JP2007217364A - Novel metal complex and luminescent material obtained using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-emitting element that is capable of emitting light with high luminance and high efficiency and exhibits excellent durability, a metal complex employable for the light-emitting elements and applicable to materials for organoelectroluminescent elements, materials for electrochemiluminescent (ECL) elements, light-emitting sensors, photosensitizers, displays, fluorescent brighteners, photographic materials, laser pigments, dyes for color filters, optical communications, color conversion filters, backlights, illumination, photosensitizing pigments, various light sources and the like, and a light-emitting material using the compound. <P>SOLUTION: The metal complex is represented by general formula (1) (wherein M is iridium, platinum, rhodium or palladium; m is an integer of 1-3; n is an integer of 0-2; m+n=2 or 3; X<SP>1</SP>is an aliphatic hydrocarbon group (hydrogen atoms in the hydrocarbon group may be replaced by a fluorine atom); R<SP>1</SP>-R<SP>8</SP>are each independently a hydrogen atom or a substituent group; Q<SP>1</SP>is a counter anion; k is an integer of 1-3; and L is a bidentate ligand). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic electroluminescent element material, an electrochemiluminescence (ECL) element material, a light emitting sensor, a photosensitizer, a display, a fluorescent brightener, a photographic material, a laser dye, and a color filter. The present invention relates to a novel metal complex useful for dyes, optical communication, color conversion filters, backlights, illumination, photosensitizing dyes, various light sources and the like, and a luminescent material comprising the compound.

  Organic electroluminescent elements are attracting attention as display elements for next-generation portable information terminals and the like, and in recent years, various organic materials used for light-emitting elements have been actively developed.

  Here, with regard to the light emitting material, it can be broadly classified into a fluorescent material that utilizes light emission from an excited singlet and a phosphorescent material that utilizes light emission from an excited triplet. When light emission from an excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, so that the generation probability of luminescent excited species is 25%, and the light extraction efficiency is about Since it is 20%, the limit of the external extraction quantum efficiency is set to 5%.

  On the other hand, if an excited triplet can also be used for this, the upper limit of the internal quantum efficiency is 100%, so that in principle, the luminous efficiency is quadrupled compared to the case of an excited singlet. .

  Among them, ortho-metalated iridium complexes, which are phosphorescent materials typified by tris (2-phenylpyridine) iridium complex, are considered promising from the viewpoint of light emission efficiency, and are light emitting element materials that have attracted particular attention (patents). Reference 1). Therefore, in recent years, metal complexes used as light emitting element materials have been actively developed.

For example, as a compound related to the present invention, Patent Document 2 lists various iridium complexes. However, only iridium complexes that emit red-orange light represented by the following formula (A) are disclosed with specific demonstration examples, and no empirical support has been provided for other compounds. Furthermore, in this specification, the compound represented by the following formula (B) is exemplified as an iridium complex, but nothing is mentioned about a specific synthesis example or light emission characteristics.
Furthermore, Patent Document 3 discloses an iridium complex represented by the formula (C). This product exhibits blue light emission, but the light emission characteristics are still insufficient, and there is a problem in stability as a compound.

International Publication No. 00/70655 Pamphlet Japanese Patent Publication No. 2004-127598 Japanese Patent Publication No. 2005-298383

  An object of the present invention is to provide a light-emitting element that can emit light with high brightness and high efficiency and has excellent durability, and can be used for the light-emitting element. Materials for organic electroluminescent elements, electrochemiluminescence (ECL) element materials, light-emitting sensors , Photosensitizer, display, fluorescent brightener, photographic material, laser dye, color filter dye, optical communication, color conversion filter, backlight, illumination, photosensitizer dye, various light sources It is to provide a novel metal complex that can be applied to the above.

  As a result of intensive studies in view of the above situation, the present inventors have found that the novel metal complex represented by the general formula (1) or (2) has strong luminescence properties and is useful as a luminescent material. The present invention has been completed.

（一般式（１）中、Ｍはイリジウム、白金、ロジウムまたはパラジウムを表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎ＝２または３である。Ｘ^１は脂肪族炭化水素基（炭化水素基中の水素原子はフッ素原子に置換されても良い）を表す。Ｒ^１〜Ｒ^８は、各々独立に、水素原子または置換基を表す。Ｑ^１はカウンタ−アニオンを表す。ｋは１〜３の整数を表す。Ｌは２座配位子であり、２−フェニルキノリン誘導体、１−フェニルイソキノリン誘導体、３−フェニルイソキノリン誘導体、２−（２−ベンゾチオフェニル）ピリジン誘導体、２−チエニルピリジン誘導体、１−フェニルピラゾ−ル誘導体、１−フェニル−１Ｈ−インダゾ−ル誘導体、２−フェニルベンゾチアゾ−ル誘導体、２−フェニルチアゾ−ル誘導体、２−フェニルベンゾオキサゾ−ル誘導体、２−フェニルオキサゾ−ル誘導体、２−フラニルピリジン誘導体、２−（２−ベンゾフラニル）ピリジン誘導体、７，８−ベンゾキノリン誘導体、７，８−ベンゾキノキサリン誘導体、ジベンゾ[f,h]キノリン誘導体、ジベンゾ[f,h]キノキサリン誘導体、ベンゾ[h]−５，６−ジヒドロキノリン誘導体、９−（２−ピリジル）カルバゾ−ル誘導体、１−（２−ピリジル）インド−ル誘導体、１−（１−ナフチル）イソキノリン誘導体、１−（２−ナフチル）イソキノリン誘導体、２−（２−ナフチル）キノリン誘導体、２−（１−ナフチル）キノリン誘導体、３−（１−ナフチル）イソキノリン誘導体、３−（２−ナフチル）イソキノリン誘導体、２−（１−ナフチル）ピリジン誘導体、２−（２−ナフチル）ピリジン誘導体、６−フェニルフェナントリジン誘導体、６−（１−ナフチル）フェナントリジン誘導体、６−（２−ナフチル）フェナントリジン誘導体、ベンゾ[c]アクリジン誘導体、ベンゾ[c]フェナジン誘導体、ジベンゾ[a,c]アクリジン誘導体、ジベンゾ[a,c]フェナジン誘導体、２−フェニルキノキサリン誘導体、２，３−ジフェニルキノキサリン誘導体、２−ベンジルピリジン誘導体、２−フェニルベンゾイミダゾ−ル誘導体、３−フェニルピラゾ−ル誘導体、４−フェニルイミダゾ−ル誘導体、１−フェニルイミダゾ−ル誘導体、４−フェニルトリアゾ−ル誘導体、５−フェニルテトラゾ−ル誘導体、カルベン誘導体、２−アルケニルピリジン誘導体、２，２’−ビピリジン誘導体、１，１０−フェナントロリン誘導体、および、２，２’−ビキノリン誘導体である。）
〈２〉下記一般式（２）で表される金属錯体。

