JP2010037244A - Substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonionic, substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex having luminescence in a blue region of ≤475 nm indispensable for achieving full color display, and useful as a light-emitting material or the like for an organic luminescence element having a high melting point of ≥200°C and resisting to the Joule heat generated when applying a voltage. <P>SOLUTION: The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by general formula (1) (wherein, L is a nitrogen-containing heterocyclic carbene ligand; R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group) is useful as the light-emitting material having the characteristics of the problem. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex useful as a light-emitting material for an electroluminescent device (organic electroluminescence device).

  In recent years, organic electroluminescence elements have attracted attention as display devices for high-performance flat color displays, but as luminescent materials, fluorescent materials that utilize light emission from excited singlets of luminescent molecules are mainly used. In order to achieve higher efficiency, phosphorescent materials that use light emitted from excited triplets have been actively developed. However, the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention has not been known at all.

  An object of the present invention is to provide an organic luminescence device having a high melting point of 200 ° C. or more that can emit light of a blue region of 475 nm or less, which is indispensable for realizing a full color display, and can withstand Joule heat generated when a voltage is applied. An object of the present invention is to provide a nonionic substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex useful as a light-emitting material.

  The present invention relates to a general formula (1)

(In the formula, L represents a nitrogen-containing heterocyclic carbene ligand. R represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. Multiple hydrogen atoms are halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, dialkylamino groups, alkylcarbonyl groups, arylcarbonyl groups, alkyl mercapto groups, aryl mercapto groups. A plurality of hydrogen atoms on the carbon atom of R may be substituted with an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group. , Dialkylamino group, formyl group, alkylcarbonyl group, arylcarbonyl Group, alkylmercapto group, arylmercapto group, an alkylsulfonyl group, or when they are substituted with an arylsulfonyl group, may form a ring by bonding groups to each other are adjacent.)
This is solved by a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the following formula.

  According to the present invention, a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex useful as a light-emitting material for an organic electroluminescence element can be provided.

  The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention is represented by the general formula (1). In the general formula (1), L represents a nitrogen-containing heterocyclic carbene ligand. R represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. Note that one or more hydrogen atoms on the carbon atom of R are 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, an alkylcarbonyl group, An arylcarbonyl group, an alkyl mercapto group, an aryl mercapto group, an alkylsulfonyl group, or an arylsulfonyl group may be substituted. In addition, a plurality of hydrogen atoms on the carbon atom of R are alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, dialkylamino groups, formyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkylmercaptos. When it is substituted with a group, an aryl mercapto group, an alkylsulfonyl group, or an arylsulfonyl group, adjacent groups may be bonded to form a ring.

  The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Can be mentioned. These substituents include isomers thereof.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl. Group, cyclododecyl group and the like.

  The aryl group is preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl group, tolyl group, xylyl group, naphthyl group, dimethylnaphthyl group, anthracenyl group, phenanthrenyl group, chrysenyl group, tetraphenyl group, naphthacenyl group. Etc. These substituents include isomers thereof.

  The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a naphthylmethyl group, an indenylmethyl group, and a biphenylmethyl group.

  As the heterocyclic group, pyrrolyl group, furanyl group, thiophenyl group, indolyl group, benzofuranyl group, benzothiophenyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, quinolyl group, isoquinolyl group, quinazolyl group, quinoxalyl group Etc. Note that one or more hydrogen atoms on the carbon atom of R are 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, an alkylcarbonyl group, An arylcarbonyl group, an alkyl mercapto group, an aryl mercapto group, an alkylsulfonyl group, or an arylsulfonyl group may be substituted. In addition, a plurality of hydrogen atoms on the carbon atom of R are alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, dialkylamino groups, formyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkylmercaptos. When substituted with a group, an aryl mercapto group, an alkylsulfonyl group, or an arylsulfonyl group, adjacent groups may combine to form a ring.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As said alkyl group, a C1-C20, especially 1-12 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, nonyl Group, decyl group, undecyl group, dodecyl group and the like. These substituents include isomers thereof.

  The cycloalkyl group is particularly 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 cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms. For example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group. Group, undecenyl group, dodecenyl group and the like. These substituents include isomers thereof.

  The aryl group is preferably an aryl group having 6 to 20 carbon atoms, particularly 6 to 16 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a dimethylnaphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, A pyrenyl group etc. are mentioned. These substituents include isomers thereof.

  The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a naphthylmethyl group, an indenylmethyl group, and a biphenylmethyl group.

  As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is particularly preferable. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentanoxy group, a hexanoxy group, a heptanoxy group, an octanoxy group, a nonanoxy group, a decanoxy group Etc. These substituents include isomers thereof.

