JP2008239565A - Iridium complex, method for producing the same and organic electroluminescence by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescence (EL) improving the light-emitting efficiency and life of the organic EL element by examing a method for synthesizing a compound having an N, C-trans structure in a high efficiency and using the compound. <P>SOLUTION: As shown in formulas [(2Y), (6Z) and (6)], by reacting the iridium metal complex having an N,N-trans structure obtained by a conventional method in the presence of a compound having a hydride, isomerization progresses to obtain the iridium metal complex having the N,C-trans structure in a high efficiency. In the organic EL element in which the organic thin membrane consisting of one layer or a multiple number of layers including a light-emitting layer is nipped, it is found out that in at least one layer of the organic thin membrane layers, the obtained N,C-trans structural material shows 3 to 8 folds quantum yield of the light-emission than that of the N,N-trans structural material and the wavelength of the emitted light is shifted to a shorter wavelength. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an iridium complex, a method for producing the same, and organic electroluminescence using the iridium complex, and in particular, by using an iridium complex having a specific partial structure, the quantum yield is improved, the lifetime is long, and the light emission efficiency is high. The present invention relates to an organic electroluminescence device that can emit blue light.

In an organic electroluminescence element (hereinafter, electroluminescence may be abbreviated as EL), a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. It is a self-luminous element utilizing the principle of Eastman Kodak's C.I. W. Organic materials have been constructed since Tang et al. Reported low-voltage driven organic EL devices using stacked devices (CW Tang, SA Vanslyke, Applied Physics Letters, 51, 913, 1987, etc.) Research on organic EL elements as materials has been actively conducted. Tang et al. Use tris (8-quinolinolato) aluminum for the light emitting layer and a triphenyldiamine derivative for the hole transporting layer. The advantages of the stacked structure are that it increases the efficiency of hole injection into the light-emitting layer, blocks the electrons injected from the cathode, increases the generation efficiency of excitons generated by recombination, and generates in the light-emitting layer For example, confining excitons. As in this example, the element structure of the organic EL element includes a hole transport (injection) layer, a two-layer type of an electron transport light-emitting layer, or a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection) layer. A three-layer type is well known. In such a stacked structure element, the element structure and the formation method are devised in order to increase the recombination efficiency of injected holes and electrons.

In recent years, these organic EL elements have been actively used as display devices for color displays instead of liquid crystals, but currently they are used for in-vehicle audio (area, multicolor), mobile phone sub (rear) displays (mono, full color) ), Small displays for digital cameras (2 inches or less, full color). Furthermore, application to large screens used in televisions and the like has been actively studied. However, the current fluorescent light-emitting materials still lack the light-emitting element performance for a large screen.
In view of this, a light-emitting element using an orthometalated iridium complex (fac-tris (2-phenylpyridine) iridium) as a light-emitting material has been proposed (Non-patent Documents 1 and 2). This device utilizes a phosphorescence emission phenomenon, and has reached an external quantum yield of 8%, which exceeds the external quantum yield of 5%, which is said to be the limit of the conventional fluorescent light emitting device.

  Currently, as phosphorescent complexes, development centering on cyclometalated complexes containing Ir has been actively conducted, and complexes capable of emitting red, green and blue have been found. The compounds A and B shown below are known for red and green light emitting devices, respectively, and are already reaching the practical range. On the other hand, Compound C is known as a blue light emitting device, but it is not practical in terms of device life and efficiency. Therefore, the application range of phosphorescent materials as a color display is narrow, and development of an element having improved blue light emission characteristics is desired. In order to realize full color and whitening using phosphorescent materials, it is essential to develop a highly efficient blue phosphorescent light emitting complex. Therefore, development of blue light-emitting complexes other than Compound C has been actively conducted.

Two types of isomers are known for triscyclometal type complexes such as compound A and compound B (the figure shows the case of compound B). Non-patent document 3 describes that the fac type has a quantum yield about 10 times higher than that of the mer type, and the emission wavelength is shifted by a short wavelength of about several tens of nm. Therefore, when these are applied to an organic EL element, it is optimal to use the fac type.

On the other hand, in the biscyclometal type complex such as compound C, theoretically, four kinds of similar isomers can be considered, but only C1 shown below can be actually synthesized. For these reasons, this is the only one used in organic EL elements. According to the fac type and mer type examples of Compound A, N of the cyclometal ligand is trans to iridium as in the mer type. Similarly, compound C2 is also trans in the same manner as mer type in C. Therefore, these compounds are expected to have improved light emission characteristics as compared with the same compounds C3 and C4 (N and C are trans) as those of the fac type.

  From this point of view, if a compound having a structure in which N and C are trans can be synthesized, a more efficient organic EL device can be realized. Examples of such compounds are slightly known in Patent Document 1 and Patent Document 2, but there is no description of the synthesis method in the former, and in the latter, the same synthesis method as in the past is used, and a very slight amount is produced. N and C isolated the trans structure. Therefore, there has been no method for synthesizing a compound having a highly efficient N, C trans structure.

JP 2006-278781 A International Publication WO2006 / 090301 D.F.O'Brien and M.A.Baldo et al "Improved energy transfer in electrophosphorescent devices" Applied Physics letters Vol. 74 No.3, pp442-444, January 18, 1999 M.A.Baldo et al "Very high-efficiency green organic light-emitting devices based on electrophosphorescence" Applied Physics letters Vol. 75 No. 1, pp4-6, July 5, 1999 J. Am. Chem. Soc., 125, 7383 (2003)

  The present invention has been made to solve the above-mentioned problems, and has studied a method for synthesizing a compound having an N, C trans structure with high efficiency. By using the compound, light emission in a blue region of an organic EL device can be achieved. Aims to improve efficiency and its lifetime

  As a result of intensive studies to achieve the above object, the present inventors proceeded with isomerization when a compound having an N, N trans structure obtained by a conventional method is reacted in the presence of a compound having a hydride. The present inventors have found that a compound having an N, C trans structure can be obtained with high efficiency. In addition, in an organic EL device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a cathode and an anode, at least one layer of the organic thin film layer is an N, C transformer structure obtained. The inventors have found that the quantum yield of light emission is 3 to 8 times higher than that of the N, N trans structure and that the light emission wavelength is also shifted by a short wavelength, thereby completing the present invention.

（式中、含窒素シクロメタル配位子のＮと他方のシクロメタル配位子のＣがイリジウム金属に対してトランス位に位置している。実線はσ結合、点線は配位結合を表す。互いの含窒素シクロメタル配位子は異なっていても、同じであってもよい。
Ｘは価数１の置換基であり、水素、ハロゲン、シアノ基、チオシアナート基、シリル基、アミド基、アルコオキシ基、アルキル基、芳香族オキシ基、芳香族基を示す。芳香族環上にはＦ原子、Ｆ置換アルキル基、シアノ基、ニトロ基、ヘテロ元素が導入されていてもよい。
Ｌはイリジウムに配位結合可能な置換基であり、周期律表第１４〜１６族原子を介しているものを示す。Ｘ及びＬは互いに結合していてもよいが、含窒素シクロメタル配位子ではない。）
本発明の３価イリジウム金属錯体化合物は、シクロメタルカルベン配位子を有する下記一般式（ＩＩＩ）又は（ＩＶ）で表される。

（式中、シクロメタルカルベン配位子のカルベンＣと他方のシクロメタル配位子のＣがイリジウム金属に対してトランス位に位置している。実線はσ結合、点線は配位結合を表す。
Ｘは価数１の置換基であり、水素、ハロゲン、シアノ基、チオシアナート基、シリル基、アミド基、アルコオキシ基、アルキル基、芳香族オキシ基、芳香族基を示す。芳香族環上にはＦ原子、Ｆ置換アルキル基、シアノ基、ニトロ基、ヘテロ元素が導入されていてもよい。
Ｌはイリジウムに配位結合可能な置換基であり、周期律表第１４〜１６族原子を介しているものを示す。Ｘ及びＬは互いに結合していてもよい。）
前記一般式（Ｉ）及び（ＩＩ）を製造する本発明の方法は、下記一般式（Ｖ）を原料にし、ヒドリドを含む化合物の存在下で異性化反応を行うものである。

前記一般式（ＩＩＩ）及び（ＩＶ）を製造する本発明の方法は、下記一般式（ＶＩ）を原料にし、ヒドリドを含む化合物の存在下で異性化反応を行うものである。

本発明の３価イリジウム金属錯体化合物は、リン原子を含むシクロメタル配位子を有する下記一般式（ＶＩＩ）で表される。

本発明の有機エレクトロルミネッセンス素子は、一対の電極間に少なくとも発光層を有する一層又は複数層からなる有機薄膜層が狭持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも１層が前記一般式（Ｉ）〜（Ｖ）のいずれかの金属錯体化合物を含有し、両極間に電圧を印加することにより発光する。 The trivalent iridium metal complex compound of the present invention is represented by the following general formula (I) or (II) having a nitrogen-containing cyclometal ligand.

(In the formula, N of the nitrogen-containing cyclometal ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. The solid line represents the σ bond and the dotted line represents the coordinate bond. The nitrogen-containing cyclometal ligands may be different or the same.
X is a substituent having a valence of 1, and represents hydrogen, halogen, cyano group, thiocyanate group, silyl group, amide group, alcoholoxy group, alkyl group, aromatic oxy group, or aromatic group. An F atom, an F-substituted alkyl group, a cyano group, a nitro group, and a hetero element may be introduced on the aromatic ring.
L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. X and L may be bonded to each other but are not nitrogen-containing cyclometal ligands. )
The trivalent iridium metal complex compound of the present invention is represented by the following general formula (III) or (IV) having a cyclometalcarbene ligand.

(In the formula, carbene C of the cyclometalcarbene ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. The solid line represents the σ bond, and the dotted line represents the coordinate bond.
X is a substituent having a valence of 1, and represents hydrogen, halogen, cyano group, thiocyanate group, silyl group, amide group, alcoholoxy group, alkyl group, aromatic oxy group, or aromatic group. An F atom, an F-substituted alkyl group, a cyano group, a nitro group, and a hetero element may be introduced on the aromatic ring.
L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. X and L may be bonded to each other. )
In the method of the present invention for producing the general formulas (I) and (II), the following general formula (V) is used as a raw material and an isomerization reaction is performed in the presence of a compound containing hydride.

In the method of the present invention for producing the general formulas (III) and (IV), the following general formula (VI) is used as a raw material, and an isomerization reaction is performed in the presence of a compound containing hydride.

The trivalent iridium metal complex compound of the present invention is represented by the following general formula (VII) having a cyclometal ligand containing a phosphorus atom.

The organic electroluminescence device of the present invention is an organic electroluminescence device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes, and at least one of the organic thin film layers is the above-mentioned It contains any of the metal complex compounds of general formulas (I) to (V), and emits light when a voltage is applied between both electrodes.