（一般式（２）中、Ｍはイリジウム、白金、ロジウムまたはパラジウムを表す。ｍは１〜３の整数を表す。ｎは０〜２の整数を表す。ｍ＋ｎ＝２または３である。Ｘ^１は脂肪族炭化水素基（炭化水素基中の水素原子はフッ素原子に置換されても良い）を表す。Ｒ^１〜Ｒ^８は、各々独立に、水素原子または置換基を表す。Ｑ^１はカウンタ−アニオンを表す。ｋは１〜３の整数を表す。Ａは−Ｃ（Ｒ^１５）−または−Ｎ−であり、Ｅは−Ｃ（Ｒ^１７）−または−Ｎ−である。Ｒ^１０〜Ｒ^１７は、各々独立に、水素原子又は置換基であり、Ｒ^１０〜Ｒ^１７の少なくとも１つは置換基である。Ｒ^１０〜Ｒ^１３よりなる群から選択された２つ以上の置換基、Ｒ^１３とＲ^１４、Ｒ^１４〜Ｒ^１７よりなる群から選択された２つ以上の置換基は、互いに連結されて飽和または不飽和の炭素環、飽和または不飽和のヘテロ環を形成していてもよい。）
〈３〉Ｒ^１０〜Ｒ^１７の少なくとも１つが、シアノ基、ヒドロキシ基、ニトロ基、トリフルオロメチル基、ハロゲン原子、置換または非置換の炭素原子数１〜２０のアルキル基、置換または非置換の炭素原子数１〜２０のアルコキシ基、置換または非置換の炭素原子数６〜２０のアリ−ル基、置換または非置換の炭素原子数７〜２０のアリ−ルアルキル基、置換または非置換の炭素原子数２〜２０のアルキルアルコキシ基、置換または非置換の炭素原子数７〜２０のアリ−ルアルコキシ基、置換または非置換の炭素原子数６〜２０のアリ−ルアミノ基、置換または非置換の炭素原子数１〜２０のアルキルアミノ基、置換または非置換の炭素原子数１〜２０のジアルキルアミノ基、または置換または非置換の炭素原子数２〜２０のヘテロ環基である前記２に記載の金属錯体。
〈４〉Ｒ^１０〜Ｒ^１７の少なくとも１つが、フェニル基、置換フェニル基、もしくは、それらを部分構造として含有する置換基である前記２又は３に記載の金属錯体。
〈５〉Ｒ^１４とＲ^１６のうち少なくとも１つが、フッ素原子である前記２乃至４何れかに記載の金属錯体。
〈６〉Ｒ^１５が電子吸引性基である前記２乃至５何れかに記載の金属錯体。
〈７〉Ａが−Ｃ（Ｒ^１５）−である前記２乃至６何れかに記載の金属錯体。
〈８〉Ａが−Ｎ−である前記２乃至７何れかに記載の金属錯体。
〈９〉Ｘ^１が炭素原子数１〜３０の脂肪族炭化水素基（炭化水素基中の水素原子はフッ素原子に置換されても良い）である前記１乃至８何れかに記載の金属錯体。
〈１０〉Ｍがイリジウムである前記１乃至９何れかに記載の金属錯体。
〈１１〉Ｍが白金である前記１乃至９何れかに記載の金属錯体。
〈１２〉前記１乃至１１何れかに記載の金属錯体からなる発光材料。
〈１３〉下記一般式（３）で表される部分構造を有する金属錯体からなる発光材料。

（一般式（３）中、Ｍはイリジウム、白金、ロジウムまたはパラジウムを表す。Ｘ^２は炭素原子数２〜３０の脂肪族炭化水素基（炭化水素基中の水素原子はフッ素原子に置換されても良い）である。Ｒ^１〜Ｒ^８は、各々独立に、水素原子または置換基を表す。）
〈１４〉Ｍがイリジウムである前記１３に記載の発光材料。
〈１５〉Ｍが白金である前記１３に記載の発光材料。
〈１６〉前記１２乃至１５何れかに記載の発光材料を用いた発光素子。 That is, according to this application, the following invention is provided.
<1> A metal complex represented by the following general formula (1).

(In general formula (1), M represents iridium, platinum, rhodium or palladium. M represents an integer of ^{1 to} 3. n represents an integer of 0 to 2. m + n = 2 or 3. X ¹ Represents an aliphatic hydrocarbon group (the hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, Q ¹ represents a counter -Represents an anion, k represents an integer of 1 to 3, L is a bidentate ligand, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothio) Phenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative, 1-phenyl-1H-indazole derivative, 2-phenylbenzothiazol derivative, 2-phenylthiazol derivative 2-phenylbenzoxazole derivative, 2-phenyloxazole derivative, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine derivative, 7,8-benzoquinoline derivative, 7,8-benzo Quinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 9- (2-pyridyl) carbazole derivatives, 1- (2 -Pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) quinoline derivatives, 3- (1-naphthyl) isoquinoline derivatives, 3- (2-naphthyl) isoquinoline derivatives, 2- (1-naphthyl) pyridine derivatives, 2- (2-na Til) pyridine derivatives, 6-phenylphenanthridine derivatives, 6- (1-naphthyl) phenanthridine derivatives, 6- (2-naphthyl) phenanthridine derivatives, benzo [c] acridine derivatives, benzo [c] phenazine derivatives Dibenzo [a, c] acridine derivatives, dibenzo [a, c] phenazine derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2-benzylpyridine derivatives, 2-phenylbenzimidazole derivatives, 3- Phenylpyrazole derivatives, 4-phenylimidazole derivatives, 1-phenylimidazole derivatives, 4-phenyltriazole derivatives, 5-phenyltetrazole derivatives, carbene derivatives, 2-alkenylpyridine derivatives, 2, A 2′-bipyridine derivative, a 1,10-phenanthroline derivative, and , A 2'-biquinoline derivatives. )
<2> A metal complex represented by the following general formula (2).

