JP5144034B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent device (hereinafter also referred to as “organic EL device”), and more particularly to an organic electroluminescent device having excellent luminescent properties.

  In recent years, organic electroluminescence devices have been actively researched and developed because they can emit light with high luminance when driven at a low voltage. In general, an organic EL element is composed of an organic compound layer including a light emitting layer and a pair of electrodes sandwiching the layer, and electrons injected from the cathode and holes injected from the anode are recombined in the light emitting layer, The generated exciton energy is used for light emission.

In recent years, the use of phosphorescent light emitting materials has led to higher efficiency of devices. As phosphorescent materials, iridium complexes and platinum complexes are known (see, for example, Patent Documents 1 to 3), but the development of devices having excellent durability and light emission characteristics has not been achieved, and these characteristics have been improved. At present, the development of phosphorescent materials is anxious.
US Patent No. 6303238 International Publication No. 00/57676 Pamphlet International Publication No. 05/42444 Pamphlet

  An object of the present invention is to provide an organic electroluminescent device having excellent light emission characteristics. Another object is to provide a metal complex compound suitable for providing the light emitting element.

As a result of studies to solve the above problems, the present inventors have a tetradentate ligand, and a metal complex having a specific alkyl group on the linking group of the ligand (particularly, the following general formula (1) Or a metal complex represented by (2)) in the organic compound layer, so that the metal complexes in the organic compound layer are associated with each other and / or other organic materials used in the organic compound layer. The present inventors have found that an organic electroluminescent element having excellent light emitting characteristics can be obtained in which association is suppressed.
That is, the present invention is as follows.

（一般式（２）中、Ｒ^６１及びＲ^６２の両方が下記置換基Ｒ^１を表すか、或いはＲ^６１
及びＲ^６２のどちらか一方が下記置換基Ｒ^１を表わし、他方はメチル基、エチル基又はア
リール基を表す。Ｒ^６３、Ｒ^６５、Ｒ^６６及びＲ^６８はそれぞれ独立に、水素原子、メチ
ル基またはフッ素原子を表す。Ｒ^６４及びＲ^６７は、水素原子を表す。Ｑはそれぞれ独立
に、ベンゼン環またはピリジン環を表す。Ｑは可能であれば、置換基を有していてもよく
、Ｑが置換基を有するときの置換基はアルキル基、シアノ基、ジメチルアミノ基、フッ素
原子またはメトキシ基である。Ｑは可能であれば、他の環と縮合環を形成しても良く、Ｑ
と縮環する環は、ベンゼン環、ピリジン環、ピラジン環、ピリミジン環、チオフェン環、
フラン環、ピロール環、イミダゾール環、ピラゾール環、オキサゾール環またはチアゾー
ル環である。Ｍ^６１は白金イオンを表す。ｎは０を表す。但し、ｎ＝０の場合、ＱとＱは
連結しない。
置換基Ｒ^１：置換基Ｒ^１は下記一般式（Ｒ−１）〜（Ｒ−９）で表される３級もしくは
４級炭素を有する炭素数３〜２０のアルキル基を表す。

一般式（Ｒ−１）において、Ｒ^１Ａは、アルキル基またはアリール基を表し、複数のＲ
^１Ａはそれぞれ同じでも、異なっていても良い。２つのＲ^１Ａは互いに結合して環を形成
しても良い。
一般式（Ｒ−２）において、Ｒ^２Ａは、３つのＲ^２Ａの合計が炭素数４以上を満たす、
アルキル基またはアリール基を表し、複数のＲ^２Ａはそれぞれ同じであっても異なってい
ても良い。但し、３つのＲ^２Ａが互いに結合して環を形成することはない。
一般式（Ｒ−３）において、Ｒ^３Ａは、アルキル基またはアリール基を表し、複数のＲ
^３Ａはそれぞれ同じでも、異なっていても良い。複数のＲ^３Ａは互いに結合して環を形成
しても良い。
一般式（Ｒ−５）において、Ｒ^５Ａは、２つのＲ^５Ａの合計が炭素数４以上を満たす、
アルキル基またはアリール基を表し、複数のＲ^５Ａはそれぞれ同じであっても異なってい
ても良い。複数のＲ^５Ａは互いに結合して環を形成しても良い。
一般式（Ｒ−７）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−７）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができ、ｓ＝１の場合、Ｒ^７Ａ
は、２つのＲ^７Ａの合計が炭素数４以上を満たす、アルキル基またはアリール基を表し、
複数のＲ^７Ａはそれぞれ同じであっても異なっていても良い。ｓが１より大きい場合は、
Ｒ^７Ａは、アルキル基またはアリール基を表す。複数のＲ^７Ａは可能であれば互いに結合
して環を形成しても良い。
一般式（Ｒ−８）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−８）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができる。Ｒ^８Ａは、アルキル
基またはアリール基を表し、複数のＲ^８Ａはそれぞれ同じでも、異なっていても良い。複
数のＲ^８Ａは互いに結合して環を形成しても良い。
一般式（Ｒ−９）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−９）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができる。Ｑ^９Ａは、炭素原子
を含み芳香族環または芳香族ヘテロ環を形成するアリール基、ヘテロアリール基を表す。
）
＜２＞
前記一般式（２）において、Ｒ^６１及びＲ^６２の両方が置換基Ｒ^１を表すか、或いはＲ
^６１及びＲ^６２のどちらか一方が置換基Ｒ^１を表わし、他方はメチル基、エチル基又はア
リール基を表し、Ｒ^６３〜Ｒ^６８は水素原子であり、Ｑがベンゼン環であり、Ｑは他の環
と縮合環を形成しないことを特徴とする＜１＞に記載の有機電界発光素子。
＜３＞
前記一般式（２）において、Ｒ^６１及びＲ^６２の少なくとも１つがイソブチル基である
ことを特徴とする＜１＞または＜２＞に記載の有機電界発光素子。
＜４＞
下記一般式（２）で表されることを特徴とする化合物。
一般式（２）

（一般式（２）中、Ｒ^６１及びＲ^６２の両方が下記置換基Ｒ^１を表すか、或いはＲ^６１
及びＲ^６２のどちらか一方が下記置換基Ｒ^１を表わし、他方はメチル基、エチル基又はア
リール基を表す。Ｒ^６３、Ｒ^６５、Ｒ^６６及びＲ^６８はそれぞれ独立に、水素原子、メチ
ル基またはフッ素原子を表す。Ｒ^６４及びＲ^６７は、水素原子を表す。Ｑはそれぞれ独立
に、ベンゼン環またはピリジン環を表す。Ｑは可能であれば、置換基を有していてもよく
、Ｑが置換基を有するときの置換基はアルキル基、シアノ基、ジメチルアミノ基、フッ素
原子またはメトキシ基である。Ｑは可能であれば、他の環と縮合環を形成しても良く、Ｑ
と縮環する環は、ベンゼン環、ピリジン環、ピラジン環、ピリミジン環、チオフェン環、
フラン環、ピロール環、イミダゾール環、ピラゾール環、オキサゾール環またはチアゾー
ル環である。Ｍ^６１は白金イオンを表す。ｎは０を表す。但し、ｎ＝０の場合、ＱとＱは
連結しない。
置換基Ｒ^１：置換基Ｒ^１は下記一般式（Ｒ−１）〜（Ｒ−９）で表される３級もしくは
４級炭素を有する炭素数３〜２０のアルキル基を表す。

