TW200946537A - Substituted ethynyl golden-cyclic alkylaminocarbene complex and organic electroluminescent element - Google Patents

Abstract

The present invention relates to a substituted ethynyl golden-cyclic alkylaminocarbene complex represented by the following general formula (1): [wherein L represents a cyclic alkylaminocarbene ligand, X represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, herein, one or more hydrogen atoms on the carbon atoms of X may be independently substituted by a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamino group which is substituted by the same or different alkyl groups, an alkylcarbonyl group, an arylcarbonyl group, an alkylmercapto group, an arylmercapto group, an alkylsulfonyl group or an arylsulfonyl group, and adjacent groups may bond to each other to form a ring when a plurality of hydrogen atoms on the carbon atoms of X are independently substituted by an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamino group which is substituted by the same or different alkyl groups, an alkylcarbonyl group, an arylcarbonyl group, an alkylmercapto group, an arylmercapto group, an alkylsulfonyl group or an arylsulfonyl group]; and an organic electroluminescent element.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substitute for an E in the form of a luminescent material for an electric field light-emitting element (organic electroluminescent device). [Prior Art] In recent years, organic electroluminescence devices have been attracting single-state luminescence with the same U-plane and color-emitting luminescence molecules from the display device, and the use of optical materials is currently in use. Leeguang # material, in order to pursue higher light materials. However, in phosphorescent ancient I, a phosphorescent organic thunder which emits triplet luminescence is made into an important 440 ΐ ΐ 造 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了The following deep blue color is the CIE (International Illumination Commission's luminescence peak maximum value, and the element of 0.18 (for example, refer to the later <) color system, its y coordinate is not up yet, and this is still completely unknown. 1). An amine-based carbon-derived complex, and an organic electroluminescent device of the 彳M generation-inspection-ring pit base.胄 作为 作为 发光 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ 第 第 第 第 第 第 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 【 【 【 【 【 Provided is an organic electroluminescence light-emitting device for emitting light and a compound for use as a compound, and the organic 200946537 excitation light element is a phosphorescent organic electroluminescence device, and is an important 440 nm for completing a full-color display. In the dark blue region below, there is a maximum value of the luminescence peak caused by the electroluminescence excitation light, and the luminescent color is a component whose C coordinate (International Commission of Illumination) color y coordinate is less than 0·18. (Means for Solving the Problem) The problem of the present invention can be solved by a substituted acetylene gold-cyclic alkylamino carbene complex represented by the formula (丨): X·~ΞΞ= AuL (1) Ο Wherein L represents a cyclic alkylamino carbene ligand; X represents a decyl, cycloalkyl, aryl, aralkyl or heterocyclic group; here, one or a number of carbon atoms of X a dialkylamine in which a hydrogen atom may be independently substituted by a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an alkoxy group, an aryloxy group, or the same or different alkyl groups. a group derived from an alkyl group, an alkylcarbonyl group, an arylcarbonyl group, a decyl fluorenyl group, an aryl fluorenyl group, an alkylsulfonyl group or an arylsulfonyl group; when a plurality of hydrogen atoms on the carbon atom of X are independently alkane a base, an alkenyl group, an aryl group, an arylalkyl group, an alkoxy group, an aryloxy group, a dialkylamino group substituted with the same or different alkyl groups, an alkylcarbonyl group, an arylcarbonyl group, an alkyl fluorenyl group, an aromatic group When a keweiyl group, a pyrenylsulfonyl group or an arylsulfonyl group is substituted, adjacent groups may be bonded to each other to form a ring. (Effects of the Invention) According to the present invention, it is possible to realize an illuminating peak maximum value of a photo-excited light in a deep blue region (410 to 440 nm) of 440 nm or less, and the luminescent color is in the case of the CIE (International Commission on Illumination) color system. The 321109 200946537 organic electroluminescence element having a y coordinate is not provided, and a acetylene gold-cyclic alkylamino group carbon ruthenium which is useful as a luminescent material of the organic electroluminescence element can be provided. σ [Embodiment] The substituted acetylene gold-ring-based aminocarbene carbene complex of the present invention is represented by the above formula (1). In the formula (1), L represents a cyclic alkylamine-like carbene ligand. X represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterodiyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and a decyl group. Wait. In particular, an alkyl group having 1 to 6 carbon atoms is particularly preferred. Again, such groups include their isomers. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a ring. Anthracenyl, cycloundecylalkyl, cyclododecacarbyl, and the like. The above aryl group is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include a benzyl group, a phenyl group, a diphenyl group, a biphenyl group, a benzyl group, a decyl group, a dimethylnaphthyl group, and an anthracene group. A group, a phenanthryl group, a fluorenyl group, a pyrenyl group, a 2-chrysenyl group, a naphthacenyl group, and the like. In particular, an aryl group having 6 to 14 carbon atoms is particularly preferred. Again, such radicals include their isomers. The above-mentioned aryl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzoinyl group, a naphthylquinone group, a fluorenyl group, a biphenylmethyl group and the like. The above heterocyclic group is preferably a saturated or unsaturated cyclic group consisting of 3 to 10 ring members containing at least one hetero atom selected from N, 0 or S 6 321109 200946537, and I exemplifies, for example, pyrrole. , furyl, thienyl, fluorenyl, benzofuranyl, *benzothiophenyl, pyridyl, pyridyl, pyrimidinyl, morphine, quinolyl, isoquinolinyl, quinazoline Quinazolinyl, quinoxalinyl, and the like. One or several hydrogen atoms on the carbon atom of X may be independently a halogen atom, a fluorenyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamine. Substituted by an alkyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylhydrazine group, an arylsulfonyl group, an alkylsulfonyl group or an arylsulfonyl group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group is preferably a carbon atom number of 1 to 2 Å, particularly preferably a carbon atom number of 1 to 12, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. Octyl, decyl, decyl, undecyl, dodecyl and the like. In particular, an alkyl group having 1 to 6 carbon atoms is particularly preferred. Again, these substituted oxime groups include their isomers. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 7 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like. The above alkenyl group is preferably an alkenyl group having 2 to 20' carbon atoms and particularly preferably 2 to 12 carbon atoms, and examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group and a heptenyl group. , octenyl, nonenyl, nonenyl, undecenyl, dodecenyl and the like. Further, such substituents include the isomers thereof. The aryl group is preferably a carbon atom having 6 to 2 Å, particularly preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a diphenyl group, a biphenyl group, and 321109 200946537. The substituents, including naphthyl, 2-methylnaphthyl, anthracenyl, phenanthryl, and thiol, include the isomers thereof. The above-mentioned aryl group is represented by a carbon atom number of 7 to 20, such as a methyl group, a phenethyl group, a naphthylmethyl group, a methyl group, a biphenylmethyl group, etc.丨 to 10 = = oxy, ethoxy, propoxy, butoxy, pentoxide:: oxygen can be listed:::iso:: group, decyloxy, decyloxy and the like. Further, these substituents are preferably an aryloxy group having an aryloxy group having 6 to 14 carbon atoms, and may be listed as a phenoxy group, a nonylphenoxy group, a xylylene group, a naphthyloxy group, or a dimethyl group. Based on tea base and so on. Further, such substituents include the isomers thereof. The dialkylamino group is preferably a dialkylamino group substituted with the same or different two groups selected from the group consisting of an alkyl group having 1 to 6 carbon atoms. In particular, there may be mentioned, for example, a dimethylamino group, a diethylamino group, a dipropylamino group and the like. Again, such substituents include the isomers thereof. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 10 carbon atoms, and examples thereof include an ethyl group, a propyl group, and a butyl group. Further, such substituents include the isomers thereof. The arylcarbonyl group is preferably an arylcarbonyl group having 7 to 11 carbon atoms, and examples thereof include a benzoyl group, a fluorophenyl fluorenyl group, and a naphthylquinone group. Again, such substituents include the isomers thereof. The alkyl fluorenyl group is preferably an alkyl fluorenyl group having 1 to 6 carbon atoms, and examples thereof include a methyl fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a pentyl group, and a hexyl fluorenyl group. Further, such substituents include the isomers thereof. 8 321109 200946537 can be listed as having a carbon number of 6 to 14 nucleus, = lifting: base sulfhydryl, methyl strepamine, dimethyl kedi, naphthyl weiji and so on. Further, such substituents include the isomers thereof. Preferably, the base group of the atomic number of 1 to 12 is recorded. For the sake of 歹J, for example, a methyl group or an ethyl group, the above-mentioned aryl group is represented by a base having 6 to 18 carbon atoms. Phenyl sulphate, toluene sulphide n soil is from the sputum: several hydrogen atoms on the carbon atom are burned by the base ketone base, base, aryloxy, two wire ^, silk ", Fang When a base is substituted or a burn is substituted, adjacent groups may be bonded to each other to form a ring. The mercapto group may, for example, be exemplified by the case where the hydrogen atoms are independently substituted by the foregoing: 2 atoms adjacent to each other, carbon atoms bonded to the atoms, adjacent substituents or 8, 9 or 10 members of the two-ring type of saturation 5, 6 or? The member has a monocyclic shape and contains a substituent selected from the group 〇5 # (which may be bonded to each other by a contiguous group and a hetero atom as described above). Examples of the ring of the cyclopentene ring, the cyclohexene ring, and the cycloheptene/ring ring include a ring, a benzo ring, a naphthalene ring, and a tetrahydrogen. Preferred examples are: x is ^N' A wire bite ring and so on. A group of aryl groups having 6 to 18 carbon atoms, "ζ ★ atomic number to 6 or a few argon atoms can be independently selected from a hard atom selected from (a) a carbon atom of f X , dimethyl Amino group, diethylene::, chlorine atom, desert atom, base, propyl alcohol, butyl alcohol, benzene-private amine, dipropylamine, ethyl acetate, rat, methyl, naphthalene Mercapto, 321109 200946537 methyl mercapto, ethyl fluorenyl, propyl fluorenyl, decyl sulfonyl, ethyl sulfonyl, propyl sulfonyl group substituted. The cyclic alkylamino carbene ligand system is represented by the following formula (2):

