JP2004175799A - Organic light emitting device material and organic light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide phosphorescent materials and polymer phosphorescent materials that emit lights of various colors that exclude green color, useful for high performance multicolor light-emitting organic EL devices. <P>SOLUTION: The present invention relates to the organic light-emitting material containing complex of gold expressed by formulas (2) and (6) in which gold atom links with at least one atom selected from carbon, oxygen and sulfur, and the organic light-emitting devices including the materials in its light-emitting layer. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to an organic light emitting device (OLED) that emits light by electric energy and can be used for a flat display panel and a backlight and an illumination light source used for the same, an electrophotograph, an optical device light source, a sign board, and the like, and light emission used for the organic light emitting device. About the material.

  Organic light-emitting devices have been shown to emit light with high brightness by CW Tang of Kodak Company in 1987 (Appl. Phys. Lett., 51, 913, 1987: Non-Patent Document 1). Improvements in the element structure have progressed rapidly, and practical use has recently begun with displays for car audio and mobile phones. In order to further expand the applications of the organic EL, development of materials for improving luminous efficiency and durability, development of full-color display, and the like are currently being actively performed.

Regarding the luminous efficiency, the current light-emitting materials utilize light emission from an excited singlet state, that is, fluorescence, and the generation ratio of an excited singlet state to an excited triplet exciton in electrical excitation is 1%. : 3, the upper limit of the internal quantum efficiency of light emission in organic EL (electroluminescence) is 25% (Monthly Display, October 1998, separate volume, “Organic EL Display”, p. 58: Non-Patent Document 2). .
On the other hand, MA Baldo et al. Obtained an external quantum efficiency of 7.5% by using an iridium complex that emits phosphorescence from an excited triplet state, which corresponds to an internal quantum efficiency of 37.5% assuming an external extraction efficiency of 20%. It has been shown that it is possible to exceed the upper limit of 25% when a fluorescent dye is used (Appl. Phys. Lett., 75, 4 pages, 1999: Non-Patent Document 3, International Publication No. 00/70655 pamphlet: Patent Document 1).

On the other hand, as for the emission color, the emission color of the iridium complex reported by Baldo et al. Is green, but in recent years, while active research is being conducted on full-color displays and white light sources using organic EL elements, other There has been a demand for the development of materials that emit light with high efficiency even in colors.
As for the method of manufacturing an organic EL element, a vacuum evaporation method has been used conventionally, but this method requires vacuum equipment, and the organic thin film can be formed to have a uniform thickness as the area becomes larger. It has problems such as difficulty.

On the other hand, the ink-jet method and the printing method, which have been developed as a film-forming technique by coating, can form a film under normal pressure, and are excellent in increasing the area of the element and in mass productivity. In film formation by these methods, it is not possible to use a low molecular compound that may cause layer separation or segregation, and therefore, it has been necessary to develop a polymer luminescent material that does not crystallize.
As described above, there has been a demand for the development of phosphorescent materials and polymer phosphorescent materials that exhibit emission colors other than green, which are required for high-performance multicolor light-emitting organic EL devices.

Appl. Phys. Lett., 51, 913, 1987 Monthly Display, October 1998 Special Volume “Organic EL Display”, p. 58 Appl. Phys. Lett., 75, 4 pages, 1999 International Publication No. 00/70655 pamphlet

  An object of the present invention is to provide a phosphorescent material useful for a high-performance multicolor organic EL device.

  As a result of various studies, the inventors have solved the problem by the following means. That is, the present invention relates to a light-emitting material using a phosphorescent gold complex useful as an organic EL light-emitting material, and a light-emitting element using these light-emitting materials.

〔式中、Ｌ¹は単座もしくは二座配位子を表わし、ｎは１〜５の整数を表わし、Ｒ¹¹は水素原子、ハロゲン原子、シアノ基、シリル基、またはヘテロ原子を有してもよいアルキル基、アリール基、アルコキシ基、アシル基、カルボキシル基またはアルコキシカルボニル基を表わす。〕
で示される化合物である前記５記載の有機発光素子材料。
７．金錯体が、式（２）

〔式中、ｎ及びＲ¹¹は前記６の記載と同じ意味を表わし、Ｒ²¹〜Ｒ²³は、それぞれ独立して水素原子、アミノ基、シアノ基、シリル基、またはヘテロ原子を有してもよいアルキル基、アリール基、アルコキシ基、アリールオキシ基またはアルキルアミノ基を表わす。〕
で示される化合物である前記６記載の有機発光素子材料。
８．金錯体が、式（３）

〔式中、Ｌ¹及びＬ²は、それぞれ独立して単座もしくは二座配位子を表わし、ｎは１〜５の整数を表わす。〕
で示される化合物である前記５記載の有機発光素子材料。
９．金錯体が、式（４）

〔式中、ｎは１〜５の整数を表わし、Ｒ²¹〜Ｒ²⁶は、それぞれ独立して水素原子、アミノ基、シアノ基、シリル基またはヘテロ原子を有してもよいアルキル基、アリール基、アルコキシ基、アリールオキシ基またはアルキルアミノ基を表わす。〕
で示される化合物である前記５記載の有機発光素子材料。
１０．非金属元素が窒素である金錯体を含む前記４に記載の有機発光素子材料。
１１．金−炭素結合を有する炭素原子との間に三重結合を形成している窒素原子がさらに別の炭素原子と結合している金錯体を含む前記１０に記載の有機発光素子材料。
１２．金錯体が、式（５）

〔式中、Ｙはアルキレン、シクロアルキレンあるいはアリーレン基を表わすか、または同一あるいは相異なる前記の２以上の基が交互に結合した有機基を表わし、Ｌ³及びＬ⁴は、それぞれ独立して単座あるいは二座配位子を表わす。〕
で示される化合物である前記１１に記載の有機発光素子材料。
１３．炭素、酸素及び硫黄の中から選ばれる少なくとも一つの原子が硫黄である金錯体を含む前記１に記載の有機発光素子材料。
１４．金錯体が、式（６）