  In the present invention, when a compound having an N, N trans structure obtained by a conventional method is reacted in the presence of a compound having a hydride, isomerization proceeds and a compound having an N, C trans structure can be obtained with high efficiency. I found. Further, it was found that the obtained N, C trans structure had a quantum yield of light emission 3 to 8 times higher than that of the N, N trans structure, and the emission wavelength was shifted by a short wavelength. When this technology is used, the possibility of breakthrough to a blue light emitting organic EL element that has not been improved in performance so far increases.

式中、含窒素シクロメタル配位子のＮと他方のシクロメタル配位子のＣがイリジウム金属に対してトランス位に位置している。実線はσ結合、点線は配位結合を表す。互いの含窒素シクロメタル配位子は異なっていても、同じであってもよい。Ｘは価数１の置換基であり、水素、ハロゲン、シアノ基、チオシアナート基、シリル基、アミド基、アルコオキシ基、アルキル基、芳香族オキシ基、芳香族基を示す。芳香族環上にはＦ原子、Ｆ置換アルキル基、シアノ基、ニトロ基、ヘテロ元素が導入されていてもよい。Ｌはイリジウムに配位結合可能な置換基であり、周期律表第１４〜１６族原子を介しているものを示す。好ましくは窒素、酸素、イオウ、リンを含むもの及び一酸化炭素である。Ｘ及びＬは互いに結合していてもよいが、含窒素シクロメタル配位子ではない。 The trivalent iridium metal complex compound of the present invention is represented by the following general formula (I) or (II) having a nitrogen-containing cyclometal ligand.

In the formula, N of the nitrogen-containing cyclometal ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. A solid line represents a σ bond and a dotted line represents a coordination bond. The nitrogen-containing cyclometal ligands may be different or the same. X is a substituent having a valence of 1, and represents hydrogen, halogen, cyano group, thiocyanate group, silyl group, amide group, alcoholoxy group, alkyl group, aromatic oxy group, or aromatic group. An F atom, an F-substituted alkyl group, a cyano group, a nitro group, and a hetero element may be introduced on the aromatic ring. L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. Nitrogen, oxygen, sulfur, phosphorus and carbon monoxide are preferred. X and L may be bonded to each other but are not nitrogen-containing cyclometal ligands.

式中、シクロメタルカルベン配位子のカルベンＣと他方のシクロメタル配位子のＣがイリジウム金属に対してトランス位に位置している。実線はσ結合、点線は配位結合を表す。Ｘは価数１の置換基であり、水素、ハロゲン、シアノ基、チオシアナート基、シリル基、アミド基、アルコオキシ基、アルキル基、芳香族オキシ基、芳香族基を示す。芳香族環上にはＦ原子、Ｆ置換アルキル基、シアノ基、ニトロ基、ヘテロ元素が導入されていてもよい。Ｌはイリジウムに配位結合可能な置換基であり、周期律表第１４〜１６族原子を介しているものを示す。好ましくは窒素、酸素、イオウ、リンを含むもの及び一酸化炭素である。Ｘ及びＬは互いに結合していてもよい。 The trivalent iridium metal complex compound of the present invention is represented by the following general formula (III) or (IV) having a cyclometalcarbene ligand.

In the formula, carbene C of the cyclometalcarbene ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. A solid line represents a σ bond, and a dotted line represents a coordination bond. X is a substituent having a valence of 1, and represents hydrogen, halogen, cyano group, thiocyanate group, silyl group, amide group, alcoholoxy group, alkyl group, aromatic oxy group, or aromatic group. An F atom, an F-substituted alkyl group, a cyano group, a nitro group, and a hetero element may be introduced on the aromatic ring. L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. Nitrogen, oxygen, sulfur, phosphorus and carbon monoxide are preferred. X and L may be bonded to each other.

式中、Ｒ¹〜Ｒ²²は、それぞれ独立に、水素原子、シアノ基、ニトロ基、ハロゲン原子、置換基を有してもよい炭素数１〜１２のアルキル基、置換基を有してもよい炭素数１〜１２のアルキルアミノ基、置換基を有してもよい炭素数６〜２０のアリールアミノ基、置換基を有してもよい炭素数１〜１２のアルコキシ基、置換基を有してもよい炭素数１〜１２のハロゲン化アルコキシ基、置換基を有してもよい炭素数６〜２０の芳香族オキシ基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基、置換基を有してもよい炭素数３〜２０の複素環基、置換基を有してもよい炭素数１〜１２のハロゲン化アルキル基、置換基を有してもよい炭素数２〜１２のアルケニル基、置換基を有してもよい炭素数２〜１２のアルキニル基、又は置換基を有してもよい炭素数３〜２０のシクロアルキル基である。隣接するＲ同士は互いに結合し、環を形成していてもよい。 In the general formulas (I) and (II), the metal complex compound of the present invention is preferably a compound in which the nitrogen-containing cyclometal ligand is represented by the following general formula.

In formula, R < ¹ > -R < ²² > may have a hydrogen atom, a cyano group, a nitro group, a halogen atom, the C1-C12 alkyl group which may have a substituent, and a substituent each independently. It has a C1-C12 alkylamino group, a C6-C20 arylamino group which may have a substituent, a C1-C12 alkoxy group which may have a substituent, and a substituent. An optionally substituted halogenated alkoxy group having 1 to 12 carbon atoms, an aromatic oxy group having 6 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 20 carbon atoms which may have a substituent. A hydrocarbon group, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 12 carbon atoms, and an optionally substituted carbon C2-C12 alkenyl group, C2-C12 alkynyl group which may have a substituent, or substituent A cycloalkyl group having 3 to 20 carbon atoms which may have. Adjacent Rs may be bonded to each other to form a ring.

式中、Ｒ²³〜Ｒ²⁹は、それぞれ独立に、水素原子、シアノ基、ニトロ基、ハロゲン原子、置換基を有してもよい炭素数１〜１２のアルキル基、置換基を有してもよい炭素数１〜１２のアルキルアミノ基、置換基を有してもよい炭素数６〜２０のアリールアミノ基、置換基を有してもよい炭素数１〜１２のアルコキシ基、置換基を有してもよい炭素数１〜１２のハロゲン化アルコキシ基、置換基を有してもよい炭素数６〜２０の芳香族オキシ基、置換基を有してもよい炭素数６〜２０の芳香族炭化水素基、置換基を有してもよい炭素数３〜２０の複素環基、置換基を有してもよい炭素数１〜１２のハロゲン化アルキル基、置換基を有してもよい炭素数２〜１２のアルケニル基、置換基を有してもよい炭素数２〜１２のアルキニル基、又は置換基を有してもよい炭素数３〜２０のシクロアルキル基である。隣接するＲ同士は互いに結合し、環を形成していてもよい。 In the general formulas (III) and (IV), the metal complex compound of the present invention is preferably a compound in which the cyclometalcarbene ligand is represented by the following general formula.

In the formula, R ^{23 to} R ²⁹ may each independently have a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a substituent. It has a C1-C12 alkylamino group, a C6-C20 arylamino group which may have a substituent, a C1-C12 alkoxy group which may have a substituent, and a substituent. An optionally substituted halogenated alkoxy group having 1 to 12 carbon atoms, an aromatic oxy group having 6 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 20 carbon atoms which may have a substituent. A hydrocarbon group, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, an optionally substituted halogenated alkyl group having 1 to 12 carbon atoms, and an optionally substituted carbon C2-C12 alkenyl group, C2-C12 alkynyl group which may have a substituent, or substituent It is a C3-C20 cycloalkyl group which may have. Adjacent Rs may be bonded to each other to form a ring.

In the metal complex compound of the present invention, L in the general formulas (I), (II), (III) and (IV) is preferably a group containing phosphorus as a coordination atom.
In the metal complex compound of the present invention, X is preferably halogen in the general formulas (I), (II), (III) and (IV).
In the metal complex compound of the present invention, in the general formulas (I), (II), (III) and (IV), the bidentate ligand formed by bonding L and X to each other is one of the following general formulas: It is preferable that it is a compound represented by these.

(In the formula, Y represents an O atom, an S atom, or C (R ⁴³ R ⁴⁴ ).
R ^{30 to} R ⁴⁴ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted carbon number. It may have an alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or a substituent. Good C1-C12 halogenated alkoxy group, C6-C20 aromatic oxy group which may have a substituent, C6-C20 aromatic hydrocarbon group which may have a substituent , A heterocyclic group having 3 to 20 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 12 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent. 12 alkenyl groups, optionally having 2-12 alkynyl groups, or having substituents It is a C3-C20 cycloalkyl group which may be. Adjacent Rs may be bonded to each other to form a ring. )

The metal complex compound of the present invention is preferably represented by any one of the following general formulas.

In the production methods (I) and (II) of the present invention, the following general formula (V) is used as a raw material, and an isomerization reaction is carried out in the presence of a compound containing hydride. Similarly, (III) and (IV) are isomerized in the presence of a compound containing hydride using the following general formula (VI) as a raw material.

In the production method of the present invention, the hydride is preferably NaH, LiAlH ₄ or NaBH ₄ .

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1 -Pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, 3-methylpentyl group and the like can be mentioned. Among these, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group are preferable. N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, neopentyl group, 1-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyl An octyl group etc. are mentioned.
Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent include, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 2-hydroxyisobutyl group, and 1,2-dihydroxyethyl. Group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl Group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl Group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t Butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2 , 3-Diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitrome Group, 1-nitroethyl group, 2-nitroethyl group, 1,2 Jinitoroechiru group, 2,3-dinitro -t- butyl group, 1,2,3-trinitro-propyl group and the like.

  Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl Group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group, 3-phenyl-1-butenyl group, etc., preferably styryl group, 2,2- A diphenyl vinyl group, a 1, 2- diphenyl vinyl group, etc. are mentioned.

Examples of the aromatic group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenyl Yl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl- 4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl Group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylyl group, 4 ″ -T-butyl-p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group And a mesityl group.
Among these, a phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-tolyl group, 3,4 -A xylyl group etc. are mentioned.

  Examples of heterocyclic groups, that is, aromatic groups into which heteroelements are introduced include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl Group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group Group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group Group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2- Phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthrin Nyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl Group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group, 1,7- Phenanthroline-6-yl group, 1,7-phenanthroline-8-yl group, 1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group 1,8-phenanthroline-3-yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthro Rin-6-yl group, 1,8-phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group 1,9-phenanthroline-3-yl group, 1,9-phenanthroline-4-yl group, 1,9-phenanthroline-5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline -7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1,10-phenanthroline-5-yl group, 2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3 Yl group, 2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9-phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9 -Phenanthroline-8-yl group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-yl group, 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl Group, 2,8-phenanthroline-5-yl group, 2,8-phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8- Phenanthroline-10-yl group, 2,7-phenanthroline-1-yl group, 2,7-phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7 Phenanthroline-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group , 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methyl Rupyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methyl Pyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1- Indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2-t-butyl 3-indolyl group, 4-t-butyl 3-indolyl group and the like can be mentioned.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
The silyl group preferably has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group.