Wherein η represents an integer from 1 to 3; R1 represents an alkyl group, a cycloalkyl group, a polycycloalkyl group or an aryl group; and R2, R3, R4 and R5, respectively, may be the same or different and represent a hydrogen atom, a halogen atom, an alkane a base, alkenyl, aryl, aralkyl, alkoxy, aryloxy, nitro, cyano group, or a dialkylamine group substituted with the same or different alkyl groups, or R2, R3, The adjacent groups of R4 and R5 may form a ring together with the carbon atoms to which they are bonded; when R1 to R5 represent a group containing a carbon atom, one or several hydrogen atoms on the carbon atom may be halogen atoms, Substituted by an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group. Here, R1 represents an alkyl group, a cycloalkyl group, a polycycloalkyl group or an aryl group, and the alkyl group, the cycloalkyl group, and the aryl group have the same meanings as defined for the substituent on the carbon atom of the above X. The polycycloalkyl group is preferably a polycycloalkyl group having 6 to 10 carbon atoms, and examples thereof include a bicyclo-[2.1.1]-hexyl group, a bicyclo-[2.2.1]-heptyl group, and a bicyclic ring. -[2. 2. 2]-octyl, bicyclo-[3. 3. 0]-octyl, bicyclo-[4. 3. 0]-fluorenyl, bicyclo-[4.4. 0]-octyl, diamond Alkyl and the like. R2, R3, R4 and R5 represent a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl 200946537-based pure group, an aryloxy group, a nitro group, a nitrogen group, or a dimercapto group substituted by the same or a non-base group. Silk, these bases have the same meaning as defined by the substituents of the above X carbon. Further, the adjacent groups of R2 and R3nR5 may form a ring with each other's carbon atoms. In the formula (2), a ring in which a ring is formed by a carbon atom bonded to the group of / and ^ may, for example, be a dilute ring, a cyclohexene ring, a cycloheptene ring, a cyclopentene ring or a cyclohexane. A carbon ring having 5 to 14 carbon atoms such as a ring, a j-ring ring, a benzene, and a naphthalene ring. Further, when R1 to R5 represent a group containing a carbon atom, one carbon atom thereof may be derived from an atom, a county, a cyclo, an alkenyl group, an aryl group, a aryl group, an alkoxy group or an aromatic group. The oxy group is substituted, and these groups have the same meanings as defined for the substituent on the carbon atom of the above X. Preferred examples of these are: R1 is an alkyl group selected from the group consisting of 1 to 20 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a polycycloalkyl group having 6 to 10 carbon atoms or a carbon number of 6 To the aryl group of 20, R2, R3, ^ and R5 are still a hydroquinone atom, a (tetra), a carbon atom to 2Q group, an alkenyl group having 2 to 20 carbon atoms, and a carbon number of 6 to 2 An aryl group, an aryl group having 7 to 2 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a aryloxy group having 6 to 14 carbon atoms, a nitro group, a cyano group, or the same or different A dialkylamino group substituted by a group of 1 to 6 carbon atoms.