  The aryloxy group is particularly preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group, a triloxy group, a xylyloxy group, a naphthoxy group, and a dimethylnaphthoxy group. These substituents include isomers thereof.

  The dialkylamino group is particularly preferably a dialkylamino group having 2 to 10 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group, and a dipropylamino group. These substituents include isomers thereof.

  The alkylcarbonyl group is particularly preferably an alkylcarbonyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, and a butanoyl group. These substituents include isomers thereof.

  The arylcarbonyl group is particularly preferably an arylcarbonyl group having 7 to 11 carbon atoms, and examples thereof include a benzoyl group, a fluorobenzoyl group, and a carbonnaphthyl group. These substituents include isomers thereof.

  The alkyl mercapto group is preferably an alkyl mercapto group having 1 to 6 carbon atoms, and examples thereof include a methyl mercapto group, an ethyl mercapto group, a propyl mercapto group, a butyl mercapto group, a pentyl mercapto group, and a hexyl mercapto group. These substituents include isomers thereof.

  The aryl mercapto group is preferably an aryl mercapto group having 6 to 14 carbon atoms, and examples thereof include a phenyl mercapto group, a tolyl mercapto group, a xylyl mercapto group, and a naphthyl mercapto group. These substituents include isomers thereof.

  As said alkylsulfonyl group, a C1-C12 alkylsulfonyl group is preferable, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group etc. are mentioned.

  The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 18 carbon atoms, and examples thereof include a phenylsulfonyl group, a tolylsulfonyl group, and a naphthylsulfonyl group.

  When a plurality of hydrogen atoms on the carbon atom of R are substituted with an alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, carboalkyl group and carboaryl group, The groups that are bonded together may form a ring.

  Examples of the ring in the case where the adjacent groups are bonded to form a ring include, for example, a cyclopentene ring, cyclohexene ring, cycloheptene ring, benzene ring, naphthalene ring, tetrahydrofuran ring, benzopyran ring, N-methylpyrrolidine ring, N-methyl piperidine ring etc. are mentioned.

  The nitrogen-containing heterocyclic carbene ligand is represented by the general formula (2) or (3)

(In the formula, R ¹ and R ² may be the same or different, and each represents an alkyl group, a cycloalkyl group, a polycycloalkyl group, or an aryl group, and R ³ , R ⁴ , R ^5, and R ⁶ are Each may be the same or different and represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, aryloxyl group, nitro group, cyano group or dialkylamino group, and is adjacent The groups may be bonded to each other to form a ring; the arbitrary hydrogen atoms of R ^{1 to} R ⁶ are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxyl group. Alternatively, it may be substituted with an aryloxyl group.)
Indicated by

In the general formulas (2) and (3), R ¹ and R ² represent an alkyl group, a cycloalkyl group, a polycycloalkyl group, or an aryl group, and the alkyl group, the cycloalkyl group, and the aryl group are the same as the above R. It is synonymous with what is defined.

  The polycycloalkyl group is preferably a polycycloalkyl group having 6 to 10 carbon atoms, and includes a bicyclo- [2.1.1] -hexyl group, a bicyclo- [2.2.1] -heptyl group, and a bicyclo- [ 2.2.2] -octyl group, bicyclo- [3.3.0] -octyl group, bicyclo- [4.3.0] -nonyl group, bicyclo- [4.4.0] -octyl group, adamantyl Groups and the like.

R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, aryloxyl group, nitro group, cyano group or dialkylamino group. As shown, the alkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, aryloxyl group or dialkylamino group has the same meaning as defined above for R.

Note that any hydrogen atom of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a halogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group or aryloxyl. It may be substituted with a group, and these groups are also synonymous with those defined for X. Among these, R ¹ and R ² are preferably a tert-butyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group or an adamantyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ is preferably a hydrogen atom or a halogen atom, particularly a chlorine atom.

  Specific examples of the nitrogen-containing heterocyclic carbene ligand (L) in the present invention include compounds represented by formulas (4) to (13).

  The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the general formula (1) of the present invention is, for example, a reaction process formula (1).

(In the formula, R and L are as defined above, and P represents a monodentate phosphine ligand.)
As shown in the above, it can be obtained by reacting a substituted ethynylgold phosphine complex with a nitrogen-containing heterocyclic carbene ligand (L).