The amino group which may have a substituent includes the following alkylamino group and arylamino group.
The substituted or unsubstituted alkoxy group is a group represented by —OY ^2, and specific examples of Y ² include the same as those described for the alkyl group, and preferred examples are also the same.
The aromatic oxy group is a group represented by —OAr ^1, and specific examples of Ar ¹ include the same as those described for the aromatic group.
Examples of the fluorine-substituted alkyl group include those obtained by substituting the hydrogen atom in the above examples of the alkyl group with a fluorine atom.
The alkylamino group is a group represented by —NHR ^1a or —NR ^2a R ^3a, and examples of R ^1a , R ^2a and R ^3a include the same as those described for the alkyl group, and are preferable. The example is similar.
The arylamino group is a group represented by —NHAr ^1a or —NAr ^2a Ar ^3a, and examples of Ar ^1a , Ar ^2a, and Ar ^3a include the same as those described for the aromatic group.
Examples of the halogenated alkoxy group include those obtained by substituting hydrogen atoms in the above-mentioned examples of alkoxy groups with fluorine atoms.
Examples of the halogenated alkyl group include those obtained by substituting hydrogen atoms in the above examples of alkyl groups with halogen atoms.
The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl.

  Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 4-methylcyclohexyl group, 3,5-tetramethylcyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like can be mentioned. Among these, Preferably, a cyclohexyl group, a cyclooctyl group, a 3,5-tetramethylcyclohexyl group etc. are mentioned.

  The substituent may be further substituted with another substituent, for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2 -Dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2 -Chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3- Lichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2,3 -Diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1 , 3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, Nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2, 3-trinitropropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group, etc.), carbon number 1 to 6 alkoxy groups (ethoxy group, methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butyl group) Toxyl group, pentoxy group, hexyloxy group, cyclopentoxy group, cyclohexyloxy group, etc.), aryl group having 5 to 40 nuclear atoms, amino group substituted with aryl group having 5 to 40 nuclear atoms, number of nuclear atoms Examples thereof include an ester group having an aryl group of 5 to 40, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a halogen atom.

  The following are mentioned as an example of the trivalent iridium metal complex compound represented by general formula (I)-(IV) used for the organic EL element of this invention.

The organic electroluminescence device of the present invention is an organic electroluminescence device in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between a pair of electrodes, and at least one of the organic thin film layers is the above-mentioned It contains at least one trivalent iridium complex compound represented by any one of the general formulas (I) to (IV) and (VII).
In the organic electroluminescence device of the present invention, the light emitting layer preferably contains at least one trivalent iridium complex compound represented by any one of the general formulas (I) to (IV) and (VII).
The organic electroluminescence device of the present invention is preferably formed by coating a layer containing the trivalent iridium complex compound.

Hereinafter, the element structure of the organic EL element of the present invention will be described.
(1) Structure of organic EL element As a typical element structure of the organic EL element of the present invention,
(1) Anode / light emitting layer / cathode
(2) Anode / hole injection layer / light emitting layer / cathode
(3) Anode / light emitting layer / electron injection layer / cathode
(4) Anode / hole injection layer / light emitting layer / electron injection layer / cathode
(5) Anode / organic semiconductor layer / light emitting layer / cathode
(6) Anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode
(7) Anode / organic semiconductor layer / light emitting layer / adhesion improving layer / cathode
(8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode
(9) Anode / insulating layer / light emitting layer / insulating layer / cathode
(10) Anode / inorganic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode
(11) Anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode
(12) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / insulating layer / cathode
(13) Structures such as anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode can be mentioned.
Of these, the configuration of (8) is preferably used.
The compound of the present invention may be used in any of the organic layers described above, but is preferably contained in the light emission band of these constituent elements.

(2) Translucent board | substrate The organic EL element of this invention is produced on a translucent board | substrate. Here, the translucent substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 to 700 nm of 50% or more.
Specifically, a glass plate, a polymer plate, etc. are mentioned. Examples of the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

(3) Anode The anode of the organic EL device of the present invention plays a role of injecting holes into the hole transport layer or the light emitting layer, and it is effective to have a work function of 4.5 eV or more. Specific examples of the anode material used in the present invention include indium tin oxide alloy (ITO), tin oxide (NESA), gold, silver, platinum, copper, and the like. The anode is preferably a material having a small work function for the purpose of injecting electrons into the electron transport layer or the light emitting layer.
The anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
Thus, when light emission from the light emitting layer is taken out from the anode, it is preferable that the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

(4) Light emitting layer The light emitting layer of an organic EL element has the following functions. That is,
(1) Injection function: When an electric field is applied, holes can be injected from the anode or hole injection layer,
Function that can inject electrons from cathode or electron injection layer
(2) Transport function: Function to move injected charges (electrons and holes) by the force of electric field
(3) Luminescent function: Provides a field for recombination of electrons and holes, and has the function to connect this to light emission. However, there may be a difference between the ease of hole injection and the ease of electron injection, and the transport capability represented by the mobility of holes and electrons may be large or small. It is preferable to move the charge.
As a method for forming the light emitting layer, for example, a known method such as an evaporation method, a spin coating method, or an LB method can be applied. The light emitting layer is particularly preferably a molecular deposited film.
Here, the molecular deposition film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidification from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom.
Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coating method or the like. In addition, a light emitting layer can be formed.
In the present invention, as long as the object of the present invention is not impaired, a known light emitting material other than the light emitting material comprising the compound having the fluoranthene structure of the present invention and the condensed ring-containing compound may be included in the light emitting layer as desired. Alternatively, a light emitting layer containing another known light emitting material may be stacked on the light emitting layer containing the light emitting material of the present invention.
Furthermore, the thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If the thickness is less than 5 nm, it is difficult to form a light emitting layer, and it may be difficult to adjust the chromaticity. If the thickness exceeds 50 nm, the driving voltage may increase.

(5) Hole injection / transport layer (hole transport zone)
The hole injecting / transporting layer is a layer that assists hole injection into the light emitting layer and transports it to the light emitting region, and has a high hole mobility and a small ionization energy of usually 5.5 eV or less. As such a hole injecting / transporting layer, a material that transports holes to the light emitting layer with a lower electric field strength is preferable, and the mobility of holes is, for example, when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied. , At least 10 ⁻⁴ cm ² / V · sec is preferable.
When the aromatic amine derivative of the present invention is used in the hole transport zone, the aromatic amine derivative of the present invention alone may form a hole injection / transport layer, or may be mixed with other materials.
The material for forming the hole injecting / transporting layer by mixing with the aromatic amine derivative of the present invention is not particularly limited as long as it has the above-mentioned preferable properties. Any material commonly used as a material and known materials used for a hole injection / transport layer of an organic EL element can be selected and used.

  Specific examples include triazole derivatives (see US Pat. No. 3,112,197), oxadiazole derivatives (see US Pat. No. 3,189,447, etc.), imidazole derivatives (Japanese Patent Publication No. 37-16096). Polyarylalkane derivatives (US Pat. Nos. 3,615,402, 3,820,989, 3,542,544, JP-B-45-555). 51-10983, JP-A-51-93224, 55-17105, 56-4148, 55-108667, 55-156953, 56-36656 Patent Publication etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729 and 4,278,746) No. 55-88064, No. 55-88065, No. 49-105537, No. 55-51086, No. 56-80051, No. 56-88141, No. 57-45545, 54-1112637, 55-74546, etc.), phenylenediamine derivatives (US Pat. No. 3,615,404, JP-B 51-10105, 46-3712, 47) No. 25336, No. 54-53435, No. 54-110536, No. 54-1119925, etc.), arylamine derivatives (US Pat. No. 3,567,450, No. 3) , 180,703 specification, 3,240,597 specification, 3,658,520 specification, 4,232,103 specification. No. 4,175,961, No. 4,012,376, JP-B-49-35702, JP-A-39-27577, JP-A-55-144250, 56-119132, 56-22437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivatives (see US Pat. No. 3,526,501, etc.), oxazole derivatives (Disclosed in US Pat. No. 3,257,203, etc.), styryl anthracene derivatives (see JP-A-56-46234, etc.), fluorenone derivatives (see JP-A-54-110837, etc.), Hydrazone derivatives (US Pat. No. 3,717,462, JP-A-54-59143, 55-52063, 55-52064) 55-46760, 55-85495, 57-11350, 57-148799, JP-A-2-311591, etc.), stilbene derivatives (JP-A-61-210363) Gazette, 61-228451, 61-14642, 61-72255, 62-47646, 62-36684, 62-10652, 62-30255 No. 60-93455, No. 60-94462, No. 60-174749, No. 60-175052, etc.), silazane derivatives (US Pat. No. 4,950,950), polysilane System (JP-A-2-204996), aniline copolymer (JP-A-2-282263), JP-A1-2 Conductive polymer oligomers disclosed in 1399 JP can (particularly thiophene oligomer).

As the material for the hole injecting / transporting layer, the above-mentioned materials can be used. Porphyrin compounds (disclosed in JP-A-63-295965), aromatic tertiary amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, 54-58445, 54-149634, 54-64299, 55-79450, 55-144250 gazette, 56-119132 gazette, 61-295558 gazette, 61-98353 gazette, 63-295695 gazette, etc.), especially using aromatic tertiary amine compounds. preferable.
In addition, for example, 4,4′-bis (N- (1-naphthyl) -N-phenylamino having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule. ) Biphenyl (hereinafter abbreviated as NPD), and 4,4 ′, 4 ″ -tris (N- () in which three triphenylamine units described in JP-A-4-308688 are linked in a starburst type. 3-methylphenyl) -N-phenylamino) triphenylamine (hereinafter abbreviated as MTDATA) and the like.
In addition to the above-mentioned aromatic dimethylidin compounds shown as the material for the light emitting layer, inorganic compounds such as p-type Si and p-type SiC can also be used as the material for the hole injection layer.

The hole injection / transport layer can be formed by thinning the above-described compound by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the hole injection / transport layer is not particularly limited, but is usually 5 nm to 5 μm. As long as the hole injection / transport layer contains the compound of the present invention in the hole transport zone, the hole injection / transport layer may be composed of one or more layers of the above-described materials, or the hole injection A layer in which a hole injection / transport layer made of a compound different from the transport layer is laminated may be used.
Further, a layer that assists hole injection or electron injection into the light-emitting layer and has a conductivity of 10 ⁻¹⁰ S / cm or more is preferable. As a material for such an organic semiconductor layer, a conductive oligomer such as a thiophene-containing oligomer, an arylamine oligomer disclosed in JP-A-8-193191, a conductive dendrimer such as an arylamine dendrimer, or the like is used. Can do.