〔式中、Ｒ³¹〜Ｒ³⁵は、それぞれ独立して水素原子、ハロゲン原子、水酸基、ニトロ基、アミノ基、シアノ基、メルカプト基、シリル基、スルホン酸基、スルホン酸エステル基、リン酸基、ホスホン酸基、またはヘテロ原子を有してもよいアルキル基、アリール基、アルコキシ基、アシル基、カルボキシル基、アルコキシカルボニル基またはアシルオキシ基を表わし、Ｘ⁺は一価の陽イオンを表わす。〕
で示される化合物である前記１３に記載の有機発光素子材料。
１５．金錯体が、式（７）

〔式中、Ｒ⁴¹〜Ｒ⁵²は、それぞれ独立して水素原子、シアノ基、シリル基、またはヘテロ原子を有してもよいアルキル基、アリール基またはアシル基を表わし、Ｚはアルキレン、シクロアルキレンあるいはアリーレン基を表わすか、または同一あるいは相異なる前記の２以上の基が交互に結合した有機基を表わす。〕
で示される化合物である前記１３に記載の有機発光素子材料。
１６．一対の電極間に、発光層を含む一層以上の有機化合物が挟持されてなる有機発光素子において、前記１乃至１５のいずれか一つに記載の有機発光素子材料を発光層に含むことを特徴とする有機発光素子。
１７．式（４）

〔式中、ｎは１〜５の整数を表わし、Ｒ²¹〜Ｒ²⁶は、それぞれ独立して水素原子、アミノ基、シアノ基、シリル基またはヘテロ原子を有してもよいアルキル基、アリール基、アルコキシ基、アリールオキシ基またはアルキルアミノ基を表わす（ただし、Ｒ²¹〜Ｒ²⁶がすべてシクロヘキサン環であり、かつｎが１または２である場合を除く。）。〕で示される化合物。 1. An organic light-emitting device material, wherein gold includes a gold complex bonded to at least one atom selected from carbon, oxygen and sulfur.
2. 2. The organic light-emitting device material according to 1, wherein at least one atom selected from carbon, oxygen, and sulfur bonded to gold contains a gold complex bonded to only one atom in addition to gold.
3. 2. The organic light-emitting device material according to the above 1, including a gold complex in which at least one atom selected from carbon, oxygen and sulfur is carbon.
4. 4. The organic light-emitting device material according to the above item 3, including a gold complex in which a carbon atom bonded to gold is bonded to a nonmetal element by a triple bond and bonded to gold by a single bond.
5. 5. The organic light emitting device material according to the above 4, wherein the material includes a gold complex in which the nonmetal element is carbon.
6. The gold complex has the formula (1)

[Wherein L ¹ represents a monodentate or bidentate ligand, n represents an integer of 1 to 5, and R ¹¹ may have a hydrogen atom, a halogen atom, a cyano group, a silyl group, or a hetero atom. It represents a good alkyl group, aryl group, alkoxy group, acyl group, carboxyl group or alkoxycarbonyl group. ]
6. The organic light emitting device material according to the above 5, which is a compound represented by the formula:
7. The gold complex has the formula (2)

[In the formula, n and R ¹¹ represent the same meaning as described in the above 6, and R ^{21 to} R ²³ each independently have a hydrogen atom, an amino group, a cyano group, a silyl group, or a hetero atom. It represents a good alkyl group, aryl group, alkoxy group, aryloxy group or alkylamino group. ]
7. The organic light-emitting device material according to the above 6, which is a compound represented by the formula:
8. The gold complex has the formula (3)

[Wherein, L ¹ and L ² each independently represent a monodentate or bidentate ligand, and n represents an integer of 1 to 5. ]
6. The organic light emitting device material according to the above 5, which is a compound represented by the formula:
9. The gold complex has the formula (4)

[In the formula, n represents an integer of 1 to 5, and R ^{21 to} R ²⁶ each independently represent a hydrogen atom, an amino group, a cyano group, an alkyl group which may have a silyl group or a hetero atom, an aryl group. , An alkoxy group, an aryloxy group or an alkylamino group. ]
6. The organic light emitting device material according to the above 5, which is a compound represented by the formula:
10. 5. The organic light-emitting device material according to the above 4, which contains a gold complex in which the nonmetal element is nitrogen.
11. 11. The organic light-emitting device material according to the above item 10, including a gold complex in which a nitrogen atom forming a triple bond with a carbon atom having a gold-carbon bond is further bonded to another carbon atom.
12. The gold complex has the formula (5)

[In the formula, Y represents an alkylene, cycloalkylene, or arylene group, or an organic group in which the same or different two or more groups are alternately bonded, L ³ and L ⁴ each independently represent a monodentate Alternatively, it represents a bidentate ligand. ]
12. The organic light-emitting device material according to the above 11, which is a compound represented by the formula:
13. 2. The organic light-emitting device material according to the above 1, which comprises a gold complex in which at least one atom selected from carbon, oxygen and sulfur is sulfur.
14． The gold complex has the formula (6)

[Wherein, R ^{31 to} R ³⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, a silyl group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group. , A phosphonic acid group, or an alkyl group, an aryl group, an alkoxy group, an acyl group, a carboxyl group, an alkoxycarbonyl group or an acyloxy group which may have a hetero atom, and X ⁺ represents a monovalent cation. ]
14. The organic light-emitting device material according to the above 13, which is a compound represented by the formula:
15. The gold complex has the formula (7)

[In the formula, R ^{41 to} R ⁵² each independently represent a hydrogen atom, a cyano group, a silyl group, or an alkyl group, an aryl group or an acyl group which may have a hetero atom, and Z represents an alkylene, a cycloalkylene. Alternatively, it represents an arylene group or an organic group in which the same or different two or more groups are alternately bonded. ]
14. The organic light-emitting device material according to the above 13, which is a compound represented by the formula:
16. An organic light-emitting element in which one or more organic compounds including a light-emitting layer are sandwiched between a pair of electrodes, wherein the organic light-emitting element material according to any one of 1 to 15 is included in the light-emitting layer. Organic light emitting device.
17. Equation (4)

[In the formula, n represents an integer of 1 to 5, and R ^{21 to} R ²⁶ each independently represent a hydrogen atom, an amino group, a cyano group, an alkyl group which may have a silyl group or a hetero atom, an aryl group. , An alkoxy group, an aryloxy group or an alkylamino group (except when R ^{21 to} R ²⁶ are all cyclohexane rings and n is 1 or 2). ] The compound shown by these.

