _{1 to} R ₈ ) each independently represent a hydrogen atom or a substituent. This substituent is synonymous with the substituent selected from the substituent group A. Preferred groups of R _{1 to} R ₈ include hydrogen atom, alkyl group, cycloalkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group. Group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably hydrogen atom, alkyl group, aryl group, sulfonyl group, halogen atom, cyano group, nitro group, heterocyclic group, most preferably hydrogen atom, alkyl group, aryl group, halogen An atom or a cyano group. When R _{1 to} R ₈ can be further substituted, they may have a substituent. R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₁ and R ₃ , R ₂ and R ₄ , R ₁ and R ₄ , R ₅ and R ₆ , R on the same benzene ring ₆ and R ₇ , R ₇ and R ₈ , R ₅ and R ₇ , R ₆ and R ₈ , and R ₅ and R ₈ may be bonded to each other to form a ring. R ₂ and R ₆ are preferably both hydrogen atoms. In particular, when Y ₁ or Y ₂ is a single bond, it is preferable that both R ₂ and R ₆ are hydrogen atoms.

The general formula (IIA) is preferably represented by the general formula (IIB).
Hereinafter, general formula (IIB) is demonstrated. In the general formula (IIB), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , A ₁ , Y ₁ , Y ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined in general formula (IIA).

The general formula (IIB) is preferably represented by the general formula (IIB1) or (IIB2).
Hereinafter, general formula (IIB1) is demonstrated. In the general formula (IIB1), A ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as those in the general formula (IIB). R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ (R _{11 to} R ₁₄ ) each independently represent a hydrogen atom or a substituent. This substituent is synonymous with the substituent selected from the substituent group A. Preferred examples of R _{11 to} R ₁₄ include a hydrogen atom, alkyl group, cycloalkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group. Group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring And a silyl group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom and a cyano group, and still more preferably a hydrogen atom, an alkyl group and an aryl group. When R _{11 to} R ₁₄ can be further substituted, they may have a substituent.

Next, general formula (IIB2) is demonstrated. In the general formula (IIB2), A ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as those in the general formula (IIB), and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ have the same meanings as those in formula (IIB1).

The general formula (III) is preferably represented by the general formula (IIIA).
Hereinafter, general formula (IIIA) is demonstrated. In the general formula (IIIA), Z ₁ , Z ₂ , Z ₃ , Z ₅ , Z ₆ , Z ₇ , A ₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ , Z ₃₆ , Z ₃₇ , Z ₃₈ , Y ₁ and Y ₂ is synonymous with those of the general formula (III).

  The compound of the present invention may be a low molecular compound, and is an oligomeric 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. It may be. In the case of an oligomer compound or a polymer compound, the structure represented by the general formula may be included in the polymer main chain, or may be included in the polymer side chain. The polymer compound may be a homopolymer compound or a copolymer. The compound of the present invention is preferably a low molecular compound.

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

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

  The compound of the present invention can be synthesized, for example, by reacting a corresponding dicarbonyl compound with hydrazine hydrate with reference to the method described in Synthesis, 5, 409-411, (1986), By synthesizing the corresponding ligand by reacting with an alkyl halide or phosgene, and then reacting the obtained organic ligand with an appropriate platinum source as described above in a solvent as described above. Although it can synthesize | combine, it is not limited to the method quoted here.

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

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

  The compound of the present invention and the ligand forming the partial structure of the target complex are preferably 0.1 equivalents to 10 equivalents, more preferably 0.3 equivalents to 6 equivalents, still more preferably, relative to the platinum compound. It can be synthesized by adding 0.5 equivalent to 4 equivalents. Examples of the platinum compound include halides (for example, platinum chloride, potassium chloroplatinate), carboxylates (for example, platinum acetate), diketonates (for example, platinum acetylacetonate), and organic ligands. Examples thereof include platinum compounds (such as dichlorocyclooctadienyl platinum) or hydrates thereof.

  Next, specific synthesis examples of exemplary compounds (1), (101), (102) and (114) among the compounds represented by the general formula (I) of the present invention will be shown. It is not limited.