Rl is particularly preferably a tributyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group or an adamantyl group. In addition, r2, r3, r4 & r5 are preferably a nitrogen atom or an alkyl group having a reverse atomic number of 1 to 6, when the adjacent sulfhydryl groups of R2, R3, and R5 are bonded to each other. When the atoms form a ring together, it is preferred to form a ring of 11 321 109 200946537, and it is preferred to form a cyclohexane ring or a methyl-4-propylhexane ring. Specific examples of the nitrogen-containing heterocyclic carbene ligand (L) of the present invention include compounds represented by the formulae (3) to (18).

12 321109 200946537 The substituted acetylene gold-cyclic alkylamino carbon-based carbon compound represented by the formula (1) of the present invention can be, for example, represented by the reaction formula [1], by substituting a block of gold The phosphine complex is reacted with a cyclic alkylamino carbene ligand (L) to obtain: [Reaction step (1)]

_ L

X--一ΑυΡ -► X-===一uL

-P (3) (1) In the formula, X and L are synonymous with the above, and P is a monodentate phosphine complex. The monodentate phosphine ligand may be exemplified by bis(pentafluorophenyl)phenylphosphine, (4-bromophenyl)diphenylphosphine, diallylphenylphosphine, dicyclohexylphenylphosphine, and diethyl Phenylphosphine, 4-(didecylamino)phenyl diphenylphosphine, dinonylphenylphosphine, diphenyl(2-methoxyphenyl)phosphine, diphenyl (pentafluorophenyl) Phosphine, diphenylpropylphosphine, diphenyl-2-pyridylphosphine, diphenyl(p-tolyl)phosphine, diphenylvinylphosphine, ethyldiphenylphosphine, isopropyl Phenylphosphine, decyldiphenylphosphine, triphenylphosphonium phosphine, tributylphosphine, tri-tert-butylphosphine, tricyclodecylphosphine, tricyclopentylphosphine, triethylphosphine, tri-2 -furylphosphine, triisobutylphosphine, triisopropylphosphine, tripropylphosphine, tridecylphosphine, trioctylphosphine, triphenylphosphine, tris(4-chlorophenyl)phosphine, tris(3) -Chlorophenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(3-fluorophenyl)phosphine, tris(4-methoxybenzene) Phosphine, tris(3-decyloxyphenyl)phosphine, tris(2-decyloxyphenyl)phosphine, tris(4-trifluorodecylphenyl)phosphine, tris(pentafluoro Phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(2,4,6-tridecylphenyl)phosphine, tri-tolylphosphine, tri-o-tolylphosphine, three pairs Tolylphosphine, benzyldiphenylphosphine, bis(2-decyloxyphenyl)phenylphosphine, diphenylcyclohexylphosphine, 2-(di-tertiary 13 321109 200946537 phosphinyl)biphenyl , 2-(dicyclohexylphosphino)biphenyl, neomenthyl diphenyl phosphine, p-tolyl diphenylphosphine, di-propylpropyl, di(2,4,4_dioxin A pentyl group, a tris(1_caiji) scale, a tris(hydroxyindenyl)phosphine, a tris(hydroxypropyl)phosphine, and the like. These can be used directly as a commercial item. The above-mentioned substituted acetylene gold phosphine complex can be obtained, for example, by reacting a gold halide phosphine complex with a substituted acetylene in the presence of a base as shown in the reaction scheme [2]: [Reaction step (2) Alkali