一般式（Ｒ−１）において、Ｒ^１Ａは、アルキル基またはアリール基を表し、複数のＲ
^１Ａはそれぞれ同じでも、異なっていても良い。２つのＲ^１Ａは互いに結合して環を形成
しても良い。
一般式（Ｒ−２）において、Ｒ^２Ａは、３つのＲ^２Ａの合計が炭素数４以上を満たす、
アルキル基またはアリール基を表し、複数のＲ^２Ａはそれぞれ同じであっても異なってい
ても良い。但し、３つのＲ^２Ａが互いに結合して環を形成することはない。
一般式（Ｒ−３）において、Ｒ^３Ａは、アルキル基またはアリール基を表し、複数のＲ
^３Ａはそれぞれ同じでも、異なっていても良い。複数のＲ^３Ａは互いに結合して環を形成
しても良い。
一般式（Ｒ−５）において、Ｒ^５Ａは、２つのＲ^５Ａの合計が炭素数４以上を満たす、
アルキル基またはアリール基を表し、複数のＲ^５Ａはそれぞれ同じであっても異なってい
ても良い。複数のＲ^５Ａは互いに結合して環を形成しても良い。
一般式（Ｒ−７）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−７）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができ、ｓ＝１の場合、Ｒ^７Ａ
は、２つのＲ^７Ａの合計が炭素数４以上を満たす、アルキル基またはアリール基を表し、
複数のＲ^７Ａはそれぞれ同じであっても異なっていても良い。ｓが１より大きい場合は、
Ｒ^７Ａは、アルキル基またはアリール基を表す。複数のＲ^７Ａは可能であれば互いに結合
して環を形成しても良い。
一般式（Ｒ−８）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−８）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができる。Ｒ^８Ａは、アルキル
基またはアリール基を表し、複数のＲ^８Ａはそれぞれ同じでも、異なっていても良い。複
数のＲ^８Ａは互いに結合して環を形成しても良い。
一般式（Ｒ−９）において、ｓは１以上の整数を表す。ｓは、一般式（Ｒ−９）で表さ
れる基の炭素数が２０以下であれば任意の整数を取ることができる。Ｑ^９Ａは、炭素原子
を含み芳香族環または芳香族ヘテロ環を形成するアリール基、ヘテロアリール基を表す。
）
＜５＞
発光層中に、少なくとも１種の一般式（２）で表される化合物と、少なく
とも１種のホスト材料を含有することを特徴とする＜１＞〜＜３＞のいずれか１項に記載
の有機電界発光素子。
＜６＞
発光層中に、少なくとも１種の一般式（２）で表される化合物と、少なく
とも１種の燐光発光材料を含有することを特徴とする＜１＞〜＜３＞のいずれか１項に記
載の有機電界発光素子。
本発明は上記の＜１＞〜＜６＞に関するものであるが、その他の事項についても記載し
た。
〔１〕一対の電極間に、発光層を含む有機化合物層を有する有機電界発光素子であって、
下記一般式（１）で表される４座配位子を有する金属錯体の少なくとも一種を有機化合物
層に含有することを特徴とする有機電界発光素子。
一般式（１） <1>
An organic electroluminescent element having an organic compound layer including a light emitting layer between a pair of electrodes, wherein at least one metal complex having a tetradentate ligand represented by the following general formula (2) is used as the organic compound layer An organic electroluminescent element characterized by containing.
General formula (2)

(In general formula (2), both R ⁶¹ and R ⁶² represent the following substituent R ¹ , or R ⁶¹
And R ⁶² represents the following substituent R ¹ , and the other represents a methyl group, an ethyl group or an aryl group. R ⁶³ , R ⁶⁵ , R ⁶⁶ and R ⁶⁸ each independently represent a hydrogen atom, a methyl group or a fluorine atom. R ⁶⁴ and R ⁶⁷ represent a hydrogen atom. Each Q independently represents a benzene ring or a pyridine ring. Q may have a substituent, if possible, and when Q has a substituent, the substituent is an alkyl group, a cyano group, a dimethylamino group, a fluorine atom or a methoxy group. Q may form a condensed ring with other rings, if possible.
Rings condensed with benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, thiophene ring,
A furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring or a thiazole ring. M ⁶¹ represents a platinum ion. n represents 0. However, when n = 0, Q and Q are not connected.
Substituent R ¹ : Substituent R ¹ represents a C 3-20 alkyl group having a tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9).

In General Formula (R-1), R ^1A represents an alkyl group or an aryl group, and a plurality of R
^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In the general formula (R-2), R ^2A has a total of three R ^2A satisfying 4 or more carbon atoms.
Represents an alkyl group or an aryl group, and the plurality of R ^2A may be the same or different from each other; However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents an alkyl group or an aryl group, and a plurality of R
^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In the general formula (R-5), R ^5A is a total of two R ^5A satisfying 4 or more carbon atoms.
Represents an alkyl group or an aryl group, and the plurality of R ^5A may be the same or different from each other; A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A
Represents an alkyl group or an aryl group in which the total of two R ^7A satisfies 4 or more carbon atoms,
The plurality of R ^7A may be the same or different. If s is greater than 1,
R ^7A represents an alkyl group or an aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents an alkyl group or an aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle.
)
<2>
In the general formula (2), both R ⁶¹ and R ⁶² represent the substituent R ¹ or R
^{One of 61} and R ⁶² represents the substituent R ¹ , the other represents a methyl group, an ethyl group or an aryl group, R ^{63 to} R ⁶⁸ are hydrogen atoms, Q is a benzene ring, Q is other The organic electroluminescent device according to <1>, wherein a condensed ring is not formed with the ring.
<3>
In the general formula (2), the organic electroluminescent device according to <1> or <2>, wherein the at least one of an isobutyl group R ⁶¹ and R ^62.
<4>
The compound represented by following General formula (2).
General formula (2)

(In general formula (2), both R ⁶¹ and R ⁶² represent the following substituent R ¹ , or R ⁶¹
And R ⁶² represents the following substituent R ¹ , and the other represents a methyl group, an ethyl group or an aryl group. R ⁶³ , R ⁶⁵ , R ⁶⁶ and R ⁶⁸ each independently represent a hydrogen atom, a methyl group or a fluorine atom. R ⁶⁴ and R ⁶⁷ represent a hydrogen atom. Each Q independently represents a benzene ring or a pyridine ring. Q may have a substituent, if possible, and when Q has a substituent, the substituent is an alkyl group, a cyano group, a dimethylamino group, a fluorine atom or a methoxy group. Q may form a condensed ring with other rings, if possible.
Rings condensed with benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, thiophene ring,
A furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring or a thiazole ring. M ⁶¹ represents a platinum ion. n represents 0. However, when n = 0, Q and Q are not connected.
Substituent R ¹ : Substituent R ¹ represents a C 3-20 alkyl group having a tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9).