Embodiment of the Invention

Hereinafter, the present invention will be described specifically.
The present invention provides a phosphorescent gold complex useful as an organic EL light emitting material, a light emitting material using the same, and a light emitting element using these light emitting materials. The light-emitting material may be a low-molecular gold complex alone, a polymer material obtained by polymerizing a component containing a gold complex, or a composite material in which a light-emitting material containing a gold complex and a material not containing a gold complex are mixed. Absent.

  The valence of gold in the gold complex is not particularly limited, but is preferably monovalent to tetravalent, and more preferably monovalent. Further, the gold complex may be an ionic complex having a charge on the central metal, in which case there is a counter ion for neutralizing the charge.

The bond in the present specification represents a chemical bond such as a covalent bond, a coordination bond, and a donative bond. Further, a triple bond, a single bond, and the like represent a formal bond order.
The organic light-emitting device material of the present invention contains a gold complex in which gold has a bond with an atom selected from carbon, oxygen and sulfur. Examples of the gold complex having a gold-carbon bond include an alkyl complex, an alkynyl complex, an alkylidene complex, an aryl complex, an alkene complex, an alkyne complex, a carbonyl complex, an acyl complex, a cyanide complex, an isocyanide complex, and a carbide complex. Examples of a gold complex in which gold has a bond to any one of oxygen and sulfur include an alkoxy complex, an aryloxy complex, a silyloxy complex, a carboxylate complex, an isocyanate complex, an oxide complex, and oxygen in these exemplified complexes. Homologues in which an atom is substituted with a sulfur atom can be given. In the definition of the formula symbols of the formulas (1), (2), (4), (6) and (7), the hetero atom of the alkyl group which may have a hetero atom is substituted by the alkyl group. Although it is not particularly limited as long as it is inserted, an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom are preferable.
Non-metal elements capable of forming a triple bond with a carbon atom bonded to gold include boron, carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, and the like.

L ^{1 to} L ⁴ in the formulas (1), (3) and (5) each represent a monodentate or bidentate ligand, and are not particularly limited as long as they can form a complex with gold. Ligand (phosphine ligand, phosphite ligand, phosphide ligand, etc.), nitrogen ligand (amine ligand, pyridine ligand, nitrile ligand, phenylpyridine ligand, Schiff base, etc.) ), Alkyl ligands, alkynyl ligands, carbonyl ligands, cyanide ligands, isocyanide ligands, diketonate ligands, carboxylate ligands, dithiocarbamate ligands and the like. Ligands, pyridine ligands and cyanide ligands are preferred. Further, L ¹ and L ² or L ³ and L ⁴ may be the same combination of ligands or different combinations.

As the substituents R ^{11 to} R ⁵² in each formula, for example, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, a silyl group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group, Phosphonic acid group, alkyl group (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, hexyl, cyclopentyl group, cyclohexyl group, etc.), allyl group, alkynyl group (ethynyl group, propynyl group, phenylethynyl group) , Silylethynyl group, etc.), aryl group (phenyl group, naphthyl group, biphenyl group, vinylphenyl group, tolyl group, etc.), aralkyl group (benzyl group, phenethyl group, cumyl group, etc.), heteroaryl group (pyridyl group, pyrrolyl) Group, imidazolyl group, quinolyl group, isoquinolyl group, thienyl group, Benzothienyl group, furyl group, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tertiary butoxy group, etc.), aryloxy group (phenoxy group, crezolyl group, etc.), Ester groups such as acetoxy group, carboxyl group, ethoxycarbonyl group and the like, organic groups such as acyl group (formyl group, acetyl group and the like), alkylamino group, alkylthio group and the like. These organic groups further include a halogen atom, a hydroxyl group, It may have a substituent such as a nitro group or an amino group, and these organic groups may be bonded to each other at one or more positions. Among them, preferred groups vary depending on the nature of the atom or atomic group to which the substituent R is bonded, but are not particularly limited as long as chemical stability is not impaired.

N in each formula is a parameter that greatly contributes to the emission color of phosphorescence, and represents an integer of 1 to 5, preferably 1 to 4.
Y and Z in the formulas (5) and (7) represent two isocyanide groups or an organic group bridging a phosphorus atom, for example, an alkylene group such as methylene, ethylene, propylene, butylene and hexylene, and a cycloalkylene group such as a cyclohexylene group. Groups, o-phenylene group, naphthylene group, arylene group such as ferrocenylene group, p-menthylene group, xylylene group, binaphthylene group and the like.

X ⁺ in the formula (6) represents a monovalent cation, and examples thereof include an alkali metal ion, an ammonium ion, an alkylammonium ion, a phosphonium ion, an imidazolium ion, and a pyridinium ion. In addition, one divalent cation such as an alkaline earth metal ion may be present for two gold complex ions.

Any of the gold complexes used in the light emitting device of the present invention can be produced using a gold halide compound as a starting material. For example compounds of formula (1), as shown in Scheme -1, and chloroauric complex A having a ligand L ^1, 1-alkynes or trimethylsilyl acetylene derivative, the stoichiometric amount of a strong base (e.g., sodium methoxide C) It is obtained by reacting in the presence. Instead of a strong base, a stoichiometric amount of an alkylamine (eg, triethylamine, isopropylamine, butylamine, pyrrolidine, etc.) and a catalytic amount (preferably 0.01 to 0.1 equivalent) of a copper (I) halide (eg, copper iodide, copper bromide) , Copper chloride). Gold complex A can be synthesized by the action of the ligand L ¹ in the gold chloride (I). Compounds of formula (1) can also be obtained by the action of the ligand L ¹ in the compound B gold and carbon are bonded as shown in Scheme -1. Compound B can be synthesized from gold (III) chloride by a known method (for example, J. Chem. Soc., P. 3220, 1962).