X-:·Τ7" + AAuP -► X- ~· ί· -AuP (4) (5) (6) where 'X and P are synonymous with the above' Y represents a halogen atom (for example, refer to journa 1 of Chemical Society, Dalton Trans., 411 (1986)). Further, the above-mentioned gold phosphine complex can be synthesized according to a known method (for example, refer to Experimental Chemistry Lecture 4th Edition, Maruzen Society, p. 455, vol. 18 (1991)). The above-mentioned substituted acetylene may be directly used as a commercially available product, and may be synthesized by substituting an aromatic desert compound according to a known method (for example, referring to journal 〇f)

Organic Chemical, 1985, Vol. 50, 1763.). The cyclic alkylamino carbene ligand is obtained by reacting a corresponding cyclic iminium salt with a test (for example, lithium diisopropylguanidinium) by a known method. (For example, refer to the International Publication No. 2006/138166 manual). In the synthesis of 14 321109 200946537 of the substituted acetylene gold-cyclic alkylamino carbene complex of the present invention, the cyclic alkylamino group is finely coordinated with respect to the substituted ethyl gold phosphine complex j mole. It is better to use a fine amount of material to the 1G material, and the Euler is better. 4 In the present invention, the substituted ethylidene-ring-cyclic mercaptoamine-based carbon is returned to the wrong Γ=Γ solvent, and there is no particular limitation as long as it does not hinder the reaction, for example, use: four-hearted, four 4 tons _ ❹ 乙基 ethyl ether, diisopropyl ether, dibutyl test, etc.; aliphatic hydrocarbons such as barium, hexane, octane; benzene, toluene, _ HP —~ τ, one Aromatic hydrocarbons; a toluene aromatic hydrocarbon such as I-methyl, emulsifiable, dichloropropan (tetra), aliphatic hydrocarbons. Also, these solvents can be used! 2 or more kinds are mixed or mixed. π

The amount of the solvent used is appropriately adjusted depending on the homogeneity and the mixing property of the reaction liquid, and is preferably from 3 to 20, more preferably from 5 to 20 L, based on 1 mol of the substituted acetylene phosphine complex. good. J. The synthesis of the substituted E-gold-cyclic anthraquinone-based carbon-diffused complex of the present invention can be carried out by mixing (4) a red nugget gold phosphine complex, a doped amine carbene ligand and a solvent, It is carried out by a method such as reacting it. The reaction temperature at this time is preferably from 〇 to 12 (rc, more preferably from 2 Torr to 1 〇〇 ° C.) The reaction pressure is not particularly limited. The substituted (tetra) gold-cyclo(tetra) amide base complex of the present invention After the reaction is completed, it is isolated and produced by methods such as neutralization, extraction, filtration, concentration, distillation, recrystallization, sublimation, chromatography, etc. The substituted ethylidene gold-cyclic mercaptoamine group of the present invention. Examples of the carbon-binding complex compound include compounds represented by the formulae (19) to (49). 15 321109 200946537

(31) (32) (33) (34) ❹

(35) (36) (37) (38) 16 321109 200946537

SMe (39) (40) (41) (42)