In General Formula (R-1), R ^1A represents an alkyl group or an aryl group, and a plurality of R
^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In the general formula (R-2), R ^2A has a total of three R ^2A satisfying 4 or more carbon atoms.
Represents an alkyl group or an aryl group, and the plurality of R ^2A may be the same or different from each other; However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents an alkyl group or an aryl group, and a plurality of R
^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In the general formula (R-5), R ^5A is a total of two R ^5A satisfying 4 or more carbon atoms.
Represents an alkyl group or an aryl group, and the plurality of R ^5A may be the same or different from each other; A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A
Represents an alkyl group or an aryl group in which the total of two R ^7A satisfies 4 or more carbon atoms,
The plurality of R ^7A may be the same or different. If s is greater than 1,
R ^7A represents an alkyl group or an aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents an alkyl group or an aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle.
)
<5>
<1> to <3>, wherein the light emitting layer contains at least one compound represented by the general formula ( 2) and at least one host material. Organic electroluminescent device.
<6>
<1> to <3>, wherein the light emitting layer contains at least one compound represented by the general formula ( 2) and at least one phosphorescent light emitting material. Organic electroluminescent element.
The present invention relates to the above <1> to <6>, but other matters are also described.
[1] An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes,
An organic electroluminescent device comprising at least one metal complex having a tetradentate ligand represented by the following general formula (1) in an organic compound layer.
General formula (1)

(In the general formula (1), Q ²¹ and Q ²² each independently represent an atomic group coordinated to a metal. Q ²³ represents an atomic group coordinated to a metal by bonding with L ²³ by a carbon atom. , Q ²⁴ represents an atomic group bonded to L ²¹ and coordinated to a metal, and L ²¹ , L ²² , L ²³ , and L ²⁴ each independently represent a single bond or a linking group. ^At least one of ²¹ , L ²² , L ²³ , and L ²⁴ is a linking group, and has at least one or more of the following substituents R ¹ on at least one of the linking groups, M ²¹ is Represents a metal ion, and the bond between the metal ion and Q ²¹ , Q ²² , Q ²³ , and Q ²⁴ may be a covalent bond, a coordinate bond, or an ionic bond, where n represents 0 or 1, where n = 0 In this case, Q ²³ and Q ²⁴ are not consolidated.
Substituent R ¹ : Substituent R ¹ is a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms having tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9). Represent.

In General Formula (R-1), R ^1A represents a substituted or unsubstituted alkyl group or an aryl group, and the plurality of R ^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In General Formula (R-2), R ^2A represents a substituted or unsubstituted alkyl group or aryl group in which the total of three R ^2A satisfies 4 or more carbon atoms, and the plurality of R ^2A are the same. May be different. However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents a substituted or unsubstituted alkyl group or an aryl group, and the plurality of R ^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In General Formula (R-5), R ^5A represents a substituted or unsubstituted alkyl group or aryl group in which the total of two R ^5A satisfies 4 or more carbon atoms, and the plurality of R ^5A are the same. May be different. A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the number of carbon atoms of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A is the sum of two R ^7A A substituted or unsubstituted alkyl group or aryl group satisfying 4 or more carbon atoms is represented, and the plurality of R ^7A may be the same or different. When s is greater than 1, R ^7A represents a substituted or unsubstituted alkyl group or aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents a substituted or unsubstituted alkyl group or aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle. Q ^9A may have a substituent. )
[2] The organic electroluminescent element as described in [1] above, wherein the general formula (1) is represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ⁶¹ and R ⁶² each independently represents a hydrogen atom or a substituent, provided that at least one of R ⁶¹ and R ⁶² represents the substituent R ^1. R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ each independently represent a hydrogen atom or a substituent, and Q independently represents an atomic group that includes two carbon atoms and coordinates to a metal with carbon atoms. L ⁶⁴ represents a single bond or a linking group, M ⁶¹ represents a metal ion, n represents 0 or 1, provided that when n = 0, Q and Q are not linked.)
[3] The organic electroluminescent element as described in [2] above, wherein in the general formula (2), at least one of R ⁶¹ and R ⁶² is an isobutyl group.
[4] A compound represented by the following general formula (2):
General formula (2)

(In the general formula (2), R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a substituent, provided that at least one of R ⁶¹ and R ⁶² represents the following substituent R ^1: R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ each independently represents a hydrogen atom or a substituent, and Q independently represents an atomic group that includes two carbon atoms and coordinates to a metal with carbon atoms. L ⁶⁴ represents a single bond or a linking group, M ⁶¹ represents a metal ion, n represents 0 or 1, provided that when n = 0, Q and Q are not linked.
Substituent R ¹ : Substituent R ¹ is a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms having tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9). Represent.

In General Formula (R-1), R ^1A represents a substituted or unsubstituted alkyl group or an aryl group, and the plurality of R ^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In General Formula (R-2), R ^2A represents a substituted or unsubstituted alkyl group or aryl group in which the total of three R ^2A satisfies 4 or more carbon atoms, and the plurality of R ^2A are the same. May be different. However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents a substituted or unsubstituted alkyl group or an aryl group, and the plurality of R ^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In General Formula (R-5), R ^5A represents a substituted or unsubstituted alkyl group or aryl group in which the total of two R ^5A satisfies 4 or more carbon atoms, and the plurality of R ^5A are the same. May be different. A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the number of carbon atoms of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A is the sum of two R ^7A A substituted or unsubstituted alkyl group or aryl group satisfying 4 or more carbon atoms is represented, and the plurality of R ^7A may be the same or different. When s is greater than 1, R ^7A represents a substituted or unsubstituted alkyl group or aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents a substituted or unsubstituted alkyl group or aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle. Q ^9A may have a substituent. )
[5] The above [1] to [3], wherein the light emitting layer contains at least one compound represented by the general formula (1) or (2) and at least one host material. Organic electroluminescent element of any one of these.
[6] The above [1] to [3], wherein the light emitting layer contains at least one compound represented by the general formula (1) or (2) and at least one phosphorescent material. ] The organic electroluminescent element of any one of.

  An organic electric field having excellent light emission characteristics by containing in the organic compound layer the complex represented by the general formula (1) or (2) of the present invention (used herein in the same meaning as the “complex of the present invention”). A light-emitting element (used interchangeably with “an element of the present invention” in this specification) can be provided.

  In the present invention, 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, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably A prime number of 6 to 20, particularly preferably a carbon number of 6 to 12, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc., an amino group (preferably a carbon number of 0 to 30, more preferably a carbon number). 0 to 20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like, and aryloxy groups (preferably 6 carbon atoms). -30, more preferably 6-20 carbons, particularly preferably 6-12 carbons, 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). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.)