<Synthesis of Exemplary Compound (1) of the Present Invention>
Under a nitrogen atmosphere, a 100 mL three-necked flask was charged with 10 g (78 mmol) of 3,3-dimethyl-2,4-pentanedione (A), 27.6 mL of dimethylformamide-dimethylacetal, and 60 mL of dimethylformamide for 18 hours at 150 ° C. It was made to react with. After the reaction solution was concentrated under reduced pressure, the residue was purified by silica gel chromatography (developing solution: ethyl acetate / methanol = 9/1) to obtain 4.83 g of Compound (B) (yield 26%).
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 7.57 (d, J = 12.6 Hz, 2H), 5.05 (d, J = 12.6 Hz, 2H), 3.01 (Broad s, 6H), 2.78 (broad s, 6H), 1.32 (s, 6H).

Under a nitrogen atmosphere, a 300 mL three-necked flask was charged with 2.70 g (21.0 mmol) of Compound (B), 1.19 g (23.8 mmol) of hydrazine monohydrate, and 200 mL of ethanol, and heated to reflux for 7 hours. The reaction solution was concentrated, and the residue was purified by silica gel chromatography (developing solution: ethyl acetate / ethanol = 8/2) to obtain 1.77 g of compound (C) (yield 89%).
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 7.49 (d, J = 2.1 Hz, 2H), 6.19 (d, J = 2.1 Hz, 2H), 1.74 (S, 6H).

In a 200 mL three-necked flask under a nitrogen atmosphere, 1.00 g (4.20 mmol) of compound (C), 11.57 g (56.4 mmol) of iodobenzene, 81.1 mg (0.567 mmol) of copper oxide, 311 mg of salicylaldoxime ( 2.27 mmol), 7.39 g (38.3 mmol) of cesium carbonate, and 100 mL of butyronitrile were charged and reacted at 140 ° C. for 16 hours. The reaction was filtered and concentrated. The obtained residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 10/1) to obtain 1.43 g of Compound (D) (yield 77%).
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 7.80 (d, J = 2.7 Hz, 2H), 7.71-7.68 (m, 4H), 7.45-7 .39 (m, 4H), 7.25-7.20 (m, 2H), 6.32 (d, J = 2.4 Hz, 2H), 1.85 (s, 6H).

Under a nitrogen atmosphere, a 50 mL eggplant flask was charged with 50 mg (0.152 mmol) of compound (D), 40.5 mg (0.152 mmol) of platinum chloride and 3 mL of benzonitrile, and heated at 200 ° C. for 5 hours. After cooling to room temperature, 40 mL of hexane was added to the reaction solution, and the precipitated brown solid was purified by silica gel chromatography (developing solution: chloroform) to obtain 17.6 mg of Exemplified Compound (1) of the present invention. Yield 22%. The exemplary compound (1) of the present invention emitted light at 460 nm in a dichloromethane solution at room temperature.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 8.15 (dd, J = 1.2, 7.2 Hz, ³ J _Pt-H = 56.8 Hz, 2H), 7.95 ( d, J = 2.8 Hz, 2H), 7.33 (dd, J = 1.2, 7.6 Hz, 2H), 7.24-7.14 (m, 4H), 6.59 (d, J = 2.4 Hz, 2H), 1.80 (s, 6H).

<Synthesis of Exemplary Compound (101) of the Present Invention>
In a 200 mL three-necked flask under nitrogen atmosphere, 0.30 g (1.70 mmol) of compound (C), 4.63 g (17.0 mmol) of 3-iodobenzotrifluoride, 24 mg (0.17 mmol) of copper oxide, 93 mg of salicylaldoxime. (0.11 mmol), 2.21 g (11.5 mmol) of cesium carbonate, and 20 mL of butyronitrile were charged and reacted at 140 ° C. for 18 hours. After completion of the reaction, the reaction solution was filtered and concentrated. The obtained residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 5/1) to obtain 635 mg of compound (E) (yield 80%).
¹ H-NMR (400 MHz in CDCl ₃ ): δ (ppm) = 7.97 (brs, 2H), 7.90-7.84 (m, 4H), 7.58-7.46 (m, 4H), 6.37 (d, J = 2.4 Hz , 2H), 1.85 (s, 6H).