Gold complex represented by the formula (2) can be produced by using a phosphorus compound as a ligand L ¹ in the manufacturing method of the gold complex represented by the formula (1).
The gold complex represented by the formula (3) or the formula (4) is used as an alkyne to be reacted with the compound A represented by the scheme 1, as 0.5 equivalent of acetylene, butadiyne, hexatoin, octatetrain, decapentaine, or a terminal of these alkynes. It can be synthesized by using a silylated alkyne in which hydrogen is substituted with a silyl group.

  The compound represented by the formula (6) can be obtained by a method equivalent to a known method shown in Scheme-2 (J. Chem. Soc., Dalton Trans., P. 1845, p. 1845). And two equivalents of an alkylamine.

  The compound represented by the formula (7) is obtained by reacting a gold (I) halide (for example, gold (I) chloride) with a phosphorus compound having a 0.5 equivalent of a crosslinking group, followed by a mercaptan compound as shown in Scheme-3. Can be synthesized.

  Known compounds that can be used in the light emitting device of the present invention include, for example, J. Chem. Soc., Dalton Trans., 4227 (1996), J. Am. Chem. Soc., 123, 4985, (2001), J. Chem. Soc., Chem. Commun., 243 (1989), Inorg. Chim. Acta, 197, 177 (1992), J. Chem. Soc., Dalton Trans., 3585 (2000), Inorg. Chem., 32 , 2506 (1993) and J. Med. Chem., 30, 2181 (1987).

  Further, the gold complex in which a polymerizable functional group is introduced into the gold complex is polymerized to obtain an organic polymer light emitting device material in which the gold complex forms a part of a polymer.

  FIG. 1 is a cross-sectional view showing an example of the configuration of the organic light emitting device of the present invention. A hole transport layer (3) and a light emitting layer (3) are provided between an anode (2) and a cathode (6) provided on a transparent substrate (1). 4), an electron transport layer (5) is sequentially provided. Further, the configuration of the organic light-emitting device of the present invention is not limited to the example shown in FIG. 1, and any one of (i) a hole transport layer / a light-emitting layer and (ii) a light-emitting layer / an electron transport layer is sequentially disposed between an anode and a cathode. And (iii) a layer containing a hole-transporting material, a light-emitting material and an electron-transporting material, (iv) a layer containing a hole-transporting material and a light-emitting material, and (v) a layer containing a light-emitting material and an electron-transporting material. Layer, or (vi) a single layer of the luminescent material. Further, the light emitting layer shown in FIG. 1 is a single layer, but two or more layers may be stacked.

  As a method for forming the light-emitting material, the hole transport material, and the electron transport material used for each of the above layers, a resistance heating evaporation method, an electron beam evaporation method, a sputtering method, a coating method, a solution coating method, and the like can be used. Although not particularly limited, in the case of a low molecular compound, resistance heating evaporation and electron beam evaporation are mainly used, and in the case of a polymer material, a coating method is mainly used in many cases.

  In the organic light emitting device according to the present invention, by forming the hole transport layer and the electron transport layer on both sides or one side of the light emitting layer, it is possible to further improve the luminous efficiency and / or the durability.

  Examples of the hole transporting material forming the hole transporting layer include TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′diamine), α-NPD ( 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine) and the like Known hole transport materials such as a triphenylamine derivative, polyvinyl carbazole and poly (3,4-ethylenedioxythiophene) can be used, but are not particularly limited thereto. These hole transporting materials may be used alone or may be mixed with or laminated with different hole transporting materials. The thickness of the hole transporting layer depends on the conductivity of the hole transporting layer and cannot be unconditionally limited, but is preferably from 10 nm to 10 μm, more preferably from 10 nm to 1 μm.

As the electron transporting material for forming the electron transporting layer, known electron transporting materials such as quinolinol derivative metal complexes such as Alq ₃ (tris aluminum quinolinol), oxadiazole derivatives, and triazole derivatives can be used. Never. These electron transporting materials may be used alone or may be mixed with or laminated with different electron transporting materials. The thickness of the electron transporting layer depends on the conductivity of the electron transporting layer and cannot be unconditionally limited, but is preferably from 10 nm to 10 μm, more preferably from 10 nm to 1 μm.

  The light emitting material, the hole transporting material, and the electron transporting material used for each of the above-mentioned layers may be formed independently of each other, or may be mixed with materials having different functions. In addition, each layer can be formed using a polymer material as a binder. Examples of the polymer material used for this purpose include polymethyl methacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide. It is not done.

  As the anode material of the organic light emitting device according to the present invention, known transparent conductive materials such as conductive polymers such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, and polyaniline can be used. It is not limited to these. The electrode made of the transparent conductive material preferably has a surface resistance of 1 to 50 Ω / □ (ohm / square). As a method of forming these anode materials, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like can be used, but is not particularly limited thereto. The thickness of the anode is preferably 50 to 300 nm.

  Further, a buffer layer may be inserted between the anode and the hole transport layer or the organic layer laminated adjacent to the anode for the purpose of relaxing an injection barrier against hole injection. For this, a known material such as copper phthalocyanine is used, but is not particularly limited thereto.

  Examples of the cathode material of the organic light-emitting device according to the present invention include Al, MgAg alloy, alkaline earth metals such as Ca, alkali metals such as Li and Cs, alloys of Al and alkaline earth metals such as AlCa, AlLi, and AlCs. A known cathode material such as an alloy of an alkali metal and Al can be used, but is not particularly limited thereto. As a method for forming the cathode material, a resistance heating evaporation method, an electron beam evaporation method, a sputtering method, an ion plating method, or the like can be used, but is not particularly limited thereto. The thickness of the cathode is preferably from 10 nm to 1 μm, more preferably from 50 to 500 nm.