(6) Electron injection layer The electron injection layer is a layer that assists the injection of electrons into the light-emitting layer, and has a high electron mobility. The adhesion improving layer is particularly adhering to the cathode among the electron injection layers. It is a layer made of a good material. As a material used for the electron injection layer, a metal complex of 8-hydroxyquinoline or a derivative thereof is preferable.
Specific examples of the metal complex of 8-hydroxyquinoline or a derivative thereof include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline).
For example, Alq described in the section of the light emitting material can be used as the electron injection layer.

（式中、Ａｒ¹，Ａｒ²，Ａｒ³，Ａｒ⁵，Ａｒ⁶，Ａｒ⁹はそれぞれ置換または無置換のアリール基を示し、それぞれ互いに同一であっても異なっていてもよい。またＡｒ⁴，Ａｒ⁷，Ａｒ⁸は置換または無置換のアリーレン基を示し、それぞれ同一であっても異なっていてもよい）
ここでアリール基としてはフェニル基、ビフェニル基、アントラニル基、ペリレニル基、ピレニル基が挙げられる。また、アリーレン基としてはフェニレン基、ナフチレン基、ビフェニレン基、アントラニレン基、ペリレニレン基、ピレニレン基などが挙げられる。また、置換基としては炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基またはシアノ基等が挙げられる。この電子伝達化合物は薄膜形成性のものが好ましい。 On the other hand, examples of the oxadiazole derivative include electron transfer compounds represented by the following general formula.

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁵ , Ar ⁶ , Ar ⁹ each represents a substituted or unsubstituted aryl group, and may be the same or different from each other. Ar ⁴ , Ar ⁷ and Ar ⁸ represent a substituted or unsubstituted arylene group, which may be the same or different.
Here, examples of the aryl group include a phenyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group. Moreover, as a substituent, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned. This electron transfer compound is preferably a thin film-forming compound.

Specific examples of the electron transfer compound include the following.

A preferred form of the organic EL device of the present invention is a device containing a reducing dopant in the region for transporting electrons or the interface region between the cathode and the organic layer. Here, the reducing dopant is defined as a substance capable of reducing the electron transporting compound. Accordingly, various materials can be used as long as they have a certain reducibility, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals. At least selected from the group consisting of oxides, alkaline earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, rare earth metal organic complexes One substance can be preferably used.
More specifically, preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1 .95 eV), at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV). Particularly preferred are those having a work function of 2.9 eV or less, including at least one alkaline earth metal selected from the group consisting of: Among these, a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb, and Cs, more preferably Rb or Cs, and most preferably Cs. . These alkali metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the light emission luminance and extend the life of the organic EL element. Further, as a reducing dopant having a work function of 2.9 eV or less, a combination of these two or more alkali metals is also preferable. Particularly, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, A combination of Cs, Na and K is preferred. By including Cs in combination, the reducing ability can be efficiently exhibited, and by adding to the electron injection region, the emission luminance and the life of the organic EL element can be improved.

In the present invention, an electron injection layer composed of an insulator or a semiconductor may be further provided between the cathode and the organic layer. At this time, current leakage can be effectively prevented and the electron injection property can be improved. As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved. Specifically, preferable alkali metal chalcogenides include, for example, Li ₂ O, K ₂ O, Na ₂ S, Na ₂ Se, and Na ₂ O, and preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS, and CaSe. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.
Further, as a semiconductor constituting the electron transport layer, an oxide containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. , Nitrides or oxynitrides, or a combination of two or more. Moreover, it is preferable that the inorganic compound which comprises an electron carrying layer is a microcrystal or an amorphous insulating thin film. If the electron transport layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include the alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides described above.

(7) Cathode As the cathode, in order to inject electrons into the electron injecting / transporting layer or the light emitting layer, a material having a small work function (4 eV or less), an alloy, an electrically conductive compound and a mixture thereof are used as electrode materials. Used. Specific examples of such electrode materials include sodium, sodium / potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals.
The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
Here, when light emitted from the light emitting layer is taken out from the cathode, it is preferable that the transmittance with respect to the light emitted from the cathode is larger than 10%.
The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

(8) Insulating layer Since an organic EL element applies an electric field to an ultrathin film, pixel defects due to leakage or short-circuiting are likely to occur. In order to prevent this, it is preferable to insert an insulating thin film layer between the pair of electrodes.
Examples of the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, Examples include germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide.
A mixture or laminate of these may be used.

(9) Manufacturing method of organic EL element By forming an anode, a light emitting layer, a hole injection layer as needed, and an electron injection layer as needed by the materials and formation methods exemplified above, and further forming a cathode An organic EL element can be produced. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.
Hereinafter, an example of manufacturing an organic EL element having a structure in which an anode / a hole injection layer / a light emitting layer / an electron injection layer / a cathode are sequentially provided on a light transmitting substrate will be described.
First, a thin film made of an anode material is formed on a suitable light-transmitting substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. Next, a hole injection layer is provided on the anode. As described above, the hole injection layer can be formed by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. However, it is easy to obtain a homogeneous film and pinholes are not easily generated. It is preferable to form by a vacuum evaporation method from such points. When forming a hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used (the material of the hole injection layer), the crystal structure of the target hole injection layer, the recombination structure, etc. The source temperature is preferably 50 to 450 ° C., the degree of vacuum is 10 ⁻⁷ to 10 ⁻³ Torr, the deposition rate is 0.01 to 50 nm / second, the substrate temperature is −50 to 300 ° C., and the film thickness is preferably 5 nm to 5 μm. .

  Next, the formation of the light emitting layer in which the light emitting layer is provided on the hole injection layer is also performed by thinning the organic light emitting material using a desired organic light emitting material by a method such as vacuum deposition, sputtering, spin coating, or casting. However, it is preferably formed by a vacuum deposition method from the viewpoint that a homogeneous film is easily obtained and pinholes are hardly generated. When the light emitting layer is formed by the vacuum vapor deposition method, the vapor deposition condition varies depending on the compound used, but it can be generally selected from the same condition range as that of the hole injection layer.

  The light emitting layer of the EL device of the present invention can be formed not only by vapor deposition of the light emitting material but also by a wet process. The organic layers of the light emitting layer can be formed by dry deposition methods such as vacuum deposition, sputtering, plasma, ion plating, and coating methods such as spin coating, dipping, casting, bar coating, roll coating, flow coating, and inkjet. Can be applied.

  In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a luminescent organic solution to form a thin film, and any solvent may be used. Examples of the solvent include halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, trifluorotoluene, dibutyl ether, tetrahydrofuran, tetrahydropyran, Ether solvents such as dioxane, anisole, dimethoxyethane, etc., alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, acetone, methyl ethyl ketone, diethyl Ketone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobuty Ketone solvents such as ketone, acetonylacetone, isophorone, cyclohexanone, methylhexanone, acetophenone, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, hexane, cyclohexane, octane, decane, tetralin, ethyl acetate, butyl acetate, Examples thereof include ester solvents such as amyl acetate, chain carbonate solvents such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate, and cyclic carbonate solvents such as ethylene carbonate and propylene carbonate. Of these, hydrocarbon solvents such as toluene and dioxane and ether solvents are preferred. These solvents may be used alone or in combination of two or more. In addition, the solvent which can be used is not limited to these.

Next, an electron injection layer is provided on the light emitting layer. As with the hole injection layer and the light emitting layer, it is preferable to form by a vacuum evaporation method because it is necessary to obtain a homogeneous film. Deposition conditions can be selected from the same condition range as the hole injection layer and the light emitting layer.
Although the compound of the present invention varies depending on which layer in the emission band or the hole transport band, it can be co-deposited with other materials when the vacuum deposition method is used. Moreover, when using a spin coat method, it can be made to contain by mixing with another material.
Finally, an organic EL element can be obtained by laminating a cathode.
The cathode is made of metal, and vapor deposition or sputtering can be used. However, vacuum deposition is preferred to protect the underlying organic layer from damage during film formation.
It is preferable that the organic EL device described so far is manufactured from the anode to the cathode consistently by a single vacuum.

The formation method of each layer of the organic EL element of the present invention is not particularly limited. Conventionally known methods such as vacuum deposition and spin coating can be used. The organic thin film layer used in the organic EL device of the present invention is a vacuum deposition method, a molecular beam deposition method (MBE method) or a solution dipping method dissolved in a solvent, a spin coating method, a casting method, a bar coating method, a roll coating method, etc. It can form by the well-known method by the apply | coating method.
In any organic thin film layer, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film. Usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polyaniline, polythiophene, and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
Although the film thickness of each organic layer of the organic EL element of this invention is not specifically limited, It is necessary to set to an appropriate film thickness. In general, if the film thickness is too thin, pinholes and the like are generated, and there is a risk that sufficient light emission luminance may not be obtained even when an electric field is applied. Usually, the film thickness is preferably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.
In order to improve the stability of the organic EL device obtained by the present invention with respect to temperature, humidity, atmosphere, etc., it is possible to provide a protective layer on the surface of the device, or to protect the entire device with silicone oil, resin, etc. It is.
When a direct current voltage is applied to the organic EL element, light emission can be observed by applying a voltage of 5 to 40 V with the anode set to + and the cathode set to a negative polarity. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an alternating voltage is applied, uniform light emission is observed only when the anode has a positive polarity and the cathode has a negative polarity. The waveform of the alternating current to be applied may be arbitrary.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to these Examples.

Synthesis Example 1 (Synthesis of Metal Complex Compound 2)
The metal complex compound 2 was synthesized by the following route.

(1) Synthesis eggplant flask compound (2Y), iridium chloride hydrate ^{(4.0g, 1.34 × 10 -2 mol} ) were charged, after an internal with nitrogen, (2X) (10.3g, 5.37 × 10 - ² mol) and 2-ethoxyethanol (50 ml) were added. After stirring for 18 hours under reflux, the precipitated yellow solid was filtered off. Further, it was washed with methanol (50 ml × 2 times) and dried under reduced pressure to obtain (2Y) as a yellow powder (5.4 g, 4.44 × 10 ⁻³ mol, yield 66%).