According to the substituted acetylene gold-cyclic alkylamino carbene complex of the present invention, it can be realized in chloroform at a temperature of 77K (kelvin, that is, absolute temperature), and under ultraviolet irradiation, in a dark blue region below 440 nm. (410 to 440mn) having a maximum value of the luminescence peak caused by the electroluminescence element, and the luminescent color is a component of the CIE (International Commission on Illumination) color y coordinate of less than 0.18, indicating that the complex can be Suitable for organic electroluminescent components. Next, the embodiment of the organic electroluminescent device of the present invention will be described. The organic electroluminescent device of the present invention is obtained by including at least one of the thin layers of the organic compound containing the substituted acetylene gold-cyclic alkylamino carbene complex, preferably at the pair of electrodes. An organic electroluminescent device having a single layer or a plurality of layers of a compound layer of 17 321109 200946537. The composite test—the miscellaneous amine base complex is not particularly limited for the organic diterpenoid, but may be used in combination with the organic compound layer 其他1^ other electroluminescent elements. , hole injection materials or electronic injection materials. Further, the /in-layer, the light-emitting layer, and the electron injecting layer may be formed by two or more layers of the ruthenium structure, respectively. At this time, 'when forming a hole, the layer of the hole is called the electricity. The layer of the hiding layer, ==== the layer from the electrode ^ hole to the light-emitting layer is called the hole transport layer. Similarly, when the thickness of the electron injection layer In the case of a layer in which electrons are injected from an electrode, it is referred to as electron injection, a layer called electron transport layer that receives electrons from the electron injecting layer and carries electrons to the light-emitting layer. These layers are based on the energy level and impurity of the material. The field and the organic compound layer are selected and used in combination with the electrode, etc. The luminescent material or the host material of the organic compound layer may be used together with the substituted acetylene gold-cyclic amphoteric carbene complex. Examples thereof include various 'salt derivatives, condensed polycyclic aromatics (for example, anthracene, naphthalene, phenanthrene, ruthenium, condensate, pentacene, coronene, chrysene, fluorescein). ), perylene, rubrene and these street creatures, phthaloperylene, naphthoquinone, purple ring _ (Perinone), fluorescein, naphthoquinone, and Phenyl butadiene, tetraphenyl butadiene, coumarin, oxadiazole, aldazine , bisbenzene 18 321109 200946537 oxazoline, distyryl, pyridin, cyclopentadiene, quinoline metal complex, diphenyl ethoxylate, ethylene carbene, diamine scent, η ratio喃, π塞喃' · ("thiopyran), polymethine, morphocyanine, imidazole chelated oxinoid compound, quinacridone (quinacridone), red fluorene, stilbene derivative, aromatic hydrazine compound, aromatic hydrazine compound, etc. The known hole injecting material which can be used in the organic electroluminescent device of the present invention has an effect The hole injection material is an aromatic tertiary amine derivative, an ocyanine derivative or a triphenylene derivative. The specific form of the aromatic tertiary amine derivative is triphenylamine, trimethylamine, Tolyldiphenylamine, hydrazine, Ν'-diphenyl-N, Ν'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (hereinafter referred to as TPD) ), 11^1,,犷-(4-methylphenyl)-1, fluorenyl-phenyl-4,4'-diamine, 1^,1'^',]^-(4-methylbenzene Base) -1, -biphenyl-4,4'-diamine, hydrazine, Ν'-diphenyl-fluorene, Ν'dinaphthyl-1, fluorene-biphenyl-4,4'-diamine, hydrazine, Ν' - (methylphenyl)-indole, Ν'-(4-n-butylphenyl)-phenanthrene-9,10-diamine, 1,1-bis[4-(di-4-tolylamino)benzene The group is a cyclohexane or the like, or an oligomer or a polymer having such an aromatic tertiary amine skeleton, but is not limited thereto. Specific examples of phthalocyanine (also known as Pc) derivatives are H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, CIGaPc, Cl InPc, CISnPc, ChSiPc, (HO)AlPc, (HO Phthalocyanine derivatives such as GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc, and naphthalocyanine derivatives, but are not limited thereto. 19 321109 200946537 The specific aspect of the extended triphenyl derivative is represented by the following formula.