Under a nitrogen atmosphere, a 50 mL eggplant flask was charged with 50 mg (0.11 mmol) of compound (E), 50.5 mg (0.11 mmol) of platinum (II) chloride benzonitrile complex, and 3 mL of benzonitrile, and heated at 200 ° C. for 9 hours. . After cooling to room temperature, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (developing solution: chloroform). The obtained crude crystals were recrystallized from methanol to obtain 4 mg of the exemplary compound (101) of the present invention as a white powder (yield 5.6%). The exemplary compound (101) of the present invention emitted weak light at 453 nm in a dichloromethane solution at room temperature.
¹ H-NMR (400 MHz in CDCl ₃ ): δ (ppm) = 8.20 (d, J = 8.0 Hz, ³ J _Pt-H = 54.8 Hz, 2H), 8.04 (d, J = 2.8 Hz, 2H), 7.55-7.23 (m, 4H), 6.68 (d, J = 2.4 Hz, 2H), 1.80 (s, 6H).

<Synthesis of Compound (102) of the Present Invention>
Under nitrogen stream, compound (C) 1.0 g (5.7 mmol), m-iodobenzonitrile 12.8 g (55.9 mmol), cuprous oxide 80 mg (0.56 mmol), salicylaldoxime 0.30 g (2.2 mmol), 7.16 g (37.1 mmol) of cesium carbonate was suspended in 100 ml of n-butyronitrile and refluxed with stirring. After stirring for 17.5 hours under heating, the mixture was cooled to room temperature. The insoluble part was removed by Celite filtration, and the solvent of the filtrate was distilled off. Purification by a silica gel column (hexane: ethyl acetate = 4: 1) yielded 1.6 g (yield 75%) of compound (F) as crystals.
¹ H-NMR (400 MHz in CDCl ₃ ) 400 MHz: δ 1.84 (s, 6H), 6.39 (d, J = 2.4Hz, 2H), 7.48-7.56 (m, 4H), 7.84 (d, J = 2.8Hz , 2H), 7.91 (dt, J = 2.0 and 7.6 Hz, 2H), 8.05 (br, 2H).

Under a nitrogen atmosphere, a 50 mL eggplant flask was charged with 50 mg (0.13 mmol) of compound (F), 35.1 mg (0.13 mmol) of platinum chloride and 3 mL of benzonitrile, and heated at 200 ° C. for 5 hours. After cooling to room temperature, 40 mL of hexane was added to the reaction solution, and the precipitated brown solid was purified by silica gel chromatography (developing solution: methylene chloride → methylene chloride / methanol = 10/1) to give an exemplary compound (102) of the present invention. 10.1 mg was obtained as a white powder (yield 18%). The exemplary compound (102) of the present invention emitted weak light at 460 nm in a dichloromethane solution at room temperature.
¹ H-NMR (400 MHz in CDCl ₃ ): δ (ppm) = 8.18 (d, J = 7.6 Hz, ³ J _Pt-H = 56.8 Hz, 2H), 8.03 (d, J = 2.8 Hz, 2H), 7.55 (d, J = 1.6 Hz, 2H), 7.49 (dd, J = 1.6, 7.6 Hz 4H), 6.71 (d, J = 2.8 Hz, 2H), 1.84 (s, 6H).