(2) Synthesis of Compound (2Z) (2Y) (0.294 g, 2.42 × 10 ⁻⁴ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and THF (30 ml) was added. Then, triphenyl phosphite (0.3 ml, 1.14 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (30 ml x 2) and dried under reduced pressure to obtain (2Z) as a yellow powder (0.441 g, 4.80 x 10 ^-4 mol, yield 99.4%). It was. Single crystal X-ray structural analysis was performed using yellow plate crystals (0.426 g, 0.464 mmol, 96.0%) obtained by dissolving yellow powder in methylene chloride and crystallizing from a two-layer system with hexane. .
¹ H NMR (600 MHz, CDCl ₃ ): δ9.68 (d, J = 4.6 Hz, 1H, F ₂ ppy),
9.50 (d, J = 4.6 Hz, 1H, F ₂ ppy), 8.31 (d, J = 9.2 Hz, 1H, F ₂ ppy), 8.10 (d, J = 6.9 Hz, 1H, F ₂ ppy), 7.84 ( dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.70 (dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.12-7.09 (m, 7H, F ₂ ppy, P (OPh) ₃ ), 7.03 (t, J = 6.9 Hz, 3H, P (OPh) ₃ ), 6.96 (dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 6.76 (d, J = 9.2 Hz, 6H, P (OPh) ₃ ), 6.36 (dd, J = 11.5, 11.5 Hz, 1H, F ₂ ppy), 6.29 (dd, J = 11.5, 11.5 Hz, 1H, F ₂ ppy), 5.64 (d, J = 9.2 Hz, 1H, F ₂ ppy), 5.22 (dd, J = 9.2, 9.2 Hz, 1H, F ₂ ppy)
¹⁹ F NMR: δ-107.1 (d, J = 20.7 Hz, 1F, F ₂ ppy), -107.5 (s, 1F,
F ₂ ppy), -109.5 (s, 1F, F ₂ ppy), -110.5 (d, J = 13.8 Hz, 1F, F ₂ ppy)
³¹ P [ ¹ H] NMR (CDCl ₃ , 243 MHz): δ75.6 (s, P (OPh) ₃ )

(3) Synthesis of Compound (2) (2Z) (0.269 g, 2.93 × 10 ⁻⁴ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and then THF (20 ml) was added. Then, sodium hydride (0.047 g, 1.96 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature. The obtained suspension was centrifuged to remove the precipitate, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (20 ml × 2) and dried under reduced pressure to obtain Compound (2) as a yellow powder (0.268 g, 2.92 × 10 ⁻⁴ mol, yield 99.7%) . Single crystal X-ray structural analysis was performed using yellow plate crystals obtained by dissolving yellow powder in tetrahydrofuran and crystallizing from a two-layer system with hexane.
¹ H NMR (600 MHz, CDCl ₃ ): δ9.60 (d, J = 4.6 Hz, 1H, F ₂ ppy), 8.
22 (d, J = 6.9 Hz, 1H, F ₂ ppy), 8.13 (d, J = 6.9 Hz, 1H, F ₂ ppy), 7.94 (d, J = 11.5 Hz, 1H, F ₂ ppy), 7.73 ( dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.60 (dd, J = 8.1, 8.1 Hz, 1H, F ₂ ppy), 7.10 (dd, J = 8.1, 8.1 Hz, 6H, P (OPh ) ₃ ), 6.99-7.04 (m, 4H, F ₂ ppy, P (OPh) ₃ ), 6.87 (dd, J = 4.6, 4.6 Hz, 1H, F ₂ ppy), 6.75-6.79 (m, 7H, F ₂ ppy, P (OPh) ₃ ), 6.64 (dd, J = 9.2, 9.2 Hz, 1H, F ₂ ppy), 6.31 (dd, J = 9.2, 9.2 Hz, 1H, F ₂ ppy), 6.18 (dd, (J = 9.2 Hz, 1H, F ₂ ppy)
¹⁹ F NMR (564MHz, CDCl ₃ , ppm): δ-107.4 (d, J = 20.7 Hz, 1F,
F ₂ ppy), -108.4 (d, J = 20.7 Hz, 1F, F ₂ ppy), -109.3 (d, J = 13.8 Hz, 1F, F ₂ ppy), -110.2 (dd, J = 13.8, 13.8 Hz , 1F, F ₂ ppy)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ44.86 (s, P (OPh) ₃ ).
The X-ray structural diagram and emission spectrum of the obtained compounds (2Z) and (2) are shown in FIG. In compound (2), it can be seen that N of the two cyclometal ligands are located in the cis position relative to each other. In addition, when the emission spectra were compared, it was found that (2) emitted light at a shorter wavelength and the emission quantum yield was about three times higher.

Synthesis Example 2 (Synthesis of metal complex compound 4)
The metal complex compound 4 was synthesized by the following route.

(1) Synthesis of Compound (4Y) After placing iridium chloride hydrate (5.0 g, 1.67 × 10 ^-2 mol) in an eggplant flask and replacing the interior with nitrogen, (4X) (10.4 g, 6.70 × 10 ^-2 mol) and 2-ethoxyethanol (60 ml) were added. After stirring for 18 hours under reflux, the precipitated yellow solid was filtered off. Further, it was washed with methanol (50 ml × 2 times) and dried under reduced pressure to obtain (4Y) as a yellow powder (6.4 g, 5.96 × 10 ⁻³ mol, yield 71.5%).

(2) Synthesis of Compound (4Z) (4Y) (0.200 g, 1.87 × 10 ⁻⁴ mol) was placed in an eggplant flask, and the interior was purged with nitrogen, and then THF (20 ml) was added. Subsequently, triphenyl phosphite (0.2 ml, 7.60 × 10 ⁻⁴ mol) was added, and the mixture was stirred overnight at room temperature, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (20 ml × 2 times) and dried under reduced pressure to obtain (4Z) as a yellow powder (0.312 g, 3.69 × 10 ⁻⁴ mol, yield 98.7%). . Single crystal X-ray structural analysis was carried out by dissolving yellow powder in methylene chloride and using yellow granular crystals obtained from a two-layer system with hexane.
¹ H NMR (600 MHz, rt): δ9.60 (d, J = 6.9 Hz, 1H, ppy), 9.52 (d, J = 4.6 Hz, 1H, ppy), 7.89 (d, J = 6.9 Hz, 1H , ppy), 7.78 (dd, J = 8.1, 8.1 Hz, 1H, ppy), 7.69 (d, J = 9.2 Hz, 1H, ppy), 7.59 (d, J = 6.9 Hz, 1H, ppy), 7.57 ( d, J = 6.9 Hz, 1H, ppy), 7.49 (d, J = 9.2 Hz, 1H, ppy), 7.07 (dd, J = 8.1, 8.1 Hz, 7H, ppy, P (OPh) ₃ ), 6.99 ( t, J = 6.9, 6.9Hz, 3H, P (OPh) ₃ ), 6.87 (dd, J = 8.1, 8.1 Hz, 1H, ppy), 6.83 (dd, J = 6.9, 6.9 Hz, 1H, ppy), 6.78 (dd, J = 6.9, 6.9 Hz, 2H, ppy), 6.68 (d, J = 9.2 Hz, 6H, P (OPh) ₃ ), 6.62 (dd, J = 8.1, 8.1 Hz, 1H, ppy), 6.33 (d, J = 9.2 Hz, 1H, ppy), 5.78 (dd, J = 8.1, 8.1 Hz, 1H, ppy)
³¹ P NMR (243 MHz, rt): δ79.2 (s, P (OPh) ₃ )

Synthesis of Compound (4) (4Z) (0.100 g, 1.18 × 10 ⁻⁴ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and THF (10 ml) was added. Next, sodium hydride (0.028 g, 1.17 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature. The obtained suspension was centrifuged to remove the precipitate, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (20 ml × 2) and dried under reduced pressure to obtain (4) as a yellow powder (0.082 g, 9.73 × 10 ⁻⁵ mol, yield 82.3%). . Single crystal X-ray structural analysis was performed using yellow granular crystals obtained by dissolving yellow powder in methylene chloride and crystallizing from a two-layer system with hexane.
¹ H NMR (600 MHz, CDCl ₃ ): δ 9.45 (d, J = 4.1 Hz, 1H, ppy), 8.48 (d, J = 8.3 Hz, 1H, ppy), 7.79 (d, J = 8.3 Hz, 1H, ppy), 7.75 (d, J = 8.3 Hz, 1H, ppy), 7.70 (d, J = 8.3 Hz, 1H, ppy), 7.65 (d, J = 8.3 Hz, 1H, ppy), 7.50-7.57 (m, 2H, ppy), 7.27 (dd, J = 7.6, 7.6 Hz, 1H, ppy), 7.14 (dd, J = 7.6, 7.6 Hz, 1H, ppy), 7.06 (dd, J = 7.6, 7.6 Hz , 6H, P (OPh) ₃ ), 6.97 (dd, J = 6.9, 6.9 Hz, 3H, P (OPh) ₃ ), 6.83-6.91 (m, 3H, ppy), 6.79 (d, J = 8.3 Hz, 1H, ppy), 6.67-6.72 (m, 7H, ppy, P (OPh) ₃ ), 6.62 (dd, J = 6.9, 6.9 Hz, 1H, ppy)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ47.29 (s, 1P, P (OPh) ₃ )

  The X-ray structural diagram and emission spectrum of the obtained compounds (4Z) and (4) are shown in FIG. In compound (4), it can be seen that N of the two cyclometal ligands are located in the cis position relative to each other. It was also found that the emission quantum yield was about 8 times higher.

Synthesis Example 3 (Synthesis of metal complex compound 6)
The metal complex compound 6 was synthesized by the following route.

(1) Synthesis of compound (6Z) In eggplant flask (2Y) (0.300 g, 2.46 × 10 ⁻⁴ mol) was added, the inside was purged with nitrogen, and THF (40 ml) was added. Next, triphenylphosphine (0.133 g, 5.06 × 10 ⁻⁴ mol) was added, and the mixture was stirred overnight at room temperature, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (20 ml) and then with ether (20 ml) and dried under reduced pressure to obtain (6Z) as a yellow powder (0.396 g). δ
¹ H NMR (600 MHz, rt): δ9.30 (d, J = 5.5 Hz, 1H, F ₂ ppy), 9.25 (d, J = 5.5 Hz, 1H, F ₂ ppy), 8.88 (dd, J = 5.5, 5.5 Hz, 2H, F ₂ ppy), 8.35 (d, J = 8.2 Hz, 2H, F ₂ ppy), 8.03 (d, J = 8.2 Hz, 2H, F ₂ ppy), 8.00 (d, J = 8.2 Hz, 1H, F ₂ ppy), 7.78 (dd, J = 8.2, 11.0, 8.2 Hz, 2H, F ₂ ppy), 7.60 (d, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.55 ( dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.39 (dd, J = 8.2, 8.2Hz, 2H, F ₂ ppy), 7.35-7.25 (m, 18H, PPh ₃ ), 7.17 (dd, J = 6.9, 6.9 Hz, 12H, PPh ₃ ), 6.84-6.79 (m, 3H, F ₂ ppy), 6.40-6.33 (m, 3H, F ₂ ppy), 5.43 (d, J = 8.2 Hz, 1H, F ₂ ppy), 5.34 (d, J = 8.2 Hz, 1H, F ₂ ppy), 5.26-5.18 (m, 2H, F ₂ ppy)
³¹ P NMR (243 MHz, rt): δ-3.51 (s, 1P, PPh ₃ ), -4.58 (s, 1P, PPh ₃ )

(2) Synthesis of Compound (6) (6Z) (0.050 g) was placed in an eggplant flask, the inside was purged with nitrogen, and then THF (8 ml) was added. Then, sodium hydride (0.018 g, 7.50 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature. The obtained suspension was centrifuged to remove the precipitate, and then the solvent was distilled off. The obtained yellow powder was washed with hexane (10 ml) and dried under reduced pressure to obtain (6) as a yellow powder (0.042 g).
¹ H NMR (600 MHz, CDCl ₃ ): δ9.23 (d, J = 5.5 Hz, 1H, F ₂ ppy), 8.22 (d, J = 8.2 Hz, 1H, F ₂ ppy), 8.13 (d, J = 8.4 Hz, 1H, F ₂ ppy), 7.63 (dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.59 (dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 7.33 (dd , J = 8.2, 8.2 Hz, 6H, PPh ₃ ), 7.28-7.24 (m, 4H, F ₂ ppy, PPh ₃ ), 7.15 (d, J = 5.5 Hz, 6H, PPh ₃ ), 6.98 (m, 1H , F ₂ ppy), 6.85 (dd, J = 6.9, 6.9Hz, 1H, F ₂ ppy), 6.77 (dd, J = 5.5, 5.5 Hz, 1H, F ₂ ppy), 6.54 (dd, J = 11.0, 11.0 Hz, 1H, F ₂ ppy), 6.37 (dd, J = 8.2, 13.7 Hz, 1H, F ₂ ppy), 5.70 (d, J = 8.2 Hz, 1H, F ₂ ppy)
³¹ P NMR (243 MHz, rt): δ-6.84 (s, 1P, PPh ₃ )

Synthesis Example 4 (Synthesis of metal complex compounds 92 and 129)
The metal complex compounds 92 and 129 were synthesized by the following route.