(50) wherein Z represents 1 or a plurality of alkyl groups, cycloalkyl groups, aryl groups, arylalkyl groups or heterocyclic groups, and one or a plurality of hydrogen atoms on the carbon atom of Z may be bonded to a tooth atom, a dialkylamino group, an anthracyl group, an aryl group which is substituted by the same or different alkyl groups, or a aryl group, a aryl group, an aryl group, an aryl group, an alkoxy group, an aryloxy group Substituted by a carbonyl group or an organic decyl group. The substituent other than the organic decyl group has the same meaning as defined in the above-mentioned replaceable group on the carbon atom of X. The above-mentioned organic decyl group may, for example, be a trimethyl fluorenyl group, a triethyl sulfonium group, a tert-butyl fluorenyl decyl group, a triisopropyl decyl group, a tert-butyl bis- fluorenyl group or the like. Further, in the organic electroluminescent device of the present invention, a more effective known electron injecting material is a metal complex compound or a nitrogen-containing five-membered ring derivative. Specific examples of the metal complex compound include, for example, lithium, bis(8-mercaptoquinoline) zinc, bis(8-hydroxyquinoline) copper, bis(8-hydroxyquinoline) manganese, and the like. (8-hydroxyquinoline) aluminum (hereinafter referred to as AlQ3), tris(2- mercapto-8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) gallium, bis(10-hydroxybenzo[h] Quinoline, bis(10-hydroxybenzo[h]quinoline) zinc, bis(2-hydrazino-8-quinoline) chlorogallium, bis(2-methyl-8-quinoline) (neighbor) Indophenol) gallium, bis(2_fluorenyl-8-quinoline) 321109 20 200946537 . (1_Cai Li) Ming, bis(2-indolyl-8-quinoline) (2-naphthol) gallium, etc. However, it is not limited to this. Further, the nitrogen-containing five-membered ring derivative is preferably carbazole, thiophene, oxadiazole, 'thiazole or a diazole derivative. Specifically, for example, 2,5-bis(1-phenyl)-1,3'4-indolyl, dimethyl p〇p〇p (here, p〇p〇p represents Γ, 4-1) Bis(5-phenylindol-2-yl) stupid), 2,5-bis(1_stupyl)], 3, 4_, 2,5-bis(1-styl)-1,3 , 4-oxadiazole, 2_(4,_t-butylphenyl)_5_ ❹(4 _biphenyl)-1,3,4-oxadiazole, 2, 5-bis(phenylyl)-丨, 3, 4_oxadiazole, 1,4-bis[2-(5-phenyloxadiazolyl)]benzene, anthracene, 4-bis[2_(5-phenyloxadiazolyl)-4- Third butyl benzene], 2-(4,_t-butylphenyl)_5_(4-biphenyl)-1,3,4-thiadiazole, 2, 5-bis(1-naphthyl)-1 , 3,4-thiadiazole, 1,4-bis[2-(5-phenylthiadiazolyl)]benzene, 2_(4, _t-butylphenyl)-5-(4' )-1 3,4_triazole, 3_(4-diphenyl)_4_phenyl-5_t-butylphenyl-1,2,4-triazole, 2,5-bis(1-naphthyl) -1,3,4-triazole, 1,4-bis[2-(5-phenyltriazolyl)]benzene, etc., but is not limited thereto. In the organic electroluminescent device of the present invention, an inorganic compound layer may be provided between the light-emitting layer and the electrode in order to improve charge injection properties. Examples of the inorganic compound layer include fluorides and oxides of an alkali metal or an alkaline earth metal such as UF, U2, Ra, SrO, and Srh. The conductive material used for the anode of the organic electroluminescent device of the present invention is preferably a function having a work function of more than 4 eV, and carbon atoms, aluminum, vanadium, iron, nickel, tungsten, silver, gold, platinum, palladium may be used. And these alloys, IT〇 (a substance obtained by adding 5 to 1% by weight of tin oxide to indium oxide), an oxide metal such as tin oxide or indium oxide used for the substrate, and polyporphin 321109 can be used. 21 200946537 or gather. An organic conductive resin such as azole. The conductive material used for the cathode is preferably a work function having a work function of less than 4 eV, and alloys such as Zhen, #5, tin, sin, chin, yttrium, yttrium, yttrium, yum, yam, etc. may be used. Here, the term "alloy" means magnesium/silver, town/indium, memant, and the like. The ratio of the alloy is controlled depending on the temperature of the vapor deposition source, the ambient gas, the degree of vacuum, and the like, and is not particularly limited. The anode and the cathode may be formed by a laminate of two or more layers, if necessary. Preferably, the organic electroluminescent device of the present invention is at least one side transparent in the light-emitting wavelength region of the device. Further, the substrate is preferably transparent. The transparent electrode is obtained by using the above-mentioned conductive material and setting it by vapor deposition or sputtering to ensure a predetermined light transmittance. The electrode of the light-emitting surface is preferably such that the light transmittance is 10% or more. The substrate is not particularly limited as long as it has mechanical strength, thermal strength, and transparency, and examples thereof include a glass substrate and a transparent resin film. Examples of the transparent resin film include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polydecyl methacrylate, polyvinyl chloride, polyvinyl alcohol, and polyethylene. Polyvinyl butyral, nylon, polyetheretherketone, polybut, polyether stone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyfluorinated ethylene, tetrafluoroacetamethylene-ethylene copolymer , tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyether phthalimide, polypropylene, and the like. 22 321109 200946537 In the organic electroluminescent device of the present invention, a protective layer may be provided on the surface of the element in order to improve the stability to temperature, humidity, ambient gas, etc., or the entire element may be protected by an oil or a resin. • In addition, the formation of each layer of the organic electroluminescence element can be applied to a dry film formation method such as vacuum deposition, sputtering, plasma, or ion plating, or a wet film formation method such as a spin coating method, a dip coating method, or a flow coating method. Any method of law. The film thickness is not particularly limited, but the film thickness is usually in the range of 5 nm to 10 // m, particularly preferably in the range of 10 mn to 0.2/zm. When a wet film formation method is used, a compound represented by the above formula (1) can be dissolved or dispersed in a solvent such as ethanol, chloroform, tetrahydrofuran or dioxane to prepare a film. The dry film formation method is preferably vacuum vapor deposition, and the vacuum degree of the vacuum film is set to 2 x 10 3 Pa or less, and the substrate temperature is room temperature, and the formula (1) of the present invention which has been placed in the vapor deposition tank is used. The substituted acetylene gold-cyclic alkylamino carbene complex is heated to evaporate the material to prepare a thin Q film. At this time, in order to control the temperature of the distilled source, a thermocouple (thermocoup 1 e) or a non-contact infrared thermometer or the like which is in contact with the distillation tank is suitable. Moreover, in order to control the vapor deposition amount, it is applicable by vapor deposition film thickness. An example of a preferred embodiment of the vapor deposition film thickness gauge is a crystal unit provided on the surface of the vapor deposition source, and the vapor deposition film attached to the surface of the crystal vibrator is measured from the change in the oscillation frequency of the vibrator. The weight was determined immediately from the measured weight. The co-evaporation of the substituted acetylene gold-cyclic alkylamino carbene complex represented by the above formula (1) with a luminescent material or other host material can be carried out by using 23 321109. 200946537, respectively. And it is carried out separately by controlling the respective temperatures. *In order to improve film formation and prevent film = use of, for example, polystyrene, polycarbonate, polypropylene, etc. (4) 'melamine polyurethane, polysulfone, polymethyl methacrylate, polypropylene