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

  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 and benzenesulfonylamino), 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). To 20, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl).

  A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably carbon 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphate amide and phenyl phosphate amide), hydroxy group, mercapto group, halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group Hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic (heteroaryl) group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include nitrogen atom, oxygen Atom, sulfur atom, and specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like. (Preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl, etc.), silyloxy group (preferably 3 carbon atoms) To 40, more preferably 3 to 30 carbon atoms, particularly preferably carbon 3 to 24, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  The device of the present invention will be described in detail. The element of the present invention has at least one organic compound layer between a pair of electrodes. When the organic compound layer is a single layer, the organic compound layer includes a light emitting layer. From the property of the element, at least one of the anode and the cathode is preferably transparent or translucent.

  The element of the present invention is characterized in that the organic compound layer contains a complex having a tetradentate ligand having a specific structure. Although it does not specifically limit as an organic compound layer, In addition to a light emitting layer, a positive hole injection layer, a positive hole transport layer, an electron injection layer, an electron transport layer, a positive hole block layer, an electron block layer, an exciton block layer, a protective layer And so on. Each of these layers may have other functions.

  As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated 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.

  The complex of the present invention can be contained in any layer when the organic compound layer is composed of a plurality of layers. The complex of the present invention is preferably contained in the light emitting layer, more preferably contained in the light emitting layer as the light emitting material or host material, further preferably contained in the light emitting layer as the light emitting material, and at least one kind It is particularly preferable that it is contained in the light emitting layer together with the host material.

  The content of the phosphorescent material (the complex of the present invention and / or the phosphorescent material used together) that can be used in the present invention is in the range of 0.1% by mass to 50% by mass with respect to the total mass of the light emitting layer. Is preferable, a range of 0.2% by mass to 30% by mass is more preferable, a range of 0.3% by mass to 20% by mass is further preferable, and a range of 0.5% by mass to 15% by mass is most preferable. .

  The host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light. In this specification, “substantially no light emission” means that the light emission amount from the substantially non-light emitting compound is preferably 5% or less, more preferably 3% or less of the total light emission amount of the entire device. More preferably, it means 1% or less.

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

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

  The fluorescence wavelength in the film state of the host material contained in the light emitting layer of the present invention is preferably in the range of 400 nm to 650 nm, more preferably in the range of 420 nm to 600 nm, and in the range of 440 nm to 550 nm. More preferably.

  As the host material used in the present invention, the compounds described in paragraphs 0113 to 0161 of JP-A No. 2002-1000047 and the compounds described in paragraphs of 0087 to 0098 of JP-A No. 2004-214179 can be suitably used. It is not limited to.

  When the complex of the present invention is introduced into a layer other than the light emitting layer (for example, a charge transport layer), it is preferably contained in the layer in an amount of 10% by mass to 100% by mass, more preferably 30% by mass to 100% by mass. % Is preferably included.

Hereinafter, the complex of the present invention will be described in detail.
The general formula (1) will be described. Q ²¹ and Q ²² each independently represent an atomic group that coordinates to a metal (the bond formed by coordination includes, for example, a coordinate bond, a covalent bond, and an ionic bond). Q ²¹ and Q ²² are not particularly limited as long as they are an atomic group coordinated to a metal, but an atomic group coordinated by a carbon atom, an atomic group coordinated by a nitrogen atom, an atomic group coordinated by an oxygen atom, sulfur An atom group coordinated by an atom, an atom group coordinated by a phosphorus atom, an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, and an atom group coordinated by an oxygen atom are more preferable, carbon An atomic group coordinated by an atom and an atomic group coordinated by a nitrogen atom are more preferable.

  Examples of atomic groups coordinated by carbon atoms include aromatic hydrocarbon (aryl) groups (benzene, naphthalene, etc.), heterocyclic groups (thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole). , Pyrazole, triazole, etc.) and fused rings containing these, and tautomers thereof. These groups may further have a substituent. Examples of the substituent include the groups described in the substituent group A described above.

  Examples of the atomic group coordinated by the 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 , Having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as methylamino), arylamino groups (for example, phenylamino) and the like), acylamino groups ( Preferably it 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 a carbon number). 2 to 30, 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 preferably 7 to 12 carbon atoms). Such as phenyloxycarbonylamino), sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, methanesulfonyl Amino, benzenesulfonylamino, etc.), and imino groups. These groups may be further substituted. Examples of the substituent include the groups described in the substituent group A described above.

  As an atomic group 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 and the like), 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-naphthyl). Oxy, 2-naphthyloxy, etc.), 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, such as pyridyloxy, Pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyloxy group (preferably having 2 to 30 carbon atoms, more preferred) Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), silyloxy group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, Particularly preferred are those having 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), carbonyl groups (for example, ketone groups, ester groups, amide groups, etc.), ether groups (for example, dialkyl ether groups, diaryls). Ether group, furyl group, etc.). These groups may be further substituted. Examples of the substituent include the groups described in the substituent group A described above.

  As an atomic group coordinated by a sulfur atom, 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 and ethylthio. ), 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 C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc. ), A thiocarbonyl group (for example, a thioketone group, a thioester group, etc.), a thioether group (for example, a dialkylthio group). Ether groups, diaryl thioether, etc. thiofuryl group). These groups may be further substituted. Examples of the substituent include the groups described in the substituent group A described above.

  Examples of the atomic group coordinated by the phosphorus atom include a dialkylphosphino group, a diarylphosphino group, a trialkylphosphine, a triarylphosphine, and a phosphinin group. These groups may be further substituted. Examples of the substituent include the groups described in the substituent group A described above.

Q ²¹ and Q ²² are preferably an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, or an atom group coordinated by an oxygen atom, and an aromatic hydrocarbon group or carbon atom coordinated by a carbon atom More preferably a heterocyclic group coordinated with a nitrogen atom, a heterocyclic group coordinated with a nitrogen atom, an aromatic hydrocarbon group coordinated with a carbon atom, a heterocyclic group coordinated with a nitrogen atom is more preferred, and a coordinated group with a carbon atom. An aromatic hydrocarbon group having a 6-membered or 5-membered ring structure and a heterocyclic group having a 6-membered or 5-membered ring structure coordinated by a nitrogen atom are particularly preferred. Q ²¹ and Q ²² may have a substituent selected from the aforementioned substituent group A if possible.

Q ²³ represents an atomic group bonded to L ²³ by a carbon atom and coordinated to a metal atom. Can be coupled to L ²³ carbon atoms is not particularly limited as long as it is an atom group which is capable of coordinating to the metal. As atom coordinating group to a metal include those described in Q ^21. Among them, an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, and an atom group coordinated by an oxygen atom are preferable, and an aromatic hydrocarbon group coordinated by a carbon atom, coordinated by a carbon atom A heterocyclic group, a heterocyclic group coordinated with a nitrogen atom, an aryloxy group coordinated with an oxygen atom, a heteroaryloxy group coordinated with an oxygen atom is more preferred, an aromatic hydrocarbon group coordinated with a carbon atom, A heterocyclic group coordinated by a carbon atom and a heterocyclic group coordinated by a nitrogen atom are particularly preferred. Q ²³ may have a substituent selected from the aforementioned substituent group A if possible.