<Synthesis of Compound (114) of the Present Invention>
In a nitrogen atmosphere, a 500 mL three-necked flask was charged with 20.0 g (114 mmol) of 3-phenyl-2,4-pentanedione (purchased from Tokyo Chemical Industry) and 200 mL of dimethylformamide, and the internal temperature was 5 degrees in an ice bath. Until cooled. In the range of 5 to 15 ° C. of internal temperature, 19.1 g (8.91 mmol) of tert-butoxypotassium was added little by little, and the mixture was returned to room temperature and stirred for 1 hour. The mixture was cooled again, and 14.1 mL (226 mmol) of iodomethane was added dropwise at an internal temperature of 5 to 10 ° C. After heating up to room temperature, it stirred at 80 degreeC for 6 hours. The reaction mixture was added dropwise to aqueous hydrochloric acid (17 g of 35% aqueous hydrochloric acid, prepared from 400 mL of water), extracted with 500 mL of ethyl acetate, the organic layers were combined, washed twice with 500 mL of saturated brine, dried over anhydrous sodium sulfate, and filtered. After further concentration, the residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 10/1) to obtain 11.1 g of compound (H) (yield 51%).
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.50-7.20 (m, 5H), 2.12 (s, 6H), 1.77 (s, 3H)

Under a nitrogen atmosphere, a 100 mL three-necked flask was charged with 5.00 g (26.3 mmol) of compound (H), 8.9 mL of dimethylformamide-dimethylacetal, and 30 mL of dimethylformamide, and reacted at 150 ° C. for 14 hours. After the reaction solution was concentrated under reduced pressure, the residue was purified by silica gel chromatography (developing solution: ethyl acetate / ethanol = 8/2) to obtain 3.86 g of compound (I) (yield 48.8%). ).
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.62 (d, J = 12.3 Hz, 2H), 7.40-7.10 (m, 5H), 5.15 (d, J = 12.3 Hz, 2H), 3.05 (broad s, 6H), 2.73 (broad s, 6H), 1.72 (s, 3H).

Under a nitrogen atmosphere, 3.86 g (12.8 mmol) of Compound (I), 1.3 mL of hydrazine monohydrate, and 230 mL of ethanol were charged in a 300 mL three-necked flask and heated to reflux for 5 hours. The reaction solution was concentrated, and the residue was purified by silica gel chromatography (developing solution: ethyl acetate / ethanol = 8/2) to obtain 2.88 g of compound (J) (yield 94.1%).
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.46 (d, J = 2.1 Hz, 2H), 7.30-7.00 (m, 5H), 6.18 (d, J = 2.1 Hz, 2H), 2.07 (s , 3H).

Under a nitrogen atmosphere, in a 200 mL three-necked flask, 0.50 g (2.1 mmol) of compound (J), 5.71 g (21.0 mmol) of 3-iodobenzotrifluoride, 30 mg (0.21 mmol) of copper oxide, 115 mg of salicylaldoxime (0.84 mmol), 2.73 g (14.2 mmol) of cesium carbonate, and 30 mL of butyronitrile were charged and reacted at 140 ° C. for 18 hours. The reaction was filtered and concentrated. The obtained residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 10/1) to obtain 795 mg of Compound (K) (yield 72%).
¹ H-NMR (CDCl ₃ ): δ (ppm) = 7.97-7.82 (m, 6H), 7.57-7.47 (m, 4H), 7.58-7.46 (m, 4H), 6.39 (d, J = 2.7 Hz, 2H), 2.29 (s, 3H).

Under a nitrogen atmosphere, a 50 mL eggplant flask was charged with 393 mg (0.746 mmol) of compound (K), 199 mg (0.748 mmol) of platinum (II) chloride and 15 mL of benzonitrile, and heated at 200 ° C. for 17 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (developing solution: chloroform) and recrystallized from chloroform-methanol-hexane to obtain 180 mg of exemplary compound (114) of the present invention ( Yield 33%). The exemplified compound (114) of the present invention emitted light at 460 nm in a dichloromethane solution at room temperature.
¹ H-NMR (CDCl ₃ ): δ (ppm) = 8.24 (d, J = 7.5 Hz, ³ J _Pt-H = 55.5 Hz, 2H), 7.97 (d, J = 2.7 Hz, 2H), 7.55-7.23 (m, 9H), 6.27 (d, J = 2.7 Hz, 2H), 2.22 (s, 3H).