Insulating resins such as cellulose and cellulose, and copolymers of these, · Poly I = base, poly-m-light guide dragon; (four) phenotype, poly-scale, etc. = electricity) ± resin such as tree I; or antioxidant, Additives such as ultraviolet rays. The organic electroluminescent device of the present invention can be used for a light source such as a flat panel display such as a wall-mounted television or a mobile phone, a photocopier, a printer, a liquid backlight, or a light source of a metering shaft. Display boards, lights, etc. (Examples) Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited thereto. Yoke Example 1 ([Ν1(2,6-diisopropylphenyl)-2,2,4,4-tetradecylpyridinium-pyrrolidyl-4' fluorophenylacetylene gold (23)] Synthesis of 1~(2,6-diisopropylphenyl)__2, 2, 4, 4-tetramethyl-3 in a 30 mL Schlenk flask under argon 4-Dihydro 2H difluorosulfonium sulfonate rust salt (261 mg, 〇. 6 ^), tetrahydrofuran (6 mL), a suspension solution. Lithium diisopropyl guanamine (2. 〇M solution, 300 / / L, 0.6 mmol) was added at -78 ° C, stirred for 5 minutes, stirred at room temperature for 45 minutes, and then distilled to remove tetrahydrofuran under reduced pressure. Byproduct diisopropylamine. After adding tetrahydrofuran (8 mL) and stirring at 70 t for 5 minutes, the mixture was filtered, and the mixture was filtered, and the mixture was filtered, and the mixture was added to the filtrate, and 4-fluorophenylethynyl (triphenylphosphine) gold (116 mg '0.2 mmol) was added to the filtrate. Stir at room temperature for 2 hours. After the tetrahydrogen was distilled off under reduced pressure, dichloromethane was added and washed with water to give a pH of 7. After the sulfuric acid was dried, the solvent was distilled off under reduced pressure in an evaporator. The reaction product was purified by column chromatography (hexane / EtOAc / EtOAc / EtOAc (EtOAc) 1 H-NMR (3 0 OMHz, CDC 1 3 ) 5:7. 2 4 - 7. 4 2 (m, 5 Η) , 6. 81-6. 85 (m, 2 Η), 2· 75-2 81 (sept, 2 Η), 2. 07 (s Ο * 2Η), 1. 53 (s, 6Η), 1. 44 (d, 6Η), 1. 34 (s, 6Η), 1. 3 1 (d, 6H) EI -MS (M/Z) : 6 0 1 (M + ) , c I (m/z) : 6 〇 2 (MH + ) luminescence analysis (CHC13, 77K, Ex250nm) A(nm) :412(max)

Thermal analysis: melting point 212 ° C Elemental analysis observed C: 56. 0, Η: 5. 9, N: 2. 3 Theoretical value C: 55. 9, Η: 5. 9, Ν: 2. 3 Example 2 (Production of Organic Electroluminescence Element) 电 The electroluminescence element shown in Fig. 2 was produced as follows. A glass made of an indium tin oxide (hereinafter abbreviated as ΙΤ0) film made of EHC Corporation was used as a transparent electrode substrate, and a vacuum vapor deposition apparatus manufactured by ULVAC Co., Ltd. was used, and a vacuum of 2×10 −3 Pa or less was used on the substrate. The following steps are carried out: a hole transport layer 3 having a film thickness of 40 nm, which is composed of 2-(4,-trimethyldecylphenyl)-triazine; a light-emitting layer 4 having a film thickness of 30 nm, It is contained in a 2-methyl-1,4-bis(triphenylsulfanyl)benzene (hereinafter abbreviated as Me-p-BTPGB) as a host, and contains a phosphorescent complex (N) as a guest 25321109 200946537. -(2',6'-diisopropylphenyl)-,2,2,4,4-tetramethylpyrrolidinyl-4'fluorophenylacetylene gold (hereinafter referred to as phosphorescent complex (23) )) 5.0% by weight; '30 nm hole barrier layer 5, which is composed of 3-(4-biphenyl)-4-phenyl-5-tributylphenyl-1,2, 4-triazole (sublimation refined product, hereinafter abbreviated as TAZ); 0. 5 nm electron transport layer 6, which is composed of a fluorinated chain (hereinafter referred to as LiF), an electrode 7 of 100 nm, which is made of aluminum (hereinafter referred to as A1). In addition, the vacuum evaporation is performed by feeding the raw material into a crucible disposed facing the substrate and heating the raw material together with the crucible. Comparative Example (Production of Organic Electroluminescence Element) For the comparative example In other words, the organic electroluminescent device was fabricated in the same manner as in Example 2 except that the luminescent layer 4 was not contained in the luminescent layer 4. The ITO of the electroluminescent device of Example 2 was used. When the electrode 2 is used as a positive electrode and the A1 electrode 7 is used as a negative electrode to conduct electricity and the voltage between the electrodes is raised, the element emits blue light which is clearly visible to the naked eye from the vicinity of +12 V, and emits light at 4.6 cd/m 2 in +24 V. The current efficiency of the light emission of the element is obtained by the following equation: Current efficiency = (luminous brightness per unit area) / (current density per unit area) The current efficiency thus obtained is 0. 014cd / in + 21V A. 26 321109 200946537 The luminescence color of this element was measured using a spectrophotometer manufactured by JASCO Corporation. The chromaticity coordinates obtained from jis * Z8701 were based on the spectrum obtained at the voltage between electrodes + 19V. =0.169, y=0.139. The luminescence spectrum (in chloroform, the chloroform was measured by a phosphorescence spectrophotometer using the disc photo-complex (2 3 ) synthesized in Example 1 and the organic electroluminescent elements of Example 2 and Comparative Example The temperature of 77 K (absolute temperature), under ultraviolet irradiation. As shown in Fig. 1, the organic electroluminescent device of Example 2 has a large value of the luminescence peak φ in a deep blue region (410 to 440 nm) of 440 nm or less. On the other hand, the organic electroluminescence device of the comparative example in which the phosphorescent complex (23) is not contained in the light-emitting layer exhibits an emission peak maximum value in the vicinity of 380 nm outside the dark blue region (ultraviolet region). Further, in the electroluminescence device of the comparative example, although the ΙΤ0 electrode 2 was used as the positive electrode and the M electrode 7 was used as the negative electrode to conduct electricity and the voltage between the electrodes was raised, weak luminescence was observed only in the %-violet region. (Industrial Applicability) ❹ The invention can realize a kind of component, which is a photo-organic electroluminescent device, and is a dark blue region (4) below which is important for completing a full-color display (10). i 44〇ηιη) has the maximum value of the luminescence peak caused by the electro-excitation light, and the luminescent color clock, / especially CIE (International Commission on Illumination) color 糸 whose y coordinate does not reach 〇 180. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a can light spectrum of the complex of Example 1, and EL of the organic electroluminescence element of Example 2 and Comparative Example. Fig. 2 is an organic electroluminescence of Example 2. The construction of the components. 321109 27 200946537 [Description of main component symbols] 1 Glass substrate 2 ΙΤ0 transparent electrode 3 Hole transport layer 4 Light-emitting layer 5 Hole barrier layer 6 Electron transport layer 7 Aluminum electrode