Q ²⁴ represents an atomic group bonded to L ²¹ by a carbon atom and coordinated to a metal atom. There is no particular limitation as long as it is an atomic group that can be bonded to L ²¹ and a carbon atom and can be coordinated to a metal. As atom coordinating group to a metal include those described in Q ^21. A preferred range has the same meaning as above ^{Q 23.}

n is 0 or 1. However, in the case of n = ^{0, Q 23} and ^{Q 24} are not connected.

L ²¹ , L ²² , L ²³ and L ²⁴ each independently represent a single bond or a linking group. The linking group represented by L ²¹ , L ²² , L ²³ and L ²⁴ is not particularly limited. For example, an alkylene group, an alkenylene group, an arylene group, a heterocyclic linking group, an oxygen atom linking group, a sulfur atom linking group, silicon Examples thereof include a linking group comprising an atomic linking group, an imino linking group, a carbonyl linking group, and a combination thereof.

L ²¹ , L ²² , L ²³ and L ²⁴ are preferably a single bond, an alkylene group, an alkenylene group, an arylene group, a heterocyclic linking group, an oxygen atom linking group, a sulfur atom linking group, a silicon atom linking group, an imino linking group. , A carbonyl linking group, and a linking group consisting of a combination thereof, more preferably a linking group consisting of a single bond, an alkylene group, an arylene group, a heterocyclic linking group, an oxygen atom linking group, and a combination thereof, Preferred is a linking group comprising a single bond, an alkylene group, an arylene group, or a combination thereof.

However, at least one of L ²¹ , L ²² , L ²³ and L ²⁴ is a linking group, and has at least one or more of the following substituents R ¹ on at least one of the linking groups.

Hereinafter, the substituent R ¹ will be described. The substituent R ¹ represents an unsubstituted (or substituted) alkyl group having 3 to 20 carbon atoms and having a tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9). Among these, groups represented by general formulas (R-3) to (R-9) are preferable, groups represented by general formulas (R-4) to (R-9) are more preferable, and general formulas (R -4), (R-5) and (R-9) are more preferred, and the group represented by the general formula (R-4) is most preferred.

General formula (R-1) is demonstrated. R ^1A represents an alkyl group or an aryl group, and the plurality of R ^1A may be the same or different. Examples of the alkyl group or aryl group include methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, tert-butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, and naphthyl group. A methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a cyclohexyl group, and a phenyl group are more preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso- A propyl group and a phenyl group are more preferable. R ^1A may have a substituent selected from the aforementioned substituent group A, if possible. Two R ^1A's may combine with each other to form a ring if possible.
Examples of the ring formed by bonding two R ^1A to each other include cyclopropane, cyclobutane, cyclobutane, cyclopentane, cyclohexane and the like.

General formula (R-2) is demonstrated. R ^2A represents an alkyl group or an aryl group in which the total of three R ^2A satisfies 4 or more carbon atoms, and the plurality of R ^2A may be the same or different. As the alkyl group or aryl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group are preferable. Group, n-propyl group, n-butyl group, iso-propyl group, cyclohexyl group and phenyl group are more preferred, and ethyl group, n-propyl group, n-butyl group, iso-propyl group and phenyl group are still more preferred. R ^2A may have a substituent selected from the aforementioned substituent group A, if possible. Three R ^2A are not bonded to each other to form a ring.

General formula (R-3) is demonstrated. R ^3A represents an alkyl group or an aryl group, and the plurality of R ^3A may be the same or different. Examples of the alkyl group or aryl group include methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, tert-butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, and naphthyl group. A methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a cyclohexyl group, and a phenyl group are more preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso- A propyl group and a phenyl group are more preferable. R ^3A may have a substituent selected from the aforementioned substituent group A, if possible. A plurality of R ^3A may combine with each other to form a ring if possible. Examples of the ring formed by bonding a plurality of R ^3A to each other include bicyclo [2,2,2] octane, adamantane and the like.

  General formula (R-4) represents an isobutyl group.

General formula (R-5) is demonstrated. R ^5A represents an alkyl group or an aryl group in which the total of two R ^5A 's has 4 or more carbon atoms, and the plurality of R ^5A may be the same or different. As the alkyl group or aryl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group are preferable. Group, n-propyl group, n-butyl group, iso-propyl group, cyclohexyl group and phenyl group are more preferred, and ethyl group, n-propyl group, n-butyl group, iso-propyl group and phenyl group are still more preferred. R ^5A may have a substituent selected from the aforementioned substituent group A, if possible. A plurality of R ^5A may combine with each other to form a ring, if possible. Examples of the ring formed by bonding a plurality of R ^5A to each other include cyclopropane, cyclobutane, cyclobutane, cyclopentane, cyclohexane and the like.

  General formula (R-6) represents a 3-methyl-butyl group.

General formula (R-7) is demonstrated. s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-7) is 20 or less. s is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
When s = 1, R ^7A represents an alkyl group or an aryl group in which the total of the two R ^7As has 4 or more carbon atoms, and the plurality of R ^7A may be the same or different. As the alkyl group or aryl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group are preferable. Group, n-propyl group, n-butyl group, iso-propyl group, cyclohexyl group and phenyl group are more preferred, and ethyl group, n-propyl group, n-butyl group, iso-propyl group and phenyl group are still more preferred.
When s is greater than 1, R ^7A represents an alkyl group or an aryl group, and is a methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, tert-butyl group, cyclopropyl group, A cyclopentyl group, a cyclohexyl group, a phenyl group, and a naphthyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a cyclohexyl group, and a phenyl group are more preferable, and a methyl group, an ethyl group, An n-propyl group, an n-butyl group, an iso-propyl group, and a phenyl group are more preferable. R ^7A may have a substituent selected from the aforementioned substituent group A, if possible. A plurality of R ^7A may be bonded to each other to form a ring, if possible. ^Examples of the ring formed by bonding a plurality of R ^7A to each other include cyclopropane, cyclobutane, cyclobutane, cyclopentane, cyclohexane and the like.

General formula (R-8) is demonstrated. s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. s is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
R ^8A represents an alkyl group or an aryl group, and the plurality of R ^8A may be the same or different. Examples of the alkyl group or aryl group include methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group, tert-butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, and naphthyl group. A methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-propyl group, a cyclohexyl group, and a phenyl group are more preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso- A propyl group and a phenyl group are more preferable. R ^8A may have a substituent selected from the aforementioned substituent group A, if possible. A plurality of R ^8A may combine with each other to form a ring, if possible. Examples of the ring formed by bonding a plurality of R ^8A to each other include bicyclo [2,2,2] octane, adamantane and the like.