(In General Formula (2), M represents iridium, platinum, rhodium or palladium. M represents an integer of ^{1 to} 3. n represents an integer of 0 to 2. m + n = 2 or 3. X ¹ Represents an aliphatic hydrocarbon group (the hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, Q ¹ represents a counter - .A .k representing the anion represents an integer of 1 to 3 -C ^{(R 15)} - or a-N-, E is -C ^{(R 17)} - ^{or-N-.R 10} ~ R ¹⁷ is each independently a hydrogen atom or a substituent, and at least one of R ^{10 to} R ¹⁷ is a substituent, two or more substituents selected from the group consisting of R ^{10 to} R ¹³ ; R ¹³ and ^{R 14,} 2 or more substituents selected from the group consisting of R 14 ^{to R 17} , Are connected to each other saturated or unsaturated carbocyclic ring, it may form a heterocyclic ring, saturated or unsaturated.)
<3> At least one of R ^{10 to} R ¹⁷ is a cyano group, a hydroxy group, a nitro group, a trifluoromethyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon; An alkylalkoxy group having 2 to 20 atoms, a substituted or unsubstituted arylalkoxy group having 7 to 20 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 20 carbon atoms, a substituted or unsubstituted group; An alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted dialkylamino group having 1 to 20 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms; Metal complex according to one the two.
<4> The metal complex according to 2 or 3 above, wherein at least one of R ^{10 to} R ¹⁷ is a phenyl group, a substituted phenyl group, or a substituent containing them as a partial structure.
<5> The metal complex according to any one of 2 to 4, wherein at least one of R ¹⁴ and R ¹⁶ is a fluorine atom.
<6> The metal complex according to any one of 2 to 5, wherein R ¹⁵ is an electron-withdrawing group.
<7> The metal complex according to any one of 2 to 6, wherein A is —C (R ¹⁵ ) —.
<8> The metal complex according to any one of 2 to 7, wherein A is -N-.
<9> The metal complex according to any one of 1 to 8 above, wherein X ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms (a hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom).
<10> The metal complex according to any one of 1 to 9, wherein M is iridium.
<11> The metal complex according to any one of 1 to 9, wherein M is platinum.
<12> A light emitting material comprising the metal complex according to any one of 1 to 11 above.
<13> A luminescent material comprising a metal complex having a partial structure represented by the following general formula (3).

(In General Formula (3), M represents iridium, platinum, rhodium or palladium. X ² is an aliphatic hydrocarbon group having 2 to 30 carbon atoms (the hydrogen atom in the hydrocarbon group is substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent.)
<14> The luminescent material as described in 13 above, wherein M is iridium.
<15> The luminescent material as described in 13 above, wherein M is platinum.
<16> A light emitting device using the light emitting material according to any one of 12 to 15.

  Since the novel metal complex of the present invention exhibits high-luminance emission efficiently with low power consumption, the light-emitting element using the compound is a display element, a display, a backlight, electrophotography, an illumination light source, a recording light source, exposure. It is suitable for fields such as a light source, a reading light source, a sign, a signboard, and an interior. The compounds of the present invention can also be applied to medical uses, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, dyes for color filters, color conversion filters, optical communications, etc. is there. In addition, a high-efficiency white light-emitting element can be manufactured by combining a red light-emitting element and a red-orange light-emitting element based on a blue light-emitting element.

  The metal complex represented by the general formula (1) or (2) according to the present invention is a novel compound, and the experimental fact that they exhibit strong luminescence is a matter that has never been known so far. It is a new finding discovered for the first time by the accumulation of numerous detailed experiments. That is, the novel metal complex of the present invention is represented by the general formula (1) or (2), and by adding these novel iridium complexes to a light emitting layer of a light emitting element or a plurality of organic compound layers including a light emitting layer, A light emitting element having an excellent emission color in the light region can be obtained.

Hereinafter, the present invention will be described in more detail.
The compound of this invention should just have a structure represented by the said General formula (1) or (2), and may contain a tautomer. Further, the compound may have one transition metal atom or a so-called binuclear complex having two or more. Different metal atoms may be contained simultaneously.
Among the compounds represented by the general formula (1) or (2), the emission quantum yield in solution or in a solid state is preferably 0.01 or more, and more preferably 0.1 or more.

Symbols (R ^{1 to} R ⁸ , R ^{10 to} R ¹⁷ , M, X ¹ , X ² , L, Q ¹ , m, n, k, A, and the general formulas (1) to (3) E) will be described below.

R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, alkyl group, hydroxy group, mercapto group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group, and phenoxy group. Aryl group, alkoxy group, dialkylamino group, alkenyl group, alkynyl group, amino group, alkoxy group, aryloxy group, heteroaryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy Group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, sulfonyl group, sulfinyl group, ureido group, Phosphoric acid amide And a silyl group, these substituents may be further substituted. Preferably, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a substitution having 6 to 20 carbon atoms An aryl group, an alkoxy group having 1 to 20 carbon atoms, and a substituted alkoxy group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. 10 substituted alkyl groups. Most preferably, it is a hydrogen atom.