Next, a light emitting device containing the compound of the present invention will be described.
The light-emitting device of the present invention can be used in ordinary light-emitting systems, driving methods, usage forms, and the like except that it is a device that uses the compound of the present invention. As a typical light-emitting device, organic EL (electroluminescence) is used. It is preferably used for an element.
The compound of the present invention is preferably used as a light emitting material, a host material, an exciton block material, a charge blocking material or a charge transport material, more preferably used as a host material, a light emitting material or a charge transport material. Or the case where it utilizes as a host material is more preferable. When used as a light-emitting material, ultraviolet light emission or infrared light emission may be used, and fluorescent light emission or phosphorescence light emission may be used. When used as a charge transport material, it may be a hole transport property or an electron transport property.
When using the compound of this invention as a luminescent material in a light emitting layer, it is preferable that 0.1-40 mass% is contained in a light emitting layer, 0.5-30 mass% is more preferable, 0.5- 20% by mass is particularly preferred.
Moreover, when using as host materials other than the luminescent material in a light emitting layer, it is preferable that 60-99.9 mass% is contained in a light emitting layer, 70-99.5 mass% is more preferable, and 80-99. .5% by mass is particularly preferred.
Moreover, when contained in layers other than a light emitting layer, it is preferable that 0.1-100 mass% is contained in this layer, 0.5-100 mass% is more preferable, 10-100 mass% is especially preferable.

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

  In the element of the present invention, the function of the organic compound layer is not particularly limited, but in addition to the light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole block layer, an electron block layer , An exciton blocking layer, a protective layer, and the like. Each of these layers may have other functions.

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

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

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

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

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

<Anode>
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

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

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

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

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

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

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

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

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the device. The electrode material can be selected as appropriate.

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

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

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

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

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

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

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

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

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

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

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

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

As the phosphorescent light-emitting material that can be used, metal complexes described in International Patent Publication Nos. 04/099339, 04/006498, and 04/108857 are preferable, and the compound of the present invention is the phosphorescent material described above. It is preferable to apply in combination.
The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.

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

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

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

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

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

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

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

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

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

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

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

(Comparative example)
The cleaned ITO substrate is put into a vapor deposition apparatus, NPD is vapor-deposited by 50 nm, and CBP and Compound (1) (compound described in International Patent Publication No. 2004/108857) are vapor-deposited by 40 nm at a mass ratio of 10: 1. Further, BAlq was deposited thereon to 10 nm, and Alq was further deposited thereon to 30 nm. A patterned mask (with a light emission area of 4 mm × 5 mm) was placed on the obtained organic thin film, and after 3 nm of lithium fluoride was deposited, 60 nm of aluminum was deposited to prepare an organic EL device of Comparative Example 1. When a DC constant voltage (5 V) was applied to the obtained organic EL element, light emission was observed. Light was emitted for 10 hours at a luminance of 300 cd / m ² .

Example 1
In Comparative Example 1, an organic EL device of Example 1 was prepared in the same manner as Comparative Example 1 except that Compound (1) of the present invention was used instead of Compound (1). When a DC constant voltage (5 V) was applied to the obtained organic EL element, light emission was observed. When light was emitted for 10 hours at a luminance of 300 cd / m ² , the emission wavelength was shorter than that of the comparative example.

(Example 2)
In Comparative Example 1, an organic EL device of Example 2 was prepared in the same manner as Comparative Example 1 except that the compound (101) of the present invention was used instead of Compound (1). When a DC constant voltage (5 V) was applied to the obtained organic EL element, light emission was observed. When light was emitted for 10 hours at a luminance of 300 cd / m ² , the emission wavelength was shorter than that of the comparative example. In addition, the external quantum efficiency was lower than that of the device described in Example 1.

(Comparative Example 2)
The cleaned ITO substrate is put in a vapor deposition apparatus, NPD is vapor-deposited by 50 nm, and CBP and Compound (79) (compound described in International Publication No. 2004/108857) are vapor-deposited by 40 nm at a mass ratio of 10: 1. Further, 3 nm of BAlq was deposited thereon, and 30 nm of Alq was further deposited thereon. A patterned mask (with a light emission area of 4 mm × 5 mm) was placed on the obtained organic thin film, lithium fluoride was deposited by 3 nm, and then aluminum was deposited by 60 nm to prepare an organic EL device of Comparative Example 2. When a DC constant current having a current density of 500 A / m ² was passed through the obtained organic EL element, light emission was observed. Light was emitted for 10 hours at a luminance of 200 cd / m ² .