  Examples of the monodentate phosphine ligand (P) include bis (pentafluorophenyl) phenylphosphine, (4-bromophenyl) diphenylphosphine, diallylphenylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, and 4- (dimethylamino). Phenyldiphenylphosphine, dimethylphenylphosphine, diphenyl (2-methoxyphenyl) phosphine, diphenyl (pentafluorophenyl) phosphine, diphenylpropylphosphine, diphenyl-2-pyridylphosphine, diphenyl (p-tolyl) phosphine, diphenylvinylphosphine, ethyldiphenyl Phosphine, isopropyldiphenylphosphine, methyldiphenylphosphine, tribenzylphosphine, tributylphosphine , Tri-t-butylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, triethylphosphine, tri-2-furylphosphine, triisobutylphosphine, triisopropylphosphine, tripropylphosphine, trimethylphosphine, trioctylphosphine, triphenylphosphine , Tris (4-chlorophenyl) phosphine, tris (3-chlorophenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (4-fluorophenyl) phosphine, tris (3-fluorophenylphosphine), tris (4- Methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-trifluoromethylphenol) L) phosphine, tris (pentafluorophenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tri-m-tolylphosphine, tri-o- Tolylphosphine, tri-p-tolylphosphine, benzyldiphenylphosphine, bis (2-methoxyphenyl) phenylphosphine, diphenylcyclohexylphosphine, 2- (di-t-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, Neomenthyldiphenylphosphine, p-tolyldiphenylphosphine, triallylphosphine, 2,4,4-trimethylpentylphosphine, tri (1-naphthyl) phosphine, tris (hydroxymethyl) phosphine, tris (hydride) Roxypropyl) phosphine and the like. These can use a commercially available thing as it is.

  The substituted ethynyl gold phosphine complex is, for example, a reaction process formula (2)

(In the formula, R and P are as defined above, and Y represents a halogen atom.)
As shown in the above, it can also be obtained by reacting a gold halogenophosphine complex with a substituted ethyne.

In addition, the said gold halogenophosphine complex is compoundable by a well-known method (for example, refer nonpatent literature 1-2).
Journal of Chemical Society, Dalton Trans. , 411 (1986) Experimental Chemistry Course, 4th edition, Maruzensha, page 455, 18 (1991)).

As the nitrogen-containing heterocyclic carbene ligand, a commercially available product may be used as it is, or for example, a compound synthesized by a known method as shown in Non-Patent Document 3 or Patent Document 1 may be used. Good (see, for example, Non-Patent Document 3 and Patent Document 1).
J. et al. Am. Chem. Soc. 114, 5530 (1992) International Publication No. 98/27064 pamphlet

The substituted ethyne compound may be a commercially available product or can be synthesized by a known method as shown in Non-Patent Document 4.
European Journal of Organic Chemistry, 15, 2438 (2007)

  In the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the reaction process formula (1), the amount of the nitrogen-containing heterocyclic carbene ligand used is preferably 1 with respect to 1 mol of the substituted ethynyl gold phosphine complex. -3 mol, more preferably 1-1.5 mol.

  The solvent used in the synthesis of the above substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex is not particularly limited as long as it does not inhibit the reaction. For example, tetrahydrofuran, furan, dioxane, tetrahydropyran, diethyl ether, diisopropyl ether , Ethers such as dibutyl ether, aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane and dichloropropane Class: Halogenated aromatic hydrocarbons such as chlorobenzene are used. In addition, you may use these solvents individually or in mixture of 2 or more types.

  Although the usage-amount of the said solvent is suitably adjusted with the uniformity and stirring property of a reaction liquid, Preferably it is 1-30L with respect to 1 mol of substituted ethynyl gold phosphine complexes, More preferably, it is 5-20L.

  The above-mentioned substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex can be synthesized, for example, by the reaction of a substituted ethynylgold phosphine complex, a nitrogen-containing heterocyclic carbene ligand (nitrogen-containing heterocyclic hydrohalide and a base. ) And a solvent, and the reaction is conducted with stirring. The reaction temperature at that time is preferably 0 to 120 ° C., more preferably 20 to 100 ° C., and the reaction pressure is not particularly limited.

  The above substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex is isolated and produced by a known method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, sublimation, chromatography, etc. after completion of the reaction.

Further, the substituted ethynylgold phosphine complex of the present invention can be obtained by a method of reacting a gold halide (I) -nitrogen-containing heterocyclic carbene complex represented by the reaction process formula (3) with a substituted ethyne in addition to the above method. It is done.

(In the formula, R, Y and L are as defined above.)

As the gold halide (I) -nitrogen-containing heterocyclic carbene complex used in the above reaction, a commercially available product may be used, or it may be simply synthesized as shown in Non-Patent Document (5).
Organometallics, 24, 2411, 2005

  In the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the reaction process formula (3), the amount of the substituted ethyne used is preferably 1 mole of the gold halide (I) -nitrogen-containing heterocyclic carbene complex. Is 1 to 3 mol, more preferably 1 to 1.5 mol.