R ^{10 to} R ¹⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as 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, and particularly preferably carbon atoms). 2 to 10 such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon). 2 to 10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably carbon number) To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and the like, and amino groups (preferably having 0 to 0 carbon atoms). 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, and the like. (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), ant- Ruoxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably carbon 6-12, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1-30 carbons, more preferably having 1-20 carbons, especially Preferably it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc.), an acyl group (preferably C1-C30, more preferably C1-C20, especially preferably carbon) 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 2 carbon atoms). 12 and examples thereof include methoxycarbonyl and ethoxycarbonyl.), Arylo Xoxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more Preferably it has 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and arylthio group (preferably 6 carbon atoms). To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably carbon atoms). 1 to 20, particularly preferably 1 to 12 carbon atoms, and examples include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, and the like, and sulfonyl groups (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, a mesyl, a tosyl, etc. are mentioned. Rufinyl 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 methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, trifluoromethyl group, hydroxamic acid group, sulfino group, hydrazino group, imino group A heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, For example, nitrogen atom, oxygen atom, sulfur atom, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like can be mentioned. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl, triphenylsilyl, etc.), a silyloxy group (preferably carbon The number of carbon atoms is 3 to 40, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms. Examples thereof include trimethylsilyloxy and triphenylsilyloxy. Cyano group, hydroxy group, nitro group, trifluorome Group, halogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms A substituted or unsubstituted amino group having 0 to 10 carbon atoms, or a substituted or unsubstituted heterocyclic group having 1 to 12 carbon atoms. At least one of R ^{10 to} R ¹⁷ is a substituent.

Furthermore, two or more substituents selected from the group consisting of R ^{10 to} R ¹³ , two or more substituents selected from the group consisting of R ¹³ and R ¹⁴ , R ^{14 to} R ¹⁷ are connected to each other. It is also preferable to form a saturated or unsaturated carbocyclic ring or a saturated or unsaturated heterocyclic ring.

Further, at least one of R ^{10 to} R ¹⁷ is preferably a phenyl group, a substituted phenyl group, or a substituent containing them as a partial structure, and at least one of R ^{11 to} R ¹⁶ is a phenyl group More preferably a substituted phenyl group or a substituent containing them as a partial structure, and at least one of R ^{14 to} R ¹⁶ contains a phenyl group, a substituted phenyl group, or a partial structure thereof. Particularly preferred is a substituent. Wherein the substituents of the substituted phenyl group are the same as the substituents of R ¹⁰ to R ^17, is also desirable range same. The substituent containing a phenyl derivative represents, for example, a fluorene group, a fluorenone group, a carbazole group, a dibenzothiophene group, a dibenzofuran group, or the like.

Further, at least one of R ¹⁴ or R ¹⁶ is preferably a hydrogen atom, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aryl group, or a heterocyclic group, An atom, an alkyl group, and a fluorine atom are more preferable, and a hydrogen atom and a fluorine atom are more preferable. Preferably, at least one of R ¹⁴ or ^{R 16} is a fluorine ^atom, more preferably ^{R 14} and ^{R 16} are both fluorine atoms.

R ¹⁵ is preferably an electron-withdrawing group. Examples of the electron withdrawing group include a cyano group, a trifluoromethyl group, a pentafluorophenyl group, an acyl group, a sulfonyl group, and a halogen atom, and preferably a trifluoromethyl group, a cyano group, a trifluoromethyl group, a penta A fluorophenyl group and a fluorine atom, more preferably a cyano group, a trifluoromethyl group, and a pentafluorophenyl group. R ¹⁴ or ^{R 16} is a fluorine ^atom, it is preferred that ^{R 15} is an electron-withdrawing ^{group, R 14} and ^{R 16} are both fluorine ^atoms, and more preferably ^{R 15} is an electron-withdrawing group.

R ¹¹ and R ¹³ are each preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group. R ¹⁰ is preferably a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group or a dialkylamino group, more preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group, and most preferably a hydrogen atom. R ¹² is preferably a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group or a dialkylamino group, more preferably a hydrogen atom, a fluorine atom, an alkyl group or an alkoxy group.

  In the general formulas (1) to (3), M is iridium, platinum, rhodium, and palladium, preferably iridium or platinum, and particularly preferably iridium.

X ¹ represents an aliphatic hydrocarbon group (a hydrogen atom in the hydrocarbon may be substituted with a fluorine atom). Among the aliphatic hydrocarbon groups, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group are preferable, and an alkyl group and a substituted alkyl group are more preferable. These groups may be linear or branched, and a part of hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms. These substituents are synonymous with the substituents of R ^{10 to} R ¹⁷ , and the desirable ranges are also the same. Among the aliphatic hydrocarbon group used as X ^1, preferably having 1 to 50 carbon atom, more preferably 1 to 30 carbon atoms. Furthermore, from a viewpoint of improving the solubility to the solvent of this invention compound, C2-C30 is preferable, C3-C30 is more preferable, and C5-C30 is especially preferable.

X ² represents an aliphatic hydrocarbon group (a hydrogen atom in the hydrocarbon may be substituted with a fluorine atom). Among the aliphatic hydrocarbon groups, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group are preferable, and an alkyl group and a substituted alkyl group are more preferable. These groups may be linear or branched, and a part of hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms. These substituents are synonymous with the substituents of R ^{10 to} R ¹⁷ , and the desirable ranges are also the same. The number of carbon atoms of the aliphatic hydrocarbon group used as X ² is 2 to 30, and from the viewpoint of further improving the solubility of the compound of the present invention in a solvent, 3 to 30 carbon atoms are more preferable, The number 5 to 30 is particularly preferable.

  m represents an integer of 1 to 3, n represents an integer of 0 to 2, and m + n = 2 or 3. m = 1 or 2 is preferable, and m = 1 is particularly preferable. n represents an integer of 0 to 2. When M is iridium or rhodium, n = 1 or 2 is preferable, and n = 2 is particularly preferable. When M is platinum and palladium, n = 1 or 2 is preferable, and n = 1 is particularly preferable.

Q ¹ represents a counter-anion. The counter anion is not particularly limited, but is preferably an alkali metal ion, alkaline earth metal ion, halogen ion, perchlorate ion, PF ₆ ion, ammonium ion, CF ₃ CF ₂ CF ₂ COO ion, SbF _6. An ion, a dicyanamide ion, a bis (trifluoromethanesulfonyl) amide ion, a borate ion or a phosphonium ion.

  k represents an integer of 1 to 3. k = 1 or 2 is preferred, and k = 1 is particularly preferred.

A represents —C (R ¹⁵ ) — or —N—.

E represents -C (R < ¹⁷ >)-or -N-, more preferably -C (R < ¹⁷ >)-.

In the general formula (2), examples of a preferable structure of the bidentate ligand composed of R ^{10 to} R ¹⁷ , A, E, a nitrogen atom, and a carbon atom include the ligands shown in Table 1. However, the present invention is not limited to this.