• 28 321109

Claims (1)

200946537 ^ VII. Patent application scope: 1. A substituted acetylene gold-cyclic alkylamino carbene complex, which is represented by the formula (1): X -AuL (1) where L represents a cyclic alkylamino carbene ligand; X represents an alkyl group, a ring-based group, an aryl group, an aryl group or a heterocyclic group; and one or several hydrogen atoms on the carbon atom of the 'X' Dialkylamino group, alkyl group independently substituted by halogen atom 'alkyl, cycloalkyl, alkenyl, aryl, aralkyl, alkoxy, aryloxy, substituted with the same or different alkyl groups a carbonyl group, an arylcarbonyl group, an alkyl fluorenyl group, an aryl fluorenyl group, an alkylsulfonyl group or a fluorenyl group; when a plurality of hydrogen atoms on the carbon atom of X are independently alkyl, alkenyl, An aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamino group substituted with the same or different alkyl groups, an alkyl group, an arylcarbonyl group, an alkyl fluorenyl group, an aryl group When the alkylsulfonyl or aryl® thiol group is substituted, the adjacent groups may be bonded to each other to form a ring. 2. The substituted acetylene gold-cyclic alkylamine-based carbon complex according to the j-th aspect of the patent application, wherein the base carbon oxime ligand: R3, the above L is a cyclic alkyl group represented by the formula (2) amine (2) wherein η represents an integer from 1 to 3; 321109 29 200946537 R1 represents an alkyl group, a cycloalkyl group, a polycycloalkyl group or an aryl group; and R2, R3, R4 and R5 may each be the same or different and represent hydrogen. An atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, or a dialkylamine substituted by the same or different two alkyl groups. a group, or a contiguous group of R2, R3, R4 and R5, together with the carbon atoms to which they are bonded, form a ring; when R1 to R5 represent a group containing a carbon atom, one or a number of carbon atoms thereof The hydrogen atom may be substituted by a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group. 3. The substituted acetylene gold-cyclic alkylamino carbon-based complex according to item 2 of the patent application, wherein 'R1 is an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 7 carbon atoms a polycycloalkyl group having 6 to i carbon atoms or an aryl group having 6 to 20 carbon atoms; and R 2 , R 3 , R 4 and R 5 are independently a hydrogen atom, a halogen atom or a carbon atom having 1 to 20 carbon atoms; , an alkenyl group having 2 to 20 atomic number, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 6 to 14 carbon atoms An aryloxy group, a nitro group, a cyano group, or a dialkylamino group substituted by the same or different two alkyl groups. 4. The substituted acetylene gold-cyclic alkylamino carbene complex as claimed in claim 3, wherein the polycycloalkyl group is selected from the group consisting of bicyclo-[2.1.1]-hexyl, bicyclo-[2 · 2. 1]-Heptyl, bicyclo-[2. 2. 2]-octyl, bicyclo-[3. 3. 0]-octyl, bicyclo-[4. 3· 0]-fluorenyl, bicyclo- [4. 4. 0]- 30 321109 200946537 ~ Group of octyl and adamantyl groups. 5. A method for producing a substituted acetylene gold-cyclic alkylamino group* carbene complex according to item 1 of the patent application, which comprises a substituted acetylene phosphine complex w and a cyclic alkylamine The carbene is coordinated to carry out a reaction. 6. The production method according to claim 5, wherein the 'cyclic arylamino carbene ligand is obtained by reacting a cyclic guanamine iron salt with a test. ^ 7. The method of manufacture of claim 5 or 6 wherein the reaction is based on 1 mole of the substituted acetylene phosphine complex, using a cyclic alkylamino carbene ligand 1 to 5 Moor. 8. The production method according to any one of claims 5 to 7, wherein the reaction is carried out by mixing a substituted acetylene gold "complex with a cyclic alkylamino carbene ligand" In the presence of a solvent, it is carried out by enthalpy to 12 (the temperature of TC is stirred. 9. An organic electroluminescent device characterized in that an optical layer or a plurality of organic compounds containing a light-emitting layer is formed between a pair of electrodes. In the thin layer, the thin layer of the organic compound contains one or more substituted acetylene gold-cyclic alkylamino carbene complexes represented by the formula (1) of the first aspect of the patent application. The organic electroluminescent device of claim 9 which forms a light-emitting layer or a thin layer of an organic compound comprising a plurality of layers of the light-emitting layer between the pair of electrodes, and has phosphorescence of the phosphorescent excitation light in a deep blue region below 440 nm. The peak value of the peak, and the luminescent color of the CIE (International Commission on Illumination) color system is less than 0. 18. 321109 31