(2Z) (2.22 g, 2.42 × 10 ⁻³ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and then THF (40 ml) was added. Then, a toluene solution (15 ml) of silver trifluoromethanesulfonate (0.688 g, 2.68 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature. After centrifuging the resulting suspension to remove the precipitate, add a THF suspension (15 ml) of sodium hydride (0.288 g, 1.20 × 10 ^-2 mol) to the mother liquor and stir at room temperature overnight. did. The obtained suspension was centrifuged to remove the precipitate, and then the solvent was distilled off. This residue was dissolved in toluene (40 ml) and stirred overnight at 150 ° C. in an autoclave, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solution: methylene chloride / hexane = 1 / 2-3), then dissolved in methylene chloride and crystallized from a two-layer system with hexane to turn yellow (92) Obtained as granular crystals (0.348 g, 3.95 × 10 ⁻⁴ mol, yield 16.3%).

¹ H NMR (600 MHz, CDCl ₃ ): δ8.28 (dd, J = 8.2, 8.2 Hz, 2H), 8.09 (d, J = 8.2 Hz, 1H), 7.85 (d, J = 8.2 Hz, 1H) , 7.74 (dd, J = 6.9, 6.9 Hz, 1H), 7.67 (dd, J = 6.9, 6.9 Hz, 1H), 7.15 (m, 3H), 7.08 (dd, J = 9.6, 9.6Hz, 3H), 7.00-7.05 (m, 2H), 6.90-6.96 (m, 4H), 6.88 (dd, J = 6.9, 6.9 Hz, 1H), 6.70 (dd, J = 6.9, 6.9 Hz, 1H), 6.53 (d, J = 5.5 Hz, 2H), 6.46 (dd, J = 11.0, 11.0 Hz, 1H), 6.30 (dd, J = 9.6, 9.6 Hz, 1H), 6.22 (d, J = 8.2 Hz, 1H), 6.14 ( d, J = 8.2 Hz, 1H)
¹⁹ F NMR (564 MHz, CDCl ₃ ): δ-108.6 (s, 1F, F ₂ ppy), -109.1 (s, 1F, F ₂ ppy), -109.9 (s, 1F, F ₂ ppy), -110.0 (s, 1F, F ₂ ppy)
³¹ P [ ¹ H] NMR (243 MHz, CDCl ₃ ): δ95.9 (s, P (OC ₆ H ₄ ) (OPh) ₂ )

Moreover, the above-mentioned column purification simultaneously obtained the compound (129) as yellow granular crystals (0.080 g, 9.06 × 10 ⁻⁴ mol, yield 3.9%).

¹ H NMR (600 MHz, CDCl ₃ ): δ9.42 (d, J = 4.1 Hz, 1H), 8.24 (d, J = 5.5 Hz, 1H), 8.19 (d, J = 2.8 Hz, 1H), 7.94 (d, J = 5.5 Hz, 1H), 7.69 (dd, J = 4.8, 4.8 Hz, 1H), 7.63 (dd, J = 4.1, 4.1 Hz, 1H), 7.22 (dd, J = 4.1, 4.1 Hz, 2H), 7.14-7.08 (m, 3H), 7.05 (d, J = 4.1 Hz, 1H), 6.94-7.00 (m, 2H), 6.86-6.91 (m, 4H), 6.69 (dd, J = 4.8, 4.8 Hz, 1H), 6.50 (d, J = 5.5 Hz, 2H), 6.46 (d, J = 4.1 Hz, 2H), 6.31 (dd, J = 6.2, 6.2 Hz, 1H), 5.91 (d, J = 4.1 Hz, 1H), 5.43 (dd, J = 4.8, 4.8 Hz, 1H)
¹⁹ F NMR (564MHz, CDCl ₃ , ppm): δ-108.0 (s, 1F, F ₂ ppy), -109.3 (s, 1F, F ₂ ppy), -109.9 (d, J = 14.7, 1F, F ₂ ppy), -110.1 (s, J = 9.8 Hz, 1F, F ₂ ppy)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ120.2 (s, 1P, P (OC ₆ H ₄ ) (OPh) ₂ ).
Anal. Calcd for C ₄₀ H ₂₆ N ₂ O ₃ F ₄ PIr: C, 54.41; H, 2.97; N, 3.17. Found: C, 54.51; H, 2.88; N, 3.17.

    The X-ray structural diagrams and emission spectra of the obtained compounds (92) and (129) are shown in FIG. From the compound (92), it can be seen that Ns of the two cyclometal ligands are located in the cis position relative to each other. In addition, when the emission spectra were compared, it was found that (92) emitted light with a shorter wavelength and the emission quantum yield was about 8 times higher.

Synthesis Example 5 (Synthesis of metal complex compounds 94 and 130)
The metal complex compounds 94 and 130 were synthesized by the following route.

(4Z) (1.01 g, 1.19 × 10 ⁻³ mol) was placed in an eggplant flask, and the interior was purged with nitrogen, and then THF (40 ml) was added. Then, a toluene solution (15 ml) of silver trifluoromethanesulfonate (0.364 g, 1.42 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature. The resulting suspension was centrifuged to remove the precipitate, and then the THF suspension (15 ml) of sodium hydride (0.148 g, 6.17 × 10 ^-3 mol) was added to the mother liquor and stirred at room temperature overnight. did. The obtained suspension was centrifuged to remove the precipitate, and then the solvent was distilled off. This residue was dissolved in toluene (40 ml), stirred in an autoclave at 150 ° C. overnight, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solution: methylene chloride / hexane = 1 / 2-3), dissolved in methylene chloride, and crystallized from a two-layer system with hexane (94) (0.054 g, 6.62 × 10 ⁻⁵ mol, yield 5.6%) and (130) yellow granular crystals were obtained.

Compound (94)
¹ H NMR (600 MHz, CDCl ₃ ): δ 8.30 (d, J = 8.2 Hz, 1H), 8.26 (d, J = 5.5 Hz, 1H), 7.84 (d, J = 8.2 Hz, 1H), 7.68 (dd, J = 8.2, 8.2 Hz, 2H), 7.62 (d, J = 5.5 Hz, 1H), 7.59 (dd, J = 8.2, 8.2 Hz, 2H), 7.51 (d, J = 5.5 Hz, 1H) , 6.85-7.22 (m, 14H), 6.83 (dd, J = 6.9, 6.9 Hz, 1H), 6.79 (d, J = 8.2 Hz, 1H), 6.76 (dd, J = 6.9, 6.9 Hz, 1H), 6.66 (dd, J = 8.2, 8.2 Hz, 1H), 6.50 (d, J = 8.2 Hz, 2H), 6.22 (d, J = 8.2 Hz, 1H)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ97.10 (s, 1P, P (OPh) ₂ (OC ₆ H ₄ ))

Compound (130)
¹ H NMR (600 MHz, CDCl ₃ ): δ 9.40 (d, J = 4.6 Hz, 1H), 8.21 (d, J = 6.9 Hz, 1H), 7.80 (d, J = 9.2 Hz, 1H), 7.62 (dd, J = 6.9, 6.9 Hz, 1H), 7.60 (d, J = 6.9 Hz, 1H), 7.57-7.53 (m, 2H), 7.39 (d, J = 6.9 Hz, 1H), 7.16 (dd, J = 8.0, 8.0 Hz, 2H), 6.80-7.08 (m, 13H), 6.68 (d, J = 6.9, 6.9 Hz, 1H), 6.65 (dd, J = 8.0, 8.0 Hz, 1H), 6.52 (d , J = 6.9 Hz, 1H), 6.49 (d, J = 6.0 Hz, 2H), 6.47 (d, J = 6.0 Hz, 1H), 6.09 (dd, J = 8.0, 8.0 Hz, 1H)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ121.9 (s, 1P, P (OPh) ₂ (OC ₆ H ₄ ))

    The X-ray structural diagrams and emission spectra of the resulting compounds (94) and (130) are shown in FIG. From the compound (94), it can be seen that N of the cyclometal ligand is located at the cis position relative to each other. On the other hand, in the compound (130), N of the cyclometal ligand is in the trans position. Compound (94) showed emission spectra at 474 and 502 nm.

Synthesis Example 6 (Synthesis of metal complex compound 115)
The metal complex compound 115 was synthesized by the following route.

(1) Synthesis of Compound (115Y) (X) (2.00 g, 2.23 × 10 ⁻³ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and toluene (30 ml) was added. Subsequently, dimethyl sulfoxide (1.5 ml, 2.11 × 10 ⁻² mol) was added, and the mixture was stirred at room temperature for 4 hours. The solution was evaporated and dried under reduced pressure to obtain a yellow powder (Y). This powder was dissolved in methylene chloride (20 ml), and then a solution of (2X) (0.98 g, 5.13 × 10 ⁻³ mol) in methylene chloride (20 ml) was added dropwise. The solution was stirred overnight at room temperature, then the solvent was distilled off, washed with ether (30 ml), and dried under reduced pressure to give (115Y) as a pale yellow powder (2.46 g, 4.28 × 10 ^-3 mol). Yield 95.8%). Single crystal X-ray structural analysis was carried out by dissolving yellow powder in methylene chloride and using yellow granular crystals obtained from a two-layer system with hexane.