General formula (R-9) is demonstrated. s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. s is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle. As the aromatic ring forming an aryl group or heteroaryl group, benzene, naphthalene, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, pyrrole, imidazole, pyrazole, triazole are preferable, and benzene, thiophene, pyridine, thiazole, More preferred are pyrrole, imidazole, pyrazole and triazole, and even more preferred is benzene. Q ^9A may have a substituent selected from the aforementioned substituent group A, if possible.
As the substituent for R ^1A , R ^2A , R ^3A , R ^5A , R ^7A , R ^8A , and Q ^9A , an alkyl group, an aryl group, an alkoxy group, and a halogen atom are preferable, and an alkyl group and an aryl group are more preferable. is there.

M ²¹ represents a metal ion. The metal ion is not particularly limited, but monovalent to tetravalent metal ions are preferable, monovalent to trivalent metal ions are more preferable, and divalent metal ions are more preferable.
Specific examples of metal ions include aluminum ions, cobalt ions, nickel ions, copper ions, gallium ions, ruthenium ions, rhodium ions, palladium ions, silver ions, cerium ions, europium ions, tungsten ions, rhenium ions, osmium ions, Examples include iridium ions, platinum ions, gold ions, lead ions, and zinc ions.

  When the complex of the present invention is used as a light emitting material, the metal ions are preferably platinum ions, gold ions, iridium ions, rhenium ions, palladium ions, rhodium ions, ruthenium ions, tungsten ions, copper ions, and more preferably platinum ions. Ions, iridium ions, and rhenium ions, and more preferably platinum ions.

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

  Among the complexes represented by the general formula (1), the complex represented by the following general formula (1-a) is more preferable.

(In the general formula (1-a), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a substituent, provided that at least one of R ⁵¹ and R ⁵² represents the substituent R ¹ , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ each independently represent a hydrogen atom or a substituent, Q ⁵³ and Q ⁵⁴ are atoms bonded to a pyridine ring by a carbon atom and coordinated to a metal. L ⁵⁴ represents a single bond or a linking group, M ⁵¹ represents a metal ion, and the bond between the metal ion and Q ⁵³ or Q ⁵⁴ may be a covalent bond, a coordination bond or an ionic bond. n represents 0 or 1. However, when n = 0, Q ⁵³ and Q ⁵⁴ are not linked.)

Next, general formula (1-a) will be described. Q ⁵³ , Q ⁵⁴ , L ⁵⁴ , M ⁵¹ and n have the same meanings as Q ²³ , Q ²⁴ , L ²⁴ , M ²¹ and n in the general formula (1), respectively, and preferred ranges thereof are also the same. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a substituent. However, at least one of R ⁵¹ and R ⁵² has the same meaning as the group defined by R ¹ described above, and the preferred range is also the same. R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ each independently represent a hydrogen atom or a substituent. The substituent represented by R ^{53 to} R ⁵⁸ has the same meaning as in the substituent group A described above. R ^{53 to} R ⁵⁸ may be bonded to each other to form a ring, if possible.

When either one of R ⁵¹ and R ⁵² represents a group defined by the aforementioned substituent R ¹ , the other is a hydrogen atom or a substituent. The substituent is preferably a substituent selected from the following substituent B.
The substituent B is a primary alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, or a heterocyclic group, and more preferably a methyl group, an ethyl group, A group, an aryl group, and a heterocyclic group, more preferably a methyl group, an ethyl group, and an aryl group, and still more preferably a methyl group, an ethyl group, and a phenyl group.

R ⁵¹ and R ⁵² are more preferably groups defined by the aforementioned substituent R ¹ .

R ⁵³ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an alkylthio group, a sulfonyl group, and a hydroxy group. , A halogen atom, a cyano group, a nitro group and a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a cyano group and a heterocyclic group, still more preferably a hydrogen atom and a methyl group. , T-butyl group, trifluoromethyl group, phenyl group, fluorine atom, cyano group and pyridyl group, more preferably a hydrogen atom, methyl group and fluorine atom, and particularly preferably a hydrogen atom.

R ⁵⁴ and R ⁵⁷ are preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, or a heterocyclic group, more preferably A hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group and a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group and a heterocyclic group, and more preferably Is a hydrogen atom, methyl group, t-butyl group, dimethylamino group, diphenylamino group, methoxy group or carbazolyl group, particularly preferably a hydrogen atom.

Next, general formula (2) will be described. R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , L ⁶⁴ , M ⁶¹ , and n are R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R in the general formula (1-a). ⁵⁷ , R ⁵⁸ , L ⁵⁴ , M ⁵¹ , and n have the same meaning, and the preferred range is also the same. However, when n = 0, Q and Q are not connected. R ⁶¹ and R ⁶² each independently represents a hydrogen atom or a substituent. However, at least one of R ⁶¹ and R ⁶² has the same meaning as the group defined by R ¹ described above, and the preferred range is also the same.

When either one of R ⁶¹ and R ⁶² represents a group defined by the aforementioned substituent R ¹ , R ⁶² represents a hydrogen atom or a substituent. The substituent is preferably selected from the substituent B, and the preferred range is also synonymous.

R ⁶¹ and R ⁶² are both more preferably groups defined by the aforementioned substituent R ¹ .

Q is an atomic group including a coordinated carbon atom to a carbon atom and a metal that binds to a pyridine ring, the atom coordinating group with the carbon atom, as described in Q ²⁴ in the general formula (1) carbon An aromatic hydrocarbon group coordinated by an atom, a heterocyclic group coordinated by a carbon atom, and the like can be given.

  Q is preferably an aromatic ring group coordinated with a carbon atom, or a heterocyclic group coordinated with a carbon atom, more preferably benzene, naphthalene, thiophene, pyridine, pyrimidine, pyrrole, pyrazole, imidazole, More preferred are benzene and pyridine.

  Q may have a substituent, if possible, and examples of the substituent include the groups described in the substituent group A. The substituent for Q is preferably an alkyl group, an aryl group, a heterocyclic group or a cyano group, more preferably an alkyl group or a cyano group, still more preferably a trifluoromethyl group, a t-butyl group or a cyano group. is there.

  Q may form a condensed ring with other rings if possible. Examples of the ring condensed with Q include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, and a thiazole ring.

  Of the complexes represented by the general formulas (1), (1-a) and (2), the general formula (2) is preferable. The metal complex represented by the general formula (2) is preferably a platinum complex or a palladium complex, and most preferably a platinum complex.

  The compounds represented by the general formulas (1), (1-a) and (2) may be low molecular compounds, and oligomer compounds and polymer compounds (weight average molecular weight (polystyrene conversion) is preferably 1000 to 1000. 5000000, more preferably 2000 to 1000000, and still more preferably 3000 to 100,000. In the case of a polymer compound, structures represented by the general formulas (1), (1-a), and (2) 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 complex of the present invention is preferably a low molecular compound.