  L is a bidentate ligand, and includes 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazo- Derivatives, 1-phenyl-1H-indazole derivatives, 2-phenylbenzothiazol derivatives, 2-phenylthiazol derivatives, 2-phenylbenzoxazole derivatives, 2-phenyloxazole derivatives, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine derivative, 7,8-benzoquinoline derivative, 7,8-benzoquinoxaline derivative, dibenzo [f, h] quinoline derivative, dibenzo [f, h] quinoxaline derivative , Benzo [h] -5,6-dihydroquinoline derivative, 9- (2-pyridyl) carbazole derivative 1- (2-pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) Quinoline derivatives, 3- (1-naphthyl) isoquinoline derivatives, 3- (2-naphthyl) isoquinoline derivatives, 2- (1-naphthyl) pyridine derivatives, 2- (2-naphthyl) pyridine derivatives, 6-phenylphenanthridine derivatives , 6- (1-naphthyl) phenanthridine derivative, 6- (2-naphthyl) phenanthridine derivative, benzo [c] acridine derivative, benzo [c] phenazine derivative, dibenzo [a, c] acridine derivative, dibenzo [ a, c] phenazine derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2-benzylpyridi Derivatives, 2-phenylbenzimidazole derivatives, 3-phenylpyrazole derivatives, 4-phenylimidazole derivatives, 1-phenylimidazole derivatives, 4-phenyltriazole derivatives, 5-phenyltetrazole derivatives Derivatives, carbene derivatives, 2-alkenylpyridine derivatives, 2,2′-bipyridine derivatives, 1,10-phenanthroline derivatives, and 2,2′-biquinoline derivatives,

  Preferably, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazol derivative, 1-phenyl- 1H-indazole derivative, 2-phenylbenzothiazol derivative, 2-phenylthiazol derivative, 2-phenylbenzoxazole derivative, 2-phenyloxazole derivative, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine derivative, 7,8-benzoquinoline derivative, 7,8-benzoquinoxaline derivative, dibenzo [f, h] quinoline derivative, dibenzo [f, h] quinoxaline derivative, benzo [h] -5 , 6-Dihydroquinoline derivative, 9- (2-pyridyl) carbazole derivative, 1- (2 -Pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) quinoline derivatives, 3- (1-naphthyl) isoquinoline derivative, 3- (2-naphthyl) isoquinoline derivative, 2- (1-naphthyl) pyridine derivative, 2- (2-naphthyl) pyridine derivative, 6-phenylphenanthridine derivative, 6- (1 -Naphthyl) phenanthridine derivatives, 6- (2-naphthyl) phenanthridine derivatives, benzo [c] acridine derivatives, benzo [c] phenazine derivatives, dibenzo [a, c] acridine derivatives, dibenzo [a, c] phenazine Derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2-benzylpyridine derivatives, 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltriazole derivative, 5-phenyltetrazole derivative, A carbene derivative and a 2-alkenylpyridine derivative,

  More preferably, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothiophenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazol derivative, 1-phenyl -1H-indazole derivatives, 2-phenylbenzothiazol derivatives, 2-phenylthiazol derivatives, 2-phenylbenzoxazole derivatives, 2-phenyloxazole derivatives, 2-furanylpyridine derivatives 2- (2-benzofuranyl) pyridine derivatives, 7,8-benzoquinoline derivatives, 7,8-benzoquinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h]- 5,6-dihydroquinoline derivatives, 9- (2-pyridyl) carbazole derivatives, 1- (2-pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) quinoline derivatives, 3- (1-naphthyl) isoquinoline derivative, 3- (2-naphthyl) isoquinoline derivative, 2- (1-naphthyl) pyridine derivative, 2- (2-naphthyl) pyridine derivative, 6-phenylphenanthridine derivative, 6- (1-naphthyl) phenanthridine derivatives, 6- (2-naphthyl) phenanthridine derivatives, benzo [c] acridine derivatives, benzo [c] phenazine derivatives, dibenzo [a, c] acridine derivatives, dibenzo [a, c ] Phenazine derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2-benzylpyridine derivatives 2-phenylbenzimidazole derivative, 3-phenylpyrazole derivative, 4-phenylimidazole derivative, 1-phenylimidazole derivative, 4-phenyltriazole derivative, 5-phenyltetrazole Derivatives and 2-alkenylpyridine derivatives.

  Examples of L described in the general formula (1) are shown in Tables 2 to 4, but the present invention is not limited thereto. R in Tables 2 to 4 is a hydrogen atom or a substituent.

Examples of L described in the general formula (1) include carbene derivatives. For example, the following ligands described in International Publication WO2005 / 113704 are preferably used.

  The valence of the central metal of the compound of the present invention represented by the general formulas (1) to (3) will be described. Trivalent is preferable when M is iridium or rhodium. In the case of platinum and palladium, divalent is preferable.

  Further, the iridium complex represented by the general formula (1) or (2) is a low-molecular compound or includes a repeating unit having a partial structure represented by the general formula (1) or (2). , So-called oligomer compounds and polymer compounds (mass average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 1000000, and still more preferably 3000 to 100000).

Formula (1) in ^{~ (3), R 1 ~R} 8, X 1 ( or ^X 2), and, for bidentate be described consists of a nitrogen atom. As for the bidentate ligand, a commercially available product may be used, and a method using a method reported in the past (for example, the method described in Polyhedron, 2001, Vol. 20, p. 2935) may be used. It can be easily synthesized as in (D).

Preferred examples of the bidentate ligand are shown in Table 5.

In order to produce the metal complex represented by the general formula (1) or (2) according to the present invention, for example, according to the formula (E) or the formula (F), the crosslinking dimer and the ligand are converted into a usual method ( The reaction may be performed in the presence or absence of a solvent, in the presence or absence of a base, in the presence or absence of a silver compound as a dehalogenating agent, at room temperature or by heating. It is also preferable to carry out the reaction in a nitrogen atmosphere or an argon atmosphere. Further, the heating means is not particularly limited, but it is also preferable to irradiate microwaves in order to facilitate the reaction. Although there is no restriction | limiting in particular in the wavelength of a microwave, It is 2000-3000 MHz, Preferably it is 2400-2500 MHz. As the microwave oscillating device, all commercially available conventionally known oscillating devices can be applied. Moreover, you may use an oil bath, a mantle heater, etc. as a heating means. The crosslinking dimer can be easily obtained by using, for example, the method described in Inorganic Chemistry, 2001, 40, 1704, Inorganic Chemistry, 2002, 41, 3055.