  An insulating layer having a thickness of 0.1 to 10 nm may be inserted between the cathode and the electron transporting layer or the organic layer laminated adjacent to the cathode for the purpose of improving electron injection efficiency. As the insulating layer, known cathode materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina can be used, but are not particularly limited thereto.

  Further, a hole blocking layer may be provided adjacent to the cathode side of the light emitting layer for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining with electrons in the light emitting layer. Known materials such as a triazole derivative and an oxadiazole derivative are used for this, but are not particularly limited thereto.

  As the substrate of the organic light emitting device according to the present invention, an insulating substrate transparent to the emission wavelength of the light emitting material can be used. In addition to glass, known substrates such as transparent plastics such as PET (polyethylene terephthalate) and polycarbonate can be used. Materials can be used, but there is no particular limitation.

  The organic light emitting device of the present invention can form pixels of a matrix system or a segment system by a known method, and can be used as a backlight without forming a pixel.

Hereinafter, the present invention will be described more specifically by showing typical examples. These are merely examples for explanation, and the present invention is not limited to these.
The equipment used for the analysis in the following examples is as follows. Unless otherwise specified, commercial reagents (special grade) were used without purification.

1) ¹ H-NMR
JNM EX270,270MHz, manufactured by JEOL Ltd.
Solvent: deuterated chloroform.
2) Elemental analyzer
Model CHNS-932 manufactured by LECO.
3) GPC measurement (molecular weight measurement)
Column: Shodex KF-G + KF804L + KF802 + KF801,
Eluent: tetrahydrofuran (THF),
Temperature: 40 ° C,
Detector: RI (Shodex RI-71).
4) ICP elemental analysis ICPS 8000 manufactured by Shimadzu Corporation.

0.50ｇのチオジグリコール（4.1ｍｍｏｌ）の１０ｍｌエタノール溶液中に0.85ｇの塩化金（III）酸四水和物（2.1ｍｍｏｌ）の１０ｍｌ水溶液を加え、室温で0.5 時間撹拌した。得られた反応液を０℃に冷却し、トリフェニルホスフィン（0.54ｇ、2.1ｍｍｏｌ）の１０ｍｌアセトン−エタノール混合溶液（容積比１：１）を加えて0.5 時間撹拌した。次に反応液を１００ｍｌの水中に注ぎ、生じた沈殿をろ別して減圧乾燥した。得られた白色個体９８ｍｇを５ｍｌのメタノール中に懸濁させ、３０ｍｇのフェニルブタジイン（0.24ｍｍｏｌ）と１５ｍｇのナトリウムメトキシド（0.28ｍｍｏｌ）を加えて室温で１６時間撹拌した。減圧で溶媒を留去後、少量のジエチルエーテルを加えてグラスフィルターに通し、得られた溶液から再び減圧で溶媒を留去した。残渣をシリカゲルのカラムクロマトグラフィーで精製し、減圧乾燥することによって、目的とする化合物１−１ ６５ｍｇ（0.11ｍｍｏｌ）を薄褐色の固体として得た。同定はＣＨＮ元素分析で行った。分析結果を表１に示す。 Example 1 Synthesis of phenylbutadiynyl (triphenylphosphine) gold (I) (compound 1-1)

To a solution of 0.50 g of thiodiglycol (4.1 mmol) in 10 ml of ethanol was added 0.85 g of an aqueous solution of chloroauric acid (III) tetrahydrate (2.1 mmol), and the mixture was stirred at room temperature for 0.5 hour. The obtained reaction solution was cooled to 0 ° C., and a 10 ml acetone-ethanol mixed solution (volume ratio 1: 1) of triphenylphosphine (0.54 g, 2.1 mmol) was added thereto, followed by stirring for 0.5 hour. Next, the reaction solution was poured into 100 ml of water, and the resulting precipitate was separated by filtration and dried under reduced pressure. 98 mg of the obtained white solid was suspended in 5 ml of methanol, 30 mg of phenylbutadiyne (0.24 mmol) and 15 mg of sodium methoxide (0.28 mmol) were added, and the mixture was stirred at room temperature for 16 hours. After evaporating the solvent under reduced pressure, a small amount of diethyl ether was added and the mixture was passed through a glass filter, and the solvent was distilled off again from the obtained solution under reduced pressure. The residue was purified by silica gel column chromatography, and dried under reduced pressure to obtain 65 mg (0.11 mmol) of the desired compound 1-1 as a pale brown solid. Identification was performed by CHN elemental analysis. Table 1 shows the analysis results.

Examples 2 to 11:
Similar to the synthesis of compound 1-1, except that organophosphorus compound P (R ¹⁰¹ ) (R ¹⁰² ) (R ¹⁰³ ) is used instead of triphenylphosphine and alkyne H (C ₂ ) _n R ¹⁰⁴ is used instead of phenylbutadiyne. Compounds 1-2 to 1-11 were synthesized by the operation.

0.50ｇのチオジグリコール（4.1ｍｍｏｌ）の１０ｍｌエタノール溶液中に0.85ｇの塩化金（III）酸四水和物（2.1ｍｍｏｌ）の１０ｍｌ水溶液を加え、室温で0.5時間撹拌した。得られた反応液を０℃に冷却し、トリフェニルホスフィン（0.54ｇ、2.1ｍｍｏｌ）の１０ｍｌアセトン−エタノール混合溶液（容積比１：１）を加えて0.5時間撹拌した。次に反応液を１００ｍｌの水中に注ぎ、生じた沈殿をろ別して減圧乾燥した。得られた白色個体７８ｍｇを１０ｍｌのメタノール中に懸濁させ、8.5ｍｇのナトリウムメトキシド（0.16ｍｍｏｌ）と１９ｍｇのビス（トリメチルシリル）ヘキサトリイン（0.087 ｍｍｏｌ）を加えて室温で３時間撹拌した。生成した黄褐色の沈殿をグラスフィルターでろ取し、メタノールで洗浄後、減圧乾燥することによって化合物２−１ ６６ｍｇ（0.067ｍｍｏｌ）を黄褐色の固体として得た。同定はＣＨＮ元素分析で行った。分析結果を表２に示す。 Example 12: Synthesis of hexatriindiylbis (triphenylphosphine) digold (I) (compound 2-1)