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

  Each element constituting the element of the present invention will be described in detail.

<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 organic light emitting layer.

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

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

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching 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., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

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

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

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

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

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

In the present invention, the cathode 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 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, a hole block Examples include layers such as a layer, an electron block 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 kind or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. The light emitting layer is preferably one using the complex of the present invention as a light emitting material, and more preferably composed of at least one kind of host material and the complex of the present invention.
In addition, 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 light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, di Various complexes such as ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivative complexes and pyromethene derivative complexes, Thiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material that can be used in the present invention include, in addition to the complex of the present invention, a complex containing a transition metal atom or a lanthanoid atom.
Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

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

  Examples of the host material contained in the light emitting layer in the present invention include, in addition to the metal complex of the present invention, those mentioned above, those having a carbazole skeleton, those having a diarylamine skeleton, and pyridine skeleton. Materials having a pyrazine skeleton, those having a triazine skeleton and those having an arylsilane skeleton, and materials exemplified in the section of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later Is mentioned.

  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 include, in addition to the complex of the present invention, a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, and a pyrazolone. Derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrins A layer containing a compound, an organic silane derivative, carbon or the like is preferable.

The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above-described materials, 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 include, in addition to the complex of the present invention, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a fluorenone derivative, an anthraquinodimethane derivative, an anthrone derivative, diphenylquinone. Derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles And a layer containing various complexes typified by complexes having benzothiazole as a ligand, organosilane derivatives, and the like.

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

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

  The method for forming the protective layer is not particularly limited, 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 element of this invention may seal the whole element using a sealing container. You may enclose a water | moisture-content absorber or an inert liquid in the space between a sealing container and an 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 element of the present invention can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.

  Regarding the driving method of the element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-214447, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, etc. can be applied.

  The element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

The complex of the present invention can be synthesized by using the method described in “Journal of Chemical Society, 5008, (1952)” and the like, and the synthesis method described later.
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, Bases (including various inorganic and organic solvents such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) in the presence or absence of a solvent. In the presence or absence of a base, it can be obtained by heating at room temperature or below or heating (in addition to normal heating, a method of heating with microwaves is also effective).

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

  The reaction temperature for synthesizing the complex of the present invention varies depending on the activity of the reaction and is not particularly limited, but is preferably 0 ° C. or higher and 300 ° C. or lower, more preferably 5 ° C. or higher and 250 ° C. or lower, more preferably 10 ° C. or higher and 220 ° C. or lower. Further preferred.

  In the complex of the present invention, the ligand forming the partial structure of the target complex complex is preferably from 0.1 equivalent to 20 equivalents, more preferably from 0.3 to 10 equivalents, more preferably from the metal compound. Preferably, it can be synthesized by adding 0.5 to 6 equivalents. Examples of the metal compound include metal halides (eg, platinum chloride, iridium chloride, etc.), metal acetates (eg, palladium acetate, zinc acetate, etc.), metal acetylacetonates (eg, iridium acetylacetonate, platinum acetylacetonate, etc.) ), Or hydrates thereof.

  Next, a typical synthesis method of the complex of the present invention will be described by taking the following tetradentate platinum complex as an example.

In the above formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ have the same meaning as in the general formula (1-a), and R ⁷¹ , R ⁷² , R ⁷³ And R ⁷⁴ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the above-described substituent group A.

The complex of the present invention is the method described in Journal of Organic Chemistry 53, 786, (1988), GR Newkome et al., Page 789, left line 53 to right line 7, page 790, left line 18 to 38. It can be obtained by the method described in the row, page 790, the method described in the right column, line 19-30, and a combination thereof. 1 to 1.2 equivalents of a base such as lithium diisopropylamide, potassium t-butoxide, sodium hydride at 0 ° C. to room temperature with respect to a solution of (A) in N, N-dimethylformamide, starting from compound (A) In addition, the reaction is allowed to proceed for about 30 minutes at 0 ° C. to room temperature. On the other hand, R ¹ X (R ¹ has the same meaning as that in the general formula (1) and X represents halogen) is represented by 1.5. After adding ~ 4 equivalents of alkyl halide and reacting at room temperature for about 30 minutes to monoalkylate, again under the same conditions, 1 to 1.2 equivalents of the above base and excess alkyl halide (R ¹ X) were added. By reacting, the dialkyl-substituted product (B) can be obtained in a yield of 70 to 99%.

  The step of obtaining (C) from (B) can be synthesized by the method described in Synth. Commun. 11, 513 (1981).

  In the step of obtaining the complex (D) of the present invention from (C), the compound (C) and 1 to 1.5 equivalents of platinum chloride are dissolved in benzonitrile and heated to 130 ° C. to the reflux temperature of the benzonitrile. (Boiling point: 191 ° C.) and stirring for 30 minutes to 4 hours. Compound (D) can be purified by recrystallization using chloroform or ethyl acetate, silica gel column chromatography, sublimation purification or the like.

  In the production methods shown above, when the defined substituents change under the conditions of a certain synthesis method or are inappropriate for carrying out the method, the functional groups are protected and deprotected (for example, , Protective Groups in Organic Synthesis, TW Greene, John Wiley & Sons Inc. (1981), etc.) It can be easily manufactured by such means. Moreover, it is also possible to change the order of reaction steps such as introduction of substituents as necessary.

[Comparative Example 1]
The cleaned ITO substrate was put into a vapor deposition apparatus, 10 nm of copper phthalocyanine was vapor-deposited, and NPD (N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) was vapor-deposited thereon by 40 nm. On top of this, compound (D-1) and mCP were deposited at a ratio of 30:70 (mass ratio) of 30 nm, and BAlq was deposited thereon at a thickness of 10 nm, on which Alq (tris (8-hydroxyquinoline) was deposited. Aluminum complex) was deposited by 30 nm. A patterned mask (with a light emission area of 4 mm × 5 mm) is placed on the obtained organic thin film, and 3 nm of lithium fluoride is deposited thereon, and 100 nm of aluminum is co-deposited thereon to produce an EL device. did. As a result of applying a constant DC voltage to the EL element and emitting light using a source measure unit 2400 type manufactured by Toyo Technica, blue-green light emission was observed, but a long-wave light emission component that seems to originate from the association is also present in the vicinity of 500 to 600 nm. Observed.

[Example 1]
In the light emitting device of Comparative Example 1, an EL device was produced in the same manner as Comparative Example 1 using the complex (8) of the present invention instead of the compound (D-1). As a result of applying a constant DC voltage to the EL element and emitting light using a source measure unit 2400 type manufactured by Toyo Technica, the long wave light emission component in the vicinity of 500 to 600 nm is reduced compared to Comparative Example 1, and the blue having improved color purity. Green emission was observed.

[Example 2]
In the light emitting device of Comparative Example 1, an EL device was produced in the same manner as Comparative Example 1 using the complex (10) of the present invention instead of the compound (D-1). As a result of applying a constant DC voltage to the EL element and emitting light using a source measure unit 2400 type manufactured by Toyo Technica, the long wave light emission component in the vicinity of 500 to 600 nm is reduced compared to Comparative Example 1, and the blue having improved color purity. Green emission was observed.