¹ H NMR (600 MHz, CDCl ₃ ): δ9.76 (d, J = 4.8Hz, 1H, F ₂ ppy), 8.21 (d, J = 8.1Hz, 1H, F ₂ ppy), 7.83-7.80 (m , 2H, F ₂ ppy), 7.24 (d, J = 6.6Hz, 1H, F ₂ ppy), 6.62 (dd, J = 10.2, 11.0Hz, 1H, F ₂ ppy), 3.67 (s, 3H, dmso) , 3.63 (s, 3H, dmso), 2.93 (s, 3H, dmso), 2.64 (s, 3H, dmso), -16.50 (s, 1H, Ir-H)
IR (KBr pellets): ν (Ir-H) / cm ^-1 2104 (s), (S = O) / cm ^-1 1126 (s), 1103 (s)

(2) Synthesis of Compound (115Z) (115Y) (1.97 g, 3.43 × 10 ⁻³ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and THF (40 ml) was added. Then, a dispersion of sodium hydride (0.450 g, 1.87 × 10 ⁻² mol) in THF (30 ml) was added and stirred overnight at room temperature, followed by centrifugation, and the solvent of the mother liquor was distilled off. The obtained red-orange powder was washed with hexane (30 ml x 2) and dried under reduced pressure to give (115Z) as an orange powder (1.67 g, 3.08 x 10 ^-3 mol, yield 89.8%) Obtained.

¹ H NMR (600MHz, CDCl ₃ , ppm): δ9.78 (d, J = 5.8 Hz, 1H, F ₂ ppy), 8.25 (d, J = 9.2 Hz, 1H, F ₂ ppy), 7.81 (dd, J = 8.0, 8.0 Hz, 1H, F ₂ ppy), 7.32 (d, J = 6.9 Hz, 1H, F ₂ ppy), 7.24 (dd, J = 6.9, 6.9 Hz, 1H, F ₂ ppy), 6.51 ( dd, J = 10.9, 10.9 Hz, 1H, F ₂ ppy), 3.63 (s, 3H, dmso), 3.56 (s, 3H, dmso), 2.99 (s, 3H, dmso), 2.22 (s, 3H, dmso ), -13.32 (d, J = 5.8 Hz, 1H, Ir-H), -18.29 (d, J = 5.8 Hz, 1H, Ir-H)
IR (KBr pellets): ν (Ir-H) / cm ^-1 2117 (s), 2078 (s)

(3) Synthesis of Compound (115) (115Z) (0.757 g, 1.40 × 10 ⁻³ mol) was placed in an eggplant flask and the interior was purged with nitrogen, and then toluene (30 ml) was added. Then, triphenyl phosphite (0.896 g, 2.89 × 10 ⁻³ mol) was added and refluxed for 4 days, and then the solvent was distilled off. The obtained orange powder was washed with hexane (20 ml x 2), dried under reduced pressure, dissolved in THF (20 ml), and crystallized from a two-layer system with hexane to give (115) an orange color. Obtained as granular crystals (0.373 g, 3.47 × 10 ⁻⁴ mol, yield 24.8%).

¹ H NMR (600MHz, CDCl ₃ , ppm): δ9.24 (d, J = 5.7 Hz, 1H), 7.86 (d, J = 10.3 Hz, 1H), 6.4-7.45 (m, 31H), 6.38 (dd , J = 9.2, 9.2 Hz, 1H), 6.02 (dd, J = 7.5, 7.5 Hz, 1H), -17.49 (dd, J = 25.3, 19.5 Hz, 1H, Ir-H)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ122.1 (m, 1P, P (OPh) ₂ (OC ₆ H ₄ )), 89.0 (dd, J = 18.2, 18.2 Hz, 1P, P (OPh ₃ ))

  The X-ray structural diagrams and emission spectra of the resulting compounds (115Y) and (115) are shown in FIG. Compound (115) showed emission spectra at 443 and 466 nm.

Synthesis Example 7 (Synthesis of metal complex compound 116)
The metal complex compound 116 was synthesized by the following route.

(1) Synthesis of Compound (116Y) (X) (2.00 g, 2.23 × 10 ⁻³ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and toluene (30 ml) was added. Then, dimethyl sulfoxide (1.5 ml, 2.11 × 10 ⁻² mol) was added, and the mixture was stirred at room temperature for 4 hours. Then, the solution was distilled off and dried under reduced pressure to obtain a light yellow powder (Y). This powder was dissolved in methylene chloride (20 ml), and then a solution of (4X) (0.65 mL, 4.54 × 10 ⁻³ mol) in methylene chloride (20 ml) was added dropwise. The solution was stirred overnight at room temperature, and then the solvent was distilled off, washed with ether (30 ml), and dried under reduced pressure to give (116Y) as a yellow powder (2.38 g, 4.41 × 10 ^-3 mol, Yield 99.0%). Single crystal X-ray structural analysis was carried out by dissolving yellow powder in methylene chloride and using yellow granular crystals obtained from a two-layer system with hexane.

¹ H NMR (600 MHz, CDCl ₃ ): δ9.74 (d, J = 6.9 Hz, 1H, ppy), 8.13 (d, J = 9.2 Hz, 1H, ppy), 7.84-7.78 (m, 2H, ppy ), 7.67 (d, J = 9.2 Hz, 1H, ppy), 7.25-7.19 (m, 2H, ppy), 7.14 (dd, J = 8.0, 8.0 Hz, 1H, ppy), 3.72 (s, 3H, dmso ), 3.65 (s, 3H, dmso), 3.01 (s, 3H, dmso), 2.57 (s, 3H, dmso), -16.45 (s, 1H, Ir-H)
IR (KBr pellets): ν (Ir-H) / cm ^-1 2119 (s), (S = O) / cm ^-1 1113 (s), 1101 (s)

(2) Synthesis of Compound (116) (116Y) (0.100 g, 1.74 × 10 ⁻⁴ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and THF (10 ml) was added. Then, a dispersion of sodium hydride (0.015 g, 6.25 × 10 ⁻⁴ mol) in THF (10 ml) was added, and the mixture was stirred at room temperature overnight, then centrifuged, and the solvent of the mother liquor was distilled off. The obtained reddish orange powder was dissolved in toluene (15 ml), triphenyl phosphite (0.123 g, 4.17 × 10 ⁻⁴ mol) was added, and the mixture was refluxed for 4 days. The obtained white powder was washed with hexane (20 ml x 2), dried under reduced pressure, dissolved in tetrahydrofuran (20 ml), and crystallized from a two-layer system with hexane (116) Obtained as plate crystals (0.036 g, 3.46 × 10 ⁻⁵ mol).

¹ H NMR (600MHz, CDCl ₃ , ppm): δ9.14 (d, J = 5.7 Hz, 1H), 7.56 (d, J = 7.4 Hz, 1H), 7.53 (dd, J = 8.0 Hz, 1H), 6.6-7.43 (m, 32H), 6.41 (dd, J = 7.7, 7.7 Hz, 1H), 6.00 (dd, J = 7.7, 7.7 Hz, 1H), -17.49 (dd, J = 23.7, 20.3 Hz, 1H , Ir-H)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ124.0 (dd, J = 64.1, 64.1 Hz, 1P, P (OPh) ₂ (OC ₆ H ₄ )), 89.6 (dd, J = 51.3, 51.3 Hz , 1P, P (OPh ₃ ))

  The X-ray structural diagram and emission spectrum of the obtained compounds (116Y) and (116) are shown in FIG. Compound (116) showed emission spectra at 451, 481 and 507 nm.

Synthesis Example 8 (Synthesis of metal complex compound 117)
The metal complex compound 117 was synthesized by the following route.

Acetylacetonate sodium salt (Na (acac)) was prepared by adding acetylacetone to an ether suspension of sodium hydride and stirring for 2 hours.
(115Y) (0.356 g, 6.20 × 10 ⁻⁴ mol) was placed in an eggplant flask, the interior was purged with nitrogen, and tetrahydrofuran (20 ml) was added. Subsequently, triphenyl phosphite (0.23 ml, 8.68 × 10 ⁻⁴ mol) was added, and the mixture was stirred at 50 ° C. overnight, and then the solvent was distilled off. The obtained powder was washed with ether (20 ml), dried under reduced pressure, and then dissolved in tetrahydrofuran (20 ml). To this solution was added Na (acac) (0.085 g, 6.96 × 10 ⁻⁴ mol), and the mixture was stirred at 50 ° C. for 24 hours, and then the solvent was distilled off. The resulting yellow powder was extracted with toluene (20 ml) and centrifuged, and then the mother liquor was placed in a pressure vessel and stirred at 150 ° C. overnight. After removing the solvent of the reaction solution, purification by silica gel column chromatography (developing solution: Enka Methylene) gave a yellow powder. The obtained yellow powder was dissolved in methylene chloride and crystallized from a two-layer system with hexane to obtain (117) as yellow granular crystals (0.107 g, 1.35 × 10 ⁻⁴ mol, yield 21.8%).

¹ H NMR (600MHz, CDCl ₃ , ppm): δ8.01 (d, J = 9.2 Hz, 1H), 7.92 (d, J = 4.6 Hz, 1H), 7.70 (dd, J = 8.0, 8.0 Hz, 1H ), 7.22 (dd, J = 6.9, 6.9 Hz, 2H), 7.14 (dd, J = 6.9, 6.9 Hz, 3H), 7.10 (dd, J = 5.8, 5.8 Hz, 1H), 7.05 (d, J = 11.5 Hz, 3H), 6.88-6.96 (m, 4H), 6.57 (d, J = 6.9 Hz, 2H), 6.36 (dd, J = 10.3, 10.3 Hz, 1H), 6.19 (d, J = 6.9 Hz, 1H), 5.23 (s, 1H, acac), 1.80 (s, 3H, acac), 1.74 (s, 3H, acac)
¹⁹ F NMR (564MHz, CDCl ₃ , ppm): δ-108.8 (s, 1F, F ₂ ppy), -110.9 (d, J = 26.2 Hz, 1F, F ₂ ppy)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ78.95 (s, P (OPh) ₂ (OC ₆ H ₄ )).

  The X-ray structural diagram and emission spectrum of the obtained compound (117) are shown in FIG. Compound (117) showed emission spectra at 445 and 473 nm.

Synthesis Example 9 (Synthesis of metal complex compound 118)
The metal complex compound 118 was synthesized by the following route.

Acetylacetonate sodium salt (Na (acac)) was prepared by adding acetylacetone to an ether suspension of sodium hydride and stirring for 2 hours.
(116Y) (0.420 g, 7.80 × 10 ⁻⁴ mol) was placed in an eggplant flask, the interior was purged with nitrogen, and tetrahydrofuran (30 ml) was added. Subsequently, triphenyl phosphite (0.4 ml, 1.52 × 10 ⁻³ mol) was added, and the mixture was stirred overnight at room temperature, and then the solvent was distilled off. The obtained powder was washed with ether (30 ml), dried under reduced pressure, and then dissolved in tetrahydrofuran (30 ml). To this solution was added Na (acac) (0.114 g, 9.36 × 10 ⁻⁴ mol), and the mixture was stirred at 50 ° C. for 24 hours, and then the solvent was distilled off. The resulting yellow powder was extracted with toluene (30 ml) and centrifuged, and then the mother liquor was stirred at 100 ° C. overnight. After the solvent of this reaction solution was distilled off, purification by silica gel column chromatography (developing solution: methylene chloride) gave a yellow powder. The obtained yellow powder was dissolved in methylene chloride and crystallized from a two-layer system with hexane to obtain (118) as yellow plate crystals (0.137 g, 1.81 × 10 ^-4 mol, yield 23.3%). .