To a solution of 0.50 g of thiodiglycol (4.1 mmol) in 10 ml of ethanol was added 0.85 g of an aqueous solution of chloroauric acid (III) tetrahydrate (2.1 mmol), and the mixture was stirred at room temperature for 0.5 hour. The obtained reaction solution was cooled to 0 ° C., and a 10 ml acetone-ethanol mixed solution (volume ratio: 1: 1) of triphenylphosphine (0.54 g, 2.1 mmol) was added thereto, followed by stirring for 0.5 hour. Next, the reaction solution was poured into 100 ml of water, and the resulting precipitate was separated by filtration and dried under reduced pressure. 78 mg of the obtained white solid was suspended in 10 ml of methanol, 8.5 mg of sodium methoxide (0.16 mmol) and 19 mg of bis (trimethylsilyl) hexatriin (0.087 mmol) were added, and the mixture was stirred at room temperature for 3 hours. The formed tan precipitate was collected by filtration with a glass filter, washed with methanol, and dried under reduced pressure to obtain 66 mg (0.067 mmol) of Compound 2-166 as a tan solid. Identification was performed by CHN elemental analysis. Table 2 shows the analysis results.

Examples 13 to 15:
The compound 2-1 was obtained by using the organic phosphorus compound P (R ¹⁰⁵ ) (R ¹⁰⁶ ) (R ¹⁰⁷ ) in place of triphenylphosphine and alkyne Me ₃ Si (C ₂ ) _n SiMe ₃ in place of bis (trimethylsilyl) hexatriin. Compounds 2-2 to 2-4 were synthesized by the same operation as the synthesis. Identification was performed by CHN elemental analysis. Table 2 shows the analysis results.

0.50ｇのチオジグリコール（4.1ｍｍｏｌ）の１０ｍｌエタノール溶液中に0.85ｇの塩化金(III）酸四水和物（2.1ｍｍｏｌ）の１０ｍｌ水溶液を加え、室温で0.5 時間撹拌した。得られた反応液を０℃に冷却し、シクロヘキシルイソシアニド（0.23ｇ、2.1ｍｍｏｌ）の１０ｍｌエタノール溶液を加えて0.5時間撹拌した。次に反応液を１００ｍｌの水中に注ぎ、生じた沈殿をろ別して減圧乾燥した。得られた白色個体１００ｍｇを１０ｍｌのメタノール中に懸濁させ、１６ｍｇのナトリウムメトキシド（0.29ｍｍｏｌ）と３７ｍｇのフェニルブタジイン（0.29ｍｍｏｌ）を加えて室温で３時間撹拌した。生成した黄褐色の沈殿をグラスフィルターでろ取し、メタノールで洗浄後、減圧乾燥することによって化合物３−１ ５９ｍｇ（0.14ｍｍｏｌ）を黄褐色の固体として得た。同定はＣＨＮ元素分析で行った、分析結果を表３に示す。 Example 16:

To a solution of 0.50 g of thiodiglycol (4.1 mmol) in 10 ml of ethanol was added 0.85 g of an aqueous solution of chloroauric acid (III) tetrahydrate (2.1 mmol), and the mixture was stirred at room temperature for 0.5 hour. The obtained reaction solution was cooled to 0 ° C., a 10 ml ethanol solution of cyclohexyl isocyanide (0.23 g, 2.1 mmol) was added, and the mixture was stirred for 0.5 hour. Next, the reaction solution was poured into 100 ml of water, and the resulting precipitate was separated by filtration and dried under reduced pressure. 100 mg of the obtained white solid was suspended in 10 ml of methanol, 16 mg of sodium methoxide (0.29 mmol) and 37 mg of phenylbutadiyne (0.29 mmol) were added, and the mixture was stirred at room temperature for 3 hours. The resulting tan precipitate was collected by filtration with a glass filter, washed with methanol, and dried under reduced pressure to obtain 59 mg (0.14 mmol) of compound 3-1 as a tan solid. The identification was performed by CHN elemental analysis, and the analysis results are shown in Table 3.

Examples 17-18:
Ligand L ₅ instead of cyclohexyl isocyanide, synthetic similar operations phenyl alkyne H (C ₂₎ in place of the pig diyne _n R ¹⁰⁸ or _{Me 3 Si (C 2) n} SiMe 3 using the compound 3-1 To synthesize compounds 3-2 to 3-3.

0.40ｇの塩化金（III）ナトリウム二水和物（1.0ｍｍｏｌ）を１０ｍｌのメタノールに溶解し、0.40ｇの１，８−ジイソシアノ−ｐ−メンタン（2.1ｍｍｏｌ）を加えて室温で0.5時間撹拌した。この溶液を１時間加熱還流した後、生じた沈殿をグラスフィルターでろ別し、−２０℃に冷却することによって化合物４−１を得た（実施例１９）。１，８−ジイソシアノ−ｐ−メンタンの代わりに２，５−ジイソシアノ−２，５−ジメチルヘキサンを用いることによって化合物４−２を得た（実施例２０）。同定はＣＨＮ元素分析で行った。 Examples 19 to 20:

0.40 g of sodium gold (III) chloride dihydrate (1.0 mmol) was dissolved in 10 ml of methanol, and 0.40 g of 1,8-diisocyano-p-menthane (2.1 mmol) was added, followed by stirring at room temperature for 0.5 hour. . After heating and refluxing this solution for 1 hour, the resulting precipitate was filtered off with a glass filter and cooled to −20 ° C. to obtain compound 4-1 (Example 19). Compound 4-2 was obtained by using 2,5-diisocyano-2,5-dimethylhexane instead of 1,8-diisocyano-p-menthane (Example 20). Identification was performed by CHN elemental analysis.

Elemental analysis value Example 19 (Compound 4-1)
Calcd: C, 26.43; H, 2.85; N, 8.81. Found: C, 26.80; H, 3.09; N, 9.02.
Example 20 (Compound 4-2)
Calcd: C, 23.62; H, 2.64; N, 9.18.Found: C, 23.77; H, 2.41; N, 9.05.