[Example 3]
In the light emitting device of Comparative Example 1, an EL device was produced in the same manner as Comparative Example 1 using the complex (11) of the present invention instead of the compound (D-1). As a result of applying a constant DC voltage to the EL element and emitting light using a source measure unit 2400 type manufactured by Toyo Technica, the long wave light emission component in the vicinity of 500 to 600 nm is reduced compared to Comparative Example 1, and the blue having improved color purity. Green emission was observed.

  An organic electroluminescent device having excellent light emission characteristics could be produced even with other devices using the complex of the present invention.

Claims (6)

An organic electroluminescent element having an organic compound layer including a light emitting layer between a pair of electrodes, wherein at least one metal complex having a tetradentate ligand represented by the following general formula (2) is used as the organic compound layer An organic electroluminescent element characterized by containing.
General formula (2)

(In General Formula (2), both R ⁶¹ and R ⁶² represent the following substituent R ¹ , or one of R ⁶¹ and R ⁶² represents the following substituent R ¹ , and the other represents a methyl group, ethyl R ⁶³ , R ⁶⁵ , R ⁶⁶ and R ⁶⁸ each independently represents a hydrogen atom, a methyl group or a fluorine atom, R ⁶⁴ and R ⁶⁷ each independently represent a hydrogen atom, and Q each independently represents a group or an aryl group. Represents a benzene ring or a pyridine ring, Q may have a substituent, if possible, and when Q has a substituent, the substituent is an alkyl group, a cyano group, a dimethylamino group, a fluorine atom. Or a methoxy group, Q may form a condensed ring with other rings if possible, and the ring condensed with Q is a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a thiophene ring, a furan Ring, pyrrole , An imidazole ring, a pyrazole ring, is .M ⁶¹ is an oxazole ring or a thiazole ring represents the 0 .n is representative of the platinum ions. However, in the case of n = 0, Q and Q are not connected.
Substituent R ¹ : Substituent R ¹ represents a C 3-20 alkyl group having a tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9).

In General Formula (R-1), R ^1A represents an alkyl group or an aryl group, and the plurality of R ^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In General Formula (R-2), R ^2A represents an alkyl group or an aryl group in which the total of three R ^2A satisfies 4 or more carbon atoms, and the plurality of R ^2A may be the same or different. good. However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents an alkyl group or an aryl group, and the plurality of R ^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In General Formula (R-5), R ^5A represents an alkyl group or an aryl group in which the total of two R ^5A satisfies 4 or more carbon atoms, and the plurality of R ^5A may be the same or different. good. A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the number of carbon atoms of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A is the sum of two R ^7A An alkyl group or an aryl group satisfying 4 or more carbon atoms is represented, and a plurality of R ^7A may be the same or different. When s is larger than 1, R ^7A represents an alkyl group or an aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents an alkyl group or an aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle. ) In the general formula (2), both R ⁶¹ and R ⁶² represent the substituent R ¹ , or one of R ⁶¹ and R ⁶² represents the substituent R ¹ , and the other represents a methyl group, an ethyl group, or The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device represents an aryl group, R ^{63 to} R ⁶⁸ are hydrogen atoms, Q is a benzene ring, and Q does not form a condensed ring with other rings. In the general formula (2), the organic electroluminescent device according to claim 1 or 2 wherein at least one of R ⁶¹ and R ^62, characterized in that an isobutyl group. The compound represented by following General formula (2).
General formula (2)

(In General Formula (2), both R ⁶¹ and R ⁶² represent the following substituent R ¹ , or one of R ⁶¹ and R ⁶² represents the following substituent R ¹ , and the other represents a methyl group, ethyl R ⁶³ , R ⁶⁵ , R ⁶⁶ and R ⁶⁸ each independently represents a hydrogen atom, a methyl group or a fluorine atom, R ⁶⁴ and R ⁶⁷ each independently represent a hydrogen atom, and Q each independently represents a group or an aryl group. Represents a benzene ring or a pyridine ring, Q may have a substituent, if possible, and when Q has a substituent, the substituent is an alkyl group, a cyano group, a dimethylamino group, a fluorine atom. Or a methoxy group, Q may form a condensed ring with other rings if possible, and the ring condensed with Q is a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a thiophene ring, a furan Ring, pyrrole , An imidazole ring, a pyrazole ring, is .M ⁶¹ is an oxazole ring or a thiazole ring represents the 0 .n is representative of the platinum ions. However, in the case of n = 0, Q and Q are not connected.
Substituent R ¹ : Substituent R ¹ represents a C 3-20 alkyl group having a tertiary or quaternary carbon represented by the following general formulas (R-1) to (R-9).

In General Formula (R-1), R ^1A represents an alkyl group or an aryl group, and the plurality of R ^1A may be the same or different. Two R ^1A's may be bonded to each other to form a ring.
In General Formula (R-2), R ^2A represents an alkyl group or an aryl group in which the total of three R ^2A satisfies 4 or more carbon atoms, and the plurality of R ^2A may be the same or different. good. However, three R ^2A are not bonded to each other to form a ring.
In General Formula (R-3), R ^3A represents an alkyl group or an aryl group, and the plurality of R ^3A may be the same or different. A plurality of R ^3A may be bonded to each other to form a ring.
In General Formula (R-5), R ^5A represents an alkyl group or an aryl group in which the total of two R ^5A satisfies 4 or more carbon atoms, and the plurality of R ^5A may be the same or different. good. A plurality of R ^5A may be bonded to each other to form a ring.
In general formula (R-7), s represents an integer of 1 or more. s can take any integer as long as the number of carbon atoms of the group represented by the general formula (R-7) is 20 or less, and when s = 1, R ^7A is the sum of two R ^7A An alkyl group or an aryl group satisfying 4 or more carbon atoms is represented, and a plurality of R ^7A may be the same or different. When s is larger than 1, R ^7A represents an alkyl group or an aryl group. A plurality of R ^7A may be bonded to each other to form a ring, if possible.
In general formula (R-8), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-8) is 20 or less. R ^8A represents an alkyl group or an aryl group, and the plurality of R ^8A may be the same or different. A plurality of R ^8A may be bonded to each other to form a ring.
In general formula (R-9), s represents an integer of 1 or more. s can take any integer as long as the carbon number of the group represented by the general formula (R-9) is 20 or less. Q ^9A represents an aryl group or heteroaryl group containing a carbon atom and forming an aromatic ring or an aromatic heterocycle. ) 4. The organic electric field according to claim 1, wherein the light emitting layer contains at least one compound represented by the general formula ( 2) and at least one host material. Light emitting element. The organic material according to any one of claims 1 to 3, wherein the light emitting layer contains at least one compound represented by the general formula ( 2) and at least one phosphorescent light emitting material. Electroluminescent device.