(Example 3)
In Comparative Example 1, an organic EL device of Example 3 was prepared in the same manner as Comparative Example 1 except that the compound (114) of the present invention was used instead of BAlq. When a DC constant current having a current density of 500 A / m ² was passed through the obtained organic EL element, light emission was observed. When light was emitted for 10 hours at a luminance of 200 cd / m ² , the driving voltage was lower than that of Comparative Example 2, and the voltage increase was small.

  Similarly, a light-emitting element having excellent light-emitting performance can be manufactured using other compounds of the present invention. The compound of the present invention can emit blue to green phosphorescence, and a blue to green organic electroluminescence device can be produced by using the compound.

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

Claims (12)

An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the organic compound layer contains at least one compound represented by the following general formula (IIB1 ) in the organic compound layer Electroluminescent device.
Formula (IIB1)

In the formula, A ₁ represents —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si (R ₃₁ ) (R ₃₂ ) _{-, - N (R 35)} -, - O -, - S -, - SO -, - SO 2 -, - CO- (R 25, R 26, R 27, R 28, R 29, R 30, R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, or an aryloxy group, and R ₃₅ represents a hydrogen atom or an alkyl group. Represents a cycloalkyl group or an aryl group) . R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a cyano group, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom , an alkyl group or an aryl group . The organic electroluminescent element according to claim 1, wherein R ₂ and R ₆ are both hydrogen atoms. A ₁ is -C (R ₂₅ ) (R ₂₆ )-or -C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-(R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ And R ₃₀ each independently represents a hydrogen atom , an alkyl group, or an aryl group .) The organic electroluminescent device according to claim 1 or 2 , wherein R ₁ , R ₂ , R _Three , R _Four , R _Five , R ₆ , R ₇ And R ₈ Each independently represents a hydrogen atom, an alkyl group, or a halogen atom; ₁₁ , R ₁₂ , R ₁₃ And R ₁₄ Each independently represents a hydrogen atom or an alkyl group, The organic electroluminescent element as described in any one of Claims 1-3 characterized by the above-mentioned. The compound represented by the following general formula (IIB1 ) .
Formula (IIB1)

In the formula, A ₁ represents —C (R ₂₅ ) (R ₂₆ ) —, —C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ ) —, —Si (R ₃₁ ) (R ₃₂ ) _{-, - N (R 35)} -, - O -, - S -, - SO -, - SO 2 -, - CO- (R 25, R 26, R 27, R 28, R 29, R 30, R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, or an aryloxy group, and R ₃₅ represents a hydrogen atom or an alkyl group. Represents a cycloalkyl group or an aryl group) . R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a cyano group, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom , an alkyl group or an aryl group . A ₁ Is -C (R _{twenty five} ) (R ₂₆ )-Or -C (R ₂₇ ) (R ₂₈ ) C (R ₂₉ ) (R ₃₀ )-(R _{twenty five} , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ And R ₃₀ Each independently represents a hydrogen atom, an alkyl group or an aryl group. 6. The compound according to claim 5, wherein R ₁ , R ₂ , R _Three , R _Four , R _Five , R ₆ , R ₇ And R ₈ Each independently represents a hydrogen atom, an alkyl group, or a halogen atom; ₁₁ , R ₁₂ , R ₁₃ And R ₁₄ Each independently represents a hydrogen atom or an alkyl group, The compound of Claim 5 or 6 characterized by the above-mentioned. Light-emitting material containing a reduction compound according to any one of claims 5-7. Light-emitting layer containing a reduction compound according to any one of claims 5-7. The display element using the organic electroluminescent element as described in any one of Claims 1-4 . The display using the organic electroluminescent element as described in any one of Claims 1-4 . The illumination light source using the organic electroluminescent element as described in any one of Claims 1-4 .