  Further, it is desirable to use a reaction solvent in order to further facilitate the reaction. Although there is no restriction | limiting in particular as such a solvent, An alcohol solvent, a protic solvent, an aprotic solvent, a nitrile solvent etc. are used preferably, Specifically, chloroform, a dichloromethane, 2-methoxyethanol- , 2-ethoxyethanol, methanol, ethanol, acetonitrile and the like are preferred.

  In addition, when producing the iridium complex represented by the general formula (1) or (2), the reaction temperature, reaction pressure, and reaction time vary depending on the raw materials used, the output of the microwave, the solvent, etc. The reaction temperature is 40 to 200 ° C, preferably 50 to 150 ° C, and the reaction pressure is 1 to 30 atm, preferably 1 to 5 atm.

  The iridium complex according to the present invention can be provided after being treated according to the post-treatment of a normal synthesis reaction, and if necessary, with or without purification. As a post-treatment method, for example, extraction, cooling, crystallization by adding water or an organic solvent, an operation of distilling off the solvent from the reaction mixture, and the like can be performed alone or in combination. As a purification method, recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.

  Although the typical example of the iridium complex shown by the said General formula (1) or (2) based on this invention below is shown, this invention is not limited to these.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to this.
[Synthesis of Compound of the Present Invention]

Example 1 (Synthesis of Compound (K-1) of the Present Invention)
50 mg of the crosslinked dimer (D-1), 27 mg of the ligand (L-1), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 90 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-1), and the isolated yield was 89%.
Electro-spray ionization mass spectrometry: m / z = 758.6
¹ H-NMR (CDCl ₃ ) d 8.35 (d, 2H), 8.08 (d, 2H), 7.88-7.96 (m, 4H), 7.62 (d, 2H), 7.58 (d, 2H), 7.23 (dd, 2H), 6.93 (dd, 2H), 6.50 (dd, 2H), 5.63 (d, 2H), 3.54 (s, 3H).

Example 2 (Synthesis of the present compound (K-2))
50 mg of the crosslinked dimer (D-1), 35 mg of the ligand (L-5), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 90 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-2), and the isolation yield was 90%.
Electro-spray ionization mass spectrometry: m / z = 814.7
¹ H-NMR (CDCl ₃ ) d 8.36 (d, 2H), 7.93-7.97 (m, 4H), 7.89 (dd, 2H), 7.60-7.65 (m, 4H), 7.18 (dd, 2H), 6.96 ( dd, 2H), 6.51 (dd, 2H), 5.61 (d, 2H), 4.24 (dd, 1H), 3.69 (dd, 1H), 0.60-1.36 (m, 9H).

Example 3 (Synthesis of the present compound (K-3))
50 mg of the crosslinked dimer (D-1), 41 mg of the ligand (L-7), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was put into a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 60 minutes while argon gas was passed through. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-3), and the isolation yield was 77%.
Electro-spray ionization mass spectrometry: m / z = 856.9
¹ H-NMR (CDCl ₃ ) d 8.38 (d, 2H), 7.90-7.99 (m, 6H), 7.70-7.75 (m, 2H), 7.48 (d, 2H), 7.16 (dd, 2H), 7.02 ( dd, 2H), 6.55 (dd, 2H), 5.66 (d, 2H), 4.15 (dd, 1H), 3.65 (dd, 1H), 0.60--1.38 (m, 15H).

Example 4 (Synthesis of the present compound (K-5))
50 mg of the crosslinking dimer (D-2), 31 mg of the ligand (L-5), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 120 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-5), and the isolation yield was 92%.
Electro-spray ionization mass spectrometry: m / z = 894.8
¹ H-NMR (CDCl ₃ ) d 8.07 (d, 2H), 8.02 (brs, 2H), 7.86-7.94 (m, 6H), 7.79 (brs, 2H), 7.61 (d, 2H), 7.54 (d, 4H), 7.40 (dd, 4H), 7.30 (dd, 2H), 7.19 (dd, 2H), 7.13 (d, 2H), 6.91 (t, 2H), 6.31 (d, 2H), 4.25 (dd, 1H ), 3.72 (dd, 1H), 0.70-1.41 (m, 9H).

Example 5 (Synthesis of the present compound (K-18))
50 mg of the crosslinked dimer (D-3), 31 mg of the ligand (L-5), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 120 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-18), and the isolated yield was 76%.
Electro-spray ionization mass spectrometry: m / z = 894.8
¹ H-NMR (CDCl ₃ ) d 7.97-8.03 (m, 4H), 7.91 (dd, 2H), 7.85 (dd, 2H), 7.80 (brs, 2H), 7.71 (d, 2H), 7.61 (d, 2H), 7.29-7.34 (m, 8H), 7.22-7.28 (m, 4H), 7.13 (dd, 2H), 6.89 (dd, 2H), 6.45 (d, 2H), 4.25 (dd, 1H), 3.72 (dd, 1H), 0.70--1.38 (m, 9H).

Example 6 (Synthesis of Compound (K-13) of the present invention)
50 mg of the crosslinked dimer (D-4), 25 mg of the ligand (L-1), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 90 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained orange solid was dissolved in a mixed solvent of ethanol and water, and NH ₄ PF ₆ saturated aqueous solution was added dropwise to obtain an orange solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-13), and the isolation yield was 96%.
Electro-spray ionization mass spectrometry: m / z = 786.6
¹ H-NMR (CDCl ₃ ) d 8.92 (d, 2H), 8.23 (d, 2H), 7.98 (d, 2H), 7.93 (d, 2H), 7.86 (dd, 2H), 7.82 (dd, 2H) , 7.78 (dd, 2H), 7.56 (d, 4H), 7.48 (d, 2H), 7.04 (dd, 2H), 6.77−6.83 (m, 4H), 6.33 (d, 2H), 3.52 (s, 3H ).