１０３ｍｇのベンゼンチオール（0.93ｍｍｏｌ）と９５ｍｇのトリエチルアミン（0.93ｍｍｏｌ）を５ｍｌのＴＨＦに溶解し、公知の方法（J. Chem. Soc., Dalton Trans., 1845頁, 1973年）によって合成されるテトラブチルアンモニウムジブロモ金（Ｉ）（２７９ｍｇ、0.47ｍｍｏｌ）の５ｍｌＴＨＦ溶液に滴下した。室温で２時間撹拌後、生じた沈殿をグラスフィルターでろ別して得られた溶液から溶媒を留去した。油状の残渣をジエチルエーテルで洗浄し、メタノールから再結晶することによって化合物５−１を得た。同定はＣＨＮ元素分析で行った。分析結果を表４に示す。 Example 21:

103 mg of benzenethiol (0.93 mmol) and 95 mg of triethylamine (0.93 mmol) are dissolved in 5 ml of THF, and tetrasynthesized by a known method (J. Chem. Soc., Dalton Trans., P. 1845, 1973). Butyl ammonium dibromogold (I) (279 mg, 0.47 mmol) was added dropwise to a 5 ml THF solution. After stirring at room temperature for 2 hours, the resulting precipitate was filtered off with a glass filter, and the solvent was distilled off from the obtained solution. The oily residue was washed with diethyl ether and recrystallized from methanol to give compound 5-1. Identification was performed by CHN elemental analysis. Table 4 shows the analysis results.

Examples 22 to 28:
Compounds 5-2 to 5-8 were synthesized by the same operation as for compound 5-1 using substituted benzenethiol instead of benzenethiol.

0.50ｇのチオジグリコール（4.1ｍｍｏｌ）の１０ｍｌエタノール溶液中に0.85ｇの塩化金（III）酸四水和物（2.1ｍｍｏｌ）の１０ｍｌ水溶液を加え、室温で0.5時間撹拌した。得られた反応液を０℃に冷却し、ビス（ジフェニルホスフィノ）メタン（0.40ｇ、1.1ｍｍｏｌ）の１０ｍｌアセトン−エタノール混合溶液（容積比１：１）を加えて0.5 時間撹拌した。次に反応液を１００ｍｌの水中に注ぎ、生じた沈殿をろ別して減圧乾燥した。得られた白色個体１５０ｍｇをメタノールに懸濁させ、３５ｍｇのトリエチルアミン（0.35ｍｍｏｌ）と１９ｍｇの１，３−プロパンジチオール（0.18ｍｍｏｌ）を加えて室温で３時間撹拌した。生成した沈殿をグラスフィルターでろ取し、メタノールで洗浄後、減圧乾燥することによって化合物６−１ ８９ｍｇ（0.10ｍｍｏｌ）を黄褐色の固体として得た。同定はＣＨＮ元素分析で行った。分析結果を表５に示す。 Example 29:

To a solution of 0.50 g of thiodiglycol (4.1 mmol) in 10 ml of ethanol was added 0.85 g of an aqueous solution of chloroauric acid (III) tetrahydrate (2.1 mmol), and the mixture was stirred at room temperature for 0.5 hour. The obtained reaction solution was cooled to 0 ° C., and a mixed solution of bis (diphenylphosphino) methane (0.40 g, 1.1 mmol) in 10 ml of acetone-ethanol (volume ratio 1: 1) was added thereto, followed by stirring for 0.5 hour. Next, the reaction solution was poured into 100 ml of water, and the resulting precipitate was separated by filtration and dried under reduced pressure. 150 mg of the obtained white solid was suspended in methanol, 35 mg of triethylamine (0.35 mmol) and 19 mg of 1,3-propanedithiol (0.18 mmol) were added, and the mixture was stirred at room temperature for 3 hours. The resulting precipitate was collected by filtration with a glass filter, washed with methanol, and dried under reduced pressure to obtain 89 mg (0.10 mmol) of compound 6-1 as a tan solid. Identification was performed by CHN elemental analysis. Table 5 shows the analysis results.

Examples 30 to 34:
Bis diphosphine instead of (diphenylphosphino) methane ^{(R 114) (R 115)} P-Z-P (R 116) using (R ^117), 1,3 thiol in place of propane dithiol (R ¹¹⁸⁾ SH And (R ¹¹⁹ ) SH were used to synthesize Compounds 6-2 to 6-6 in the same manner as for Compound 6-1. Identification was performed by CHN elemental analysis. Table 5 shows the analysis results.

Examples 35 to 48: Production and Evaluation of Organic Light-Emitting Element A substrate with ITO (indium tin oxide) in which two 4 mm-wide ITO electrodes serving as anodes were formed in a stripe shape on one surface of a 25 mm square glass substrate. (Nippo Electric Co., LTD.) To produce an organic light emitting device. First, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (trade name “Baytron P”, manufactured by Bayer AG) was spin-coated on the ITO (anode) of the substrate with ITO by a spin coating method at 3,500 rpm. The coating was performed under the conditions of a coating time of 40 seconds and then dried at 60 ° C. for 2 hours under reduced pressure using a vacuum dryer to form an anode buffer layer. The thickness of the obtained anode buffer layer was about 50 nm. Next, a coating solution for forming a layer containing a light emitting material, a hole transport material, and an electron transport material was prepared. 8.2 μmol of the luminescent material of the present invention, 21.0 mg (0.11 mmol) of polyvinyl carbazole as a hole transporting material, and 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,3 as an electron transporting material. 9.0 mg (0.025 mmol) of 4-oxadiazole (PBD) (manufactured by Tokyo Kasei Kogyo) is dissolved in 2970 mg of chloroform (manufactured by Wako Pure Chemical Industries, special grade), and the obtained solution is filtered through a filter having a pore size of 0.2 μm. The coating solution was used. Next, on the anode buffer layer, the prepared coating solution was applied by spin coating under the conditions of a rotation speed of 3000 rpm and an application time of 30 seconds, and dried at room temperature (25 ° C.) for 30 minutes to form a light emitting layer. Formed. The thickness of the obtained light emitting layer was about 100 nm. Next, the substrate on which the light emitting layer was formed was placed in a vapor deposition apparatus, and calcium and aluminum were co-deposited at a weight ratio of 1:10. It was formed so as to be orthogonal to the existing direction. The thickness of the obtained cathode was about 50 nm. Finally, in an argon atmosphere, lead wires (wiring) were attached to the anode and the cathode, and four organic light-emitting devices measuring 4 mm long × 3 mm wide were manufactured. A voltage was applied to the organic EL device using a programmable DC voltage / current source TR6143 manufactured by Advantest Corporation to emit light, and the emission luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The results and emission colors are shown in Table 6 (average of four elements using each emission material).