¹ H NMR (600MHz, CDCl ₃ , ppm): δ7.88 (d, J = 5.5 Hz, 1H), 7.67 (dd, J = 6.9, 6.9 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H ), 7.36 (d, J = 5.5 Hz, 1H), 7.21 (dd, J = 6.9, 6.9 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 7.11 (dd, J = 8.2, 8.2 Hz , 2H), 7.07-7.04 (m, 3H), 6.91-6.86 (m, 6H), 6.81 (dd, J = 6.9, 6.9 Hz, 1H), 6.69 (d, J = 8.2 Hz, 1H), 6.50 ( d, J = 8.2 Hz, 1H), 5.21 (s, 1H, acac), 1.80 (s, 3H, acac), 1.72 (s, 3H, acac)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ79.58 (s, P (OPh) ₂ (OC ₆ H ₄ ))

  The X-ray structural diagram and emission spectrum of the obtained compound (118) are shown in FIG. Compound (118) exhibited an emission spectrum at 461 and 493 nm.

Synthesis Example 10 (Synthesis of metal complex compound 119)
The metal complex compound 119 was synthesized by the following route.

ナスフラスコに(116Y) (0.300 g, 5.56×10^-4 mol) を入れ、内部を窒素置換した後、トルエン(20 ml) を加えた。ついでトリフェニルホスファイト(0.347 g, 1.12×10^-3 mol) を加え、一昼夜還流した後、溶媒を留去した。得られた残渣をヘキサン (20 ml)で洗浄し、減圧下で乾燥した。得られた白色粉末をテトラヒドロフランに溶かし、ヘキサンとの二層系より結晶化することで (119)を無色粒状晶 (0.140 g, 1.21×10^-4 mol, 収率21.8%) として得た。

(116Y) (0.300 g, 5.56 × 10 ⁻⁴ mol) was placed in an eggplant flask, the inside was purged with nitrogen, and toluene (20 ml) was added. Subsequently, triphenyl phosphite (0.347 g, 1.12 × 10 ⁻³ mol) was added, and the mixture was refluxed overnight, and then the solvent was distilled off. The resulting residue was washed with hexane (20 ml) and dried under reduced pressure. The obtained white powder was dissolved in tetrahydrofuran and crystallized from a two-layer system with hexane to obtain (119) as colorless granular crystals (0.140 g, 1.21 × 10 ⁻⁴ mol, yield 21.8%).

¹ H NMR (600 MHz, CDCl ₃ ): δ8.28 (dd, J = 7.5, 7.5 Hz, 1H), 7.35 (dd, J = 8.0, 8.0 Hz, 2H), 7.25-5.92 (m, 40H)
³¹ P NMR (243MHz, CDCl ₃ , ppm): δ110.5 (dd, J = 26.0, 26.0 Hz, 1P), 84.9 (dd, J = 26.0, 26.0 Hz, 1P), 70.7 (dd, J = 26.0, (26.0 Hz, 1P)

  The X-ray structural diagram and emission spectrum of the obtained compound (119) are shown in FIG. Compound (119) showed emission spectra at 455, 483 and 511 nm.

  10 and 11 show ultraviolet-visible light absorption spectra of the various compounds obtained. Further, Table 1 shows X-ray structural analysis data, and Table 2 shows data of each bond distance and bond angle.

  As described above in detail, when a compound having an N, N trans structure obtained by a conventional method is reacted in the presence of a compound having a hydride, isomerization proceeds, and the N, C trans structure having the above-described structure is highly efficient. It was found that a trivalent iridium metal complex compound of any one of the general formulas (I) to (IV) and (VII) can be obtained. It was found that the obtained N, C trans structure had a quantum yield of light emission 3 to 8 times higher than that of the N, N trans structure, and the emission wavelength was also shifted by a short wavelength. By utilizing this technology, the possibility of breakthrough to a blue light emitting organic EL element that has not been improved so far has increased, and the present invention provides various display elements, displays, backlights, illumination light sources, signs, signs, Applicable to fields such as interior.

It is a figure which shows the X-ray figure and emission spectrum of compound (2) and (2Z). It is a figure which shows the X-ray figure and emission spectrum of compound (4) and (4Z). It is a figure which shows the X-ray figure and emission spectrum of a compound (92) and (129). It is a figure which shows the X-ray figure and emission spectrum of a compound (94) and (130). It is a figure which shows the X-ray diagram and emission spectrum of a compound (115Y) and (115). It is a figure which shows the X-ray figure and emission spectrum of a compound (116Y) and (116). FIG. 2 shows an X-ray diagram and an emission spectrum of a compound (117). It is a figure which shows the X-ray figure and emission spectrum of a compound (118). It is a figure which shows the X-ray figure and emission spectrum of a compound (119). It is a figure which shows the ultraviolet visible light absorption spectrum of the synthesize | combined complex. It is a figure which shows the ultraviolet visible light absorption spectrum of the synthesize | combined complex.

Claims (16)

A trivalent iridium metal complex compound represented by the following general formula (I) or (II) having a nitrogen-containing cyclometal ligand.

(In the formula, N of the nitrogen-containing cyclometal ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. The solid line represents the σ bond and the dotted line represents the coordinate bond. The nitrogen-containing cyclometal ligands may be different or the same.
X is a substituent having a valence of 1, and represents a hydrogen atom, a halogen atom, a cyano group, a thiocyanate group, a silyl group, an amide group, an alkoxy group, an alkyl group, an aromatic oxy group or an aromatic group. A fluorine atom, a fluorine-substituted alkyl group, a cyano group, a nitro group, or a hetero element may be introduced on the aromatic ring.
L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. X and L may be bonded to each other but are not nitrogen-containing cyclometal ligands. ) A trivalent iridium metal complex compound represented by the following general formula (III) or (IV) having a cyclometalcarbene ligand.

(In the formula, carbene C of the cyclometalcarbene ligand and C of the other cyclometal ligand are located in the trans position with respect to the iridium metal. The solid line represents the σ bond, and the dotted line represents the coordinate bond.
X is a substituent having a valence of 1, and represents hydrogen, halogen, cyano group, thiocyanate group, silyl group, amide group, alcoholoxy group, alkyl group, aromatic oxy group, or aromatic group. An F atom, an F-substituted alkyl group, a cyano group, a nitro group, and a hetero element may be introduced on the aromatic ring.
L is a substituent capable of coordinating bonding to iridium, and represents a group via atoms 14 to 16 of the periodic table. X and L may be bonded to each other. ) The metal complex compound according to claim 1, wherein in the general formula (I) or (II), the nitrogen-containing cyclometal ligand is a compound represented by the following general formula.

(In the formula, R ^{1 to} R ²² each independently have a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a substituent. An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and a substituent; C1-C12 halogenated alkoxy group which may have, C6-C20 aromatic oxy group which may have a substituent, C6-C20 aroma which may have a substituent An aromatic hydrocarbon group, a C3-C20 heterocyclic group that may have a substituent, a C1-C12 halogenated alkyl group that may have a substituent, or a substituent. C2-C12 alkenyl group, C2-C12 alkynyl group which may have a substituent, or substitution The cycloalkyl group of 3 to 20 carbon atoms which may have. Adjacent R together may be bonded to each other to form a ring.) The metal complex compound according to claim 2, wherein in the general formula (III) or (IV), the cyclometalcarbene ligand is a compound represented by the following general formula.

(Wherein R ^{23 to} R ²⁹ each independently have a hydrogen atom, a cyano group, a nitro group, a halogen atom, a C 1-12 alkyl group which may have a substituent, or a substituent. An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and a substituent; C1-C12 halogenated alkoxy group which may have, C6-C20 aromatic oxy group which may have a substituent, C6-C20 aroma which may have a substituent An aromatic hydrocarbon group, a C3-C20 heterocyclic group that may have a substituent, a C1-C12 halogenated alkyl group that may have a substituent, or a substituent. C2-C12 alkenyl group, C2-C12 alkynyl group which may have a substituent, or substitution A cycloalkyl group having 3 to 20 carbon atoms which may have a group, and adjacent Rs may be bonded to each other to form a ring.)   The metal complex compound according to claim 3 or 4, wherein L in the general formulas (I), (II), (III) and (IV) is a group containing phosphorus as a coordination atom.   The metal complex compound according to claim 3 or 4, wherein X in the general formulas (I), (II), (III) and (IV) is a halogen. In the general formulas (I), (II), (III) and (IV), the bidentate ligand formed by combining L and X with each other is a compound represented by any one of the following general formulas: Item 5. The metal complex compound according to Item 3 or 4.

(In the formula, Y represents an O atom, an S atom or C (R ⁴³ R ⁴⁴ ).
R ^{30 to} R ⁴⁴ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted carbon number. It may have an alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or a substituent. Good C1-C12 halogenated alkoxy group, C6-C20 aromatic oxy group which may have a substituent, C6-C20 aromatic hydrocarbon group which may have a substituent , A heterocyclic group having 3 to 20 carbon atoms which may have a substituent, a halogenated alkyl group having 1 to 12 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent. 12 alkenyl groups, optionally having 2-12 alkynyl groups, or having substituents It is a C3-C20 cycloalkyl group which may be. Adjacent Rs may be bonded to each other to form a ring. ) The metal complex compound of Claim 1 represented by either of the following general formula.

The metal complex compound of Claim 2 represented by either of the following general formula.

A process for producing (I) and (II) by using the following general formula (V) as a raw material and carrying out an isomerization reaction in the presence of a compound containing hydride.

A process for producing (III) and (IV) by using the following general formula (VI) as a raw material and carrying out an isomerization reaction in the presence of a compound containing hydride.

The method according to claim 10 or 11, wherein the hydride is NaH, LiAlH ₄ , or NaBH ₄ . A trivalent iridium metal complex compound represented by the following general formula (VII) having a cyclometal ligand containing a phosphorus atom.

  The organic electroluminescence device in which at least one organic thin film layer having at least one light emitting layer is sandwiched between a pair of electrodes, and at least one of the organic thin film layers is any one of claims 1, 2, and 13. An organic electroluminescence device that contains the metal complex compound described in 1 and emits light when a voltage is applied between both electrodes.   The organic electroluminescent element according to claim 14, wherein the light emitting layer contains the metal complex compound according to claim 1.   The organic electroluminescence device according to claim 14 or 15, wherein the layer containing the metal complex compound is formed by coating.

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