Example 7 (Synthesis of the present compound (K-15))
50 mg of the crosslinked dimer (D-5), 28 mg of the ligand (L-1), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 90 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-15), and the isolation yield was 92%.
Electro-spray ionization mass spectrometry: m / z = 734.6
¹ H-NMR (CDCl ₃ ) d 8.48 (d, 2H), 8.35 (d, 2H), 7.81-7.86 (m, 4H), 7.70 (d, 4H), 7.61 (dd, 2H), 7.58 (d, 2H), 7.39 (d, 2H), 7.05 (t, 2H), 6.72 (dd, 2H), 6.13 (d, 2H), 3.61 (s, 3H).

Example 8 (Synthesis of Compound (K-19) of the present invention)
50 mg of the crosslinked dimer (D-6), 32 mg of the ligand (L-7), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. The eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 4 hours while flowing argon gas. After cooling the reaction solution to room temperature, argon gas was stopped and the reaction solution was filtered. Then, the solvent was depressurizingly distilled for the filtrate using the evaporator. The obtained red solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a red solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-19).
Electro-spray ionization mass spectrometry: m / z = 1038.8

Example 9 (Synthesis of Compound (K-4) of the present invention)
50 mg of the crosslinked dimer (D-7), 41 mg of the ligand (L-7), and 10 ml of 2-ethoxyethanol were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 90 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a brown solid. This was separated and purified using alumina column chromatography (eluent: mixed solvent of dichloromethane and methanol) to obtain a yellow solid. Furthermore, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired iridium complex (K-4), and the isolated yield was 35%.
Electro-spray ionization mass spectrometry: m / z = 858.6
¹ H-NMR (CD ₂ Cl ₂ ) d 8.39 (d, 2H), 8.00-8.05 (m, 4H), 7.95 (brs, 2H), 7.65 (brs, 2H), 7.54 (d, 2H), 7.30 ( dd, 2H), 7.06 (dd, 2H), 5.65 (s, 2H), 4.18 (dd, 1H), 3.69 (dd, 1H), 0.59-1.37 (m, 15H).

Example 10 (Synthesis of the present compound (K-10))
Cross-linked dimer (D-8) (40 mg), ligand (L-7) (47 mg) and 2-ethoxyethanol (10 ml) were placed in an eggplant flask. This eggplant flask was placed in a microwave synthesizer (MicroSYNTH manufactured by Milestone General), and irradiated with microwaves (2450 MHz) for 120 minutes while venting argon gas. After the reaction solution was cooled to room temperature, the argon gas was stopped and the solvent was distilled off under reduced pressure. The obtained yellow solid was dissolved in a mixed solvent of ethanol and water, and a saturated aqueous NH ₄ PF ₆ solution was added dropwise to obtain a yellow solid. Then, it recrystallized with dichloromethane-hexane. As a result of analysis by electro-spray ionization mass spectrometry and proton NMR, the obtained compound was the desired platinum complex (K-10), and the isolation yield was 20%.
Electro-spray ionization mass spectrometry: m / z = 669.3

The light emission characteristics of the compound of the present invention are shown below.

Example 11 (Luminescence of the Compound (K-1) of the Present Invention)
After dissolving (K-1) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Wavelengths: 457 nm and 486 nm). The quantum yield of the luminescence was 0.29 according to the method described in “Study on New Experimental Chemistry 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing). Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 12 (Luminescence of the present compound (K-2))
After dissolving (K-2) in THF and venting with argon gas, an emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Wavelengths: 457 nm and 486 nm). The luminescence quantum yield was measured to be 0.35 according to the method described in “New Experimental Chemistry Lecture 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing) ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 13 (Emission of Compound (K-3) of the Present Invention)
After dissolving (K-3) in THF and venting with argon gas, the emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using RF-5300PC manufactured by Shimadzu Corporation. Wavelengths: 457 nm and 486 nm). According to the method described in “Study on New Experimental Chemistry 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing), the quantum yield of the luminescence was measured to be 0.34 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 14 (Luminescence of the present compound (K-5))
After dissolving (K-5) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Wavelengths: 494 nm and 524 nm). The quantum yield of the luminescence was measured according to the method described in “Study on New Experimental Chemistry 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing) and found 0.27 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 15 (Luminescence of the present compound (K-18))
After dissolving (K-18) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Maximum wavelengths: 521 nm and 556 nm). The quantum yield of the luminescence was measured according to the method described in “New Experimental Chemistry Lecture 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing), and was 0.60 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 16 (Luminescence of the present compound (K-13))
After dissolving (K-13) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Maximum wavelength: 650 nm). According to the method described in “New Experimental Chemistry Lecture 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing), the quantum yield of the luminescence was measured to be 0.32 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 17 (Emission of Compound (K-15) of the Present Invention)
After dissolving (K-15) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation. Maximum wavelength: 521 nm). According to the method described in “New Experimental Chemistry Lecture 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing), the quantum yield of the luminescence was 0.68 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Example 18 (Luminescence of the present compound (K-19))
After dissolving (K-19) in THF and venting with argon gas, the emission spectrum at room temperature (excitation wavelength: 350 nm) was measured using RF-5300PC manufactured by Shimadzu Corporation, and showed strong red light emission. .

Example 19 (Luminescence of the present compound (K-4))
After dissolving (K-4) in THF and venting with argon gas, the emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using RF-5300PC manufactured by Shimadzu Corporation. Wavelengths: 440 nm and 469 nm). The quantum yield of the luminescence was measured according to the method described in “Study on New Experimental Chemistry 4 Basic Technology 3 Light (II) Chapter 8 Measurement of Fluorescence and Phosphorescence” (Maruzen Publishing) and found 0.72 ( Based on a quantum yield of 0.546 in 0.5 M sulfuric acid solution of quinine sulfate).

Comparative Example 1
An iridium complex of the formula (C) described in Japanese Patent Publication No. 2005-298383 was synthesized, and an emission spectrum (excitation wavelength: 350 nm) was measured in room temperature THF. The iridium complex represented by the above formula (C) showed blue emission, but the emission quantum yield was 0.008, which was very low compared to the compound of the present invention.