  The organic light emitting device of the present invention can emit visible light from blue, which is short-wavelength light, to red, which is long-wavelength light, at a low voltage, and the organic light-emitting device of the present invention uses a phosphorescent material. Therefore, light emission from a triplet excited state, in which light emission cannot be obtained with a fluorescent material, is also possible, and electric energy given to the element can be converted to light with high efficiency. In addition, by using a high molecular compound or a mixture of a low molecular compound and a high molecular compound as a material of the light emitting element, a large-area element can be easily manufactured by a coating method.

It is an example of the sectional view of the organic light emitting element of the present invention.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Anode 3 Hole transport layer 4 Light emitting layer 5 Electron transport layer 6 Cathode

Claims (17)

  An organic light-emitting device material, wherein gold includes a gold complex bonded to at least one atom selected from carbon, oxygen and sulfur.   The organic light-emitting device material according to claim 1, wherein at least one atom selected from carbon, oxygen, and sulfur bonded to gold contains a gold complex bonded to only one atom in addition to gold.   The organic light-emitting device material according to claim 1, comprising a gold complex in which at least one atom selected from carbon, oxygen and sulfur is carbon.   The organic light emitting device material according to claim 3, wherein the carbon atom bonded to gold includes a gold complex bonded to a nonmetal element by a triple bond and bonded to gold by a single bond.   The organic light-emitting device material according to claim 4, comprising a gold complex in which the nonmetal element is carbon. The gold complex has the formula (1)

[Wherein L ¹ represents a monodentate or bidentate ligand, n represents an integer of 1 to 5, and R ¹¹ may have a hydrogen atom, a halogen atom, a cyano group, a silyl group, or a hetero atom. It represents a good alkyl group, aryl group, alkoxy group, acyl group, carboxyl group or alkoxycarbonyl group. ]
The organic light-emitting device material according to claim 5, which is a compound represented by the following formula: The gold complex has the formula (2)

[In the formula, n and R ¹¹ have the same meaning as described in claim 6, and R ^{21 to} R ²³ each independently have a hydrogen atom, an amino group, a cyano group, a silyl group, or a hetero atom. Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an alkylamino group. ]
The organic light-emitting device material according to claim 6, which is a compound represented by the following formula: The gold complex has the formula (3)

[Wherein, L ¹ and L ² each independently represent a monodentate or bidentate ligand, and n represents an integer of 1 to 5. ]
The organic light-emitting device material according to claim 5, which is a compound represented by the following formula: The gold complex has the formula (4)

[In the formula, n represents an integer of 1 to 5, and R ^{21 to} R ²⁶ each independently represent a hydrogen atom, an amino group, a cyano group, an alkyl group which may have a silyl group or a hetero atom, an aryl group. , An alkoxy group, an aryloxy group or an alkylamino group. ]
The organic light-emitting device material according to claim 5, which is a compound represented by the following formula:   The organic light-emitting device material according to claim 4, comprising a gold complex in which the nonmetal element is nitrogen.   The organic light emitting device material according to claim 10, further comprising a gold complex in which a nitrogen atom forming a triple bond with a carbon atom having a gold-carbon bond is further bonded to another carbon atom. The gold complex has the formula (5)

[In the formula, Y represents an alkylene, cycloalkylene, or arylene group, or an organic group in which the same or different two or more groups are alternately bonded, L ³ and L ⁴ each independently represent a monodentate Alternatively, it represents a bidentate ligand. ]
The organic light-emitting device material according to claim 11, which is a compound represented by the following formula:   The organic light emitting device material according to claim 1, wherein the material includes a gold complex in which at least one atom selected from carbon, oxygen, and sulfur is sulfur. The gold complex has the formula (6)

[Wherein, R ^{31 to} R ³⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, a silyl group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group. , A phosphonic acid group, or an alkyl group, an aryl group, an alkoxy group, an acyl group, a carboxyl group, an alkoxycarbonyl group or an acyloxy group which may have a hetero atom, and X ⁺ represents a monovalent cation. ]
The organic light-emitting device material according to claim 13, which is a compound represented by the following formula: The gold complex has the formula (7)

[In the formula, R ^{41 to} R ⁵² each independently represent a hydrogen atom, a cyano group, a silyl group, or an alkyl group, an aryl group or an acyl group which may have a hetero atom, and Z represents an alkylene, a cycloalkylene. Alternatively, it represents an arylene group or an organic group in which the same or different two or more groups are alternately bonded. ]
The organic light-emitting device material according to claim 13, which is a compound represented by the following formula:   An organic light-emitting element in which one or more organic compounds including a light-emitting layer are sandwiched between a pair of electrodes, wherein the organic light-emitting element material according to any one of claims 1 to 15 is included in the light-emitting layer. Organic light-emitting device. Equation (4)

[In the formula, n represents an integer of 1 to 5, and R ^{21 to} R ²⁶ each independently represent a hydrogen atom, an amino group, a cyano group, an alkyl group which may have a silyl group or a hetero atom, an aryl group. , An alkoxy group, an aryloxy group or an alkylamino group (except when R ^{21 to} R ²⁶ are all cyclohexane rings and n is 1 or 2). ] The compound shown by these.

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