  From the above examples, the compound of the present invention represented by the general formula (1) or (2) has strong luminescence and is useful as a luminescent material exhibiting various luminescent colors (blue to green to red), Materials for organic electroluminescent elements, electrochemiluminescence (ECL) element materials, luminescence sensors, photosensitizers, displays, fluorescent brighteners, photographic materials, laser dyes, dyes for color filters, light It can be applied to communication, color conversion filters, backlights, illumination, photosensitizing dyes, various light sources, and the like.

Emission spectrum of the present compound (K-1) in THF at room temperature Emission spectrum of the present compound (K-2) in THF at room temperature Emission spectrum of the present compound (K-3) in room temperature THF Emission spectrum of the present compound (K-5) in THF at room temperature Emission spectrum of the present compound (K-15) in THF at room temperature Emission spectrum of the present compound (K-18) in THF at room temperature

Claims (16)

A metal complex represented by the following general formula (1).

(In general formula (1), M represents iridium, platinum, rhodium or palladium. M represents an integer of ^{1 to} 3. n represents an integer of 0 to 2. m + n = 2 or 3. X ¹ Represents an aliphatic hydrocarbon group (the hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, Q ¹ represents a counter -Represents an anion, k represents an integer of 1 to 3, L is a bidentate ligand, 2-phenylquinoline derivative, 1-phenylisoquinoline derivative, 3-phenylisoquinoline derivative, 2- (2-benzothio) Phenyl) pyridine derivative, 2-thienylpyridine derivative, 1-phenylpyrazole derivative, 1-phenyl-1H-indazole derivative, 2-phenylbenzothiazol derivative, 2-phenylthiazol derivative 2-phenylbenzoxazole derivative, 2-phenyloxazole derivative, 2-furanylpyridine derivative, 2- (2-benzofuranyl) pyridine derivative, 7,8-benzoquinoline derivative, 7,8-benzo Quinoxaline derivatives, dibenzo [f, h] quinoline derivatives, dibenzo [f, h] quinoxaline derivatives, benzo [h] -5,6-dihydroquinoline derivatives, 9- (2-pyridyl) carbazole derivatives, 1- (2 -Pyridyl) indole derivatives, 1- (1-naphthyl) isoquinoline derivatives, 1- (2-naphthyl) isoquinoline derivatives, 2- (2-naphthyl) quinoline derivatives, 2- (1-naphthyl) quinoline derivatives, 3- (1-naphthyl) isoquinoline derivatives, 3- (2-naphthyl) isoquinoline derivatives, 2- (1-naphthyl) pyridine derivatives, 2- (2-na Til) pyridine derivatives, 6-phenylphenanthridine derivatives, 6- (1-naphthyl) phenanthridine derivatives, 6- (2-naphthyl) phenanthridine derivatives, benzo [c] acridine derivatives, benzo [c] phenazine derivatives Dibenzo [a, c] acridine derivatives, dibenzo [a, c] phenazine derivatives, 2-phenylquinoxaline derivatives, 2,3-diphenylquinoxaline derivatives, 2-benzylpyridine derivatives, 2-phenylbenzimidazole derivatives, 3- Phenylpyrazole derivatives, 4-phenylimidazole derivatives, 1-phenylimidazole derivatives, 4-phenyltriazole derivatives, 5-phenyltetrazole derivatives, carbene derivatives, 2-alkenylpyridine derivatives, 2, A 2′-bipyridine derivative, a 1,10-phenanthroline derivative, and , A 2'-biquinoline derivatives. ) A metal complex represented by the following general formula (2).

(In General Formula (2), M represents iridium, platinum, rhodium or palladium. M represents an integer of ^{1 to} 3. n represents an integer of 0 to 2. m + n = 2 or 3. X ¹ Represents an aliphatic hydrocarbon group (the hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, Q ¹ represents a counter - .A .k representing the anion represents an integer of 1 to 3 -C ^{(R 15)} - or a-N-, E is -C ^{(R 17)} - ^{or-N-.R 10} ~ R ¹⁷ is each independently a hydrogen atom or a substituent, and at least one of R ^{10 to} R ¹⁷ is a substituent, two or more substituents selected from the group consisting of R ^{10 to} R ¹³ ; R ¹³ and ^{R 14,} 2 or more substituents selected from the group consisting of R 14 ^{to R 17} , Are connected to each other saturated or unsaturated carbocyclic ring, it may form a heterocyclic ring, saturated or unsaturated.) At least one of R ^{10 to} R ¹⁷ is a cyano group, a hydroxy group, a nitro group, a trifluoromethyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon atom number. 1 to 20 alkoxy groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl groups having 7 to 20 carbon atoms, substituted or unsubstituted carbon atoms 2 -20 alkyl alkoxy groups, substituted or unsubstituted aryl alkoxy groups having 7 to 20 carbon atoms, substituted or unsubstituted aryl amino groups having 6 to 20 carbon atoms, substituted or unsubstituted carbon atoms An alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted dialkylamino group having 1 to 20 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms; Metal complex according to Motomeko 2. The metal complex according to claim 2 or 3, wherein at least one of R ^{10 to} R ¹⁷ is a phenyl group, a substituted phenyl group, or a substituent containing them as a partial structure. The metal complex according to claim 2, wherein at least one of R ¹⁴ and R ¹⁶ is a fluorine atom. 6. The metal complex according to claim 2, wherein R ¹⁵ is an electron withdrawing group. A is -C ^{(R 15)} - a metal complex according to any one of claims 2 to 6. The metal complex according to any one of claims 2 to 7, wherein A is -N-. The metal complex according to any one of claims 1 to 8, wherein X ¹ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms (a hydrogen atom in the hydrocarbon group may be substituted with a fluorine atom). The metal complex according to any one of claims 1 to 9, wherein M is iridium. The metal complex according to claim 1, wherein M is platinum. A light emitting material comprising the metal complex according to claim 1. A light emitting material comprising a metal complex having a partial structure represented by the following general formula (3).

(In General Formula (3), M represents iridium, platinum, rhodium or palladium. X ² is an aliphatic hydrocarbon group having 2 to 30 carbon atoms (the hydrogen atom in the hydrocarbon group is substituted with a fluorine atom) R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent.) The luminescent material according to claim 13, wherein M is iridium. The luminescent material according to claim 13, wherein M is platinum. A light emitting device using the light emitting material according to claim 12.

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