  The solvent used in the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the above reaction process formula (3) is not particularly limited as long as it does not inhibit the reaction. For example, methanol, ethanol, propanol, butanol, etc. Alcohols, tetrahydrofuran, furan, dioxane, tetrahydropyran, ethers such as diethyl ether, diisopropyl ether and dibutyl ether, aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatics such as benzene, toluene and xylene Hydrocarbons; Halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane, dichloropropane; and aromatic hydrocarbons such as chlorobenzene are used. In addition, these solvents may use an isomer, and may be used alone or in admixture of two or more.

  The amount of the solvent used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 1 to 30 L, more preferably 1 mol per 1 mol of the gold halide (I) -nitrogen-containing heterocyclic carbene complex. 5-20L.

  The above-mentioned substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex is synthesized, for example, by mixing a substituted ethyne, a gold halide (I) -nitrogen-containing heterocyclic carbene complex, a base and a solvent and reacting them with stirring. Etc. are performed. The reaction temperature at that time is preferably 0 to 120 ° C., more preferably 20 to 100 ° C., and the reaction pressure is not particularly limited.

The above-mentioned substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex is synthesized in the presence of a base. A metal alkoxide is preferable as the base. Alkali metal alkoxides are particularly preferable. Specific examples include lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, and potassium butoxide. It is done. Regarding the alkali metal propoxide and butoxide, isomers of alkoxy groups are also included. The amount of the base to be used is preferably 1 to 3 mol, more preferably 1 to 1.5 mol, per 1 mol of gold (I) chloride-containing nitrogen-containing heterocyclic carbene complex.

  The above substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex is isolated and produced by a known method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, sublimation, chromatography, etc. after completion of the reaction.

  Examples of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention include compounds represented by the following formulas (15) to (16).

  In addition, it was suggested that the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of this invention is used suitably as an organic electroluminescent element from the physical-property value as described in an Example.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 (Synthesis of acetylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (AcE)])
Under an argon atmosphere, 1,3-bis (2,6-diisopropylphenyl) imidazolium chloride (IPrH ⁺ Cl ⁻ ; 251 mg, 0.59 mmol), tert-butoxypotassium (85% by mass, 102 mg, 0) was added to a 25 ml Schlenk tube. .77 mmol) and tetrahydrofuran (9 ml) were added, and the mixture was stirred at room temperature for 15 minutes, and then the tetrahydrofuran was distilled off under reduced pressure. After adding toluene (9 ml) and stirring at 70 ° C. for 5 minutes, the reaction mixture was filtered and the filtrate was methylcarbonylethynyl (triphenylphosphine) gold (240 mg, 0.46 mmol), another 30 ml Schlenk with 9 ml of toluene added. Drip into the tube. After the addition, the reaction mixture was heated at 70 ° C. for 2.5 hours. After cooling the reaction mixture to room temperature, toluene was added to the reaction mixture and washed with water to adjust the pH to 7. After drying with sodium sulfate, the solvent was distilled off under reduced pressure using an evaporator. The reaction crude product was purified by column chromatography using silica gel (Hexane / AcOEt = 5/1 to 3/1), and the resulting solid was dissolved in ethyl acetate and reprecipitated with hexane to give a white solid. 0.21 g of a certain target product was obtained (yield 72%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.53-7.45 (m, 2H), 7.30-7.26 (m, 4H), 7.14 (s, 2H), 2.61-2.47 (sept, 4H), 2.15 (s, 3H), 1.33 (d, 12H), 1.21 (d, 12H)
CI-MS (M / Z): 653 (MH) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 424 (max)
Thermal analysis: Melting point: 269 ° C
Elemental analysis Observation C: 56.63, H: 5.90, N: 4.20
Theoretical value C: 57.05, H: 6.02, N: 4.29

Example 2 (Synthesis of acetylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (AcE)])
Under an argon atmosphere, a 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene gold chloride (I) [IPrAuCl: 93.2 mg, 0.15 mmol], acetylethyne (11 mg,. 158 mmol) and ethanol (3 ml) were added, and then sodium ethoxide (62 μl, 0.158 mmol: ethanol solution with a concentration of 2.55 mol / L (liter)) was added dropwise. After stirring at room temperature for 19 hours, ethanol was distilled off under reduced pressure, methylene chloride was added and the mixture was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure using an evaporator. The obtained white solid was purified by column chromatography (Hexane / AcOEt = 5/1 to 3/1), and then washed and filtered with hexane to obtain 0.093 g of the desired product as a white solid (yield) 95%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.53-7.45 (m, 2H), 7.30-7.26 (m, 4H), 7.14 (s, 2H), 2.61-2.47 (sept, 4H), 2.15 (s, 3H), 1.33 (d, 12H), 1.21 (d, 12H)
CI-MS (M / Z): 653 (MH) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 424 (max)
Thermal analysis: Melting point: 269 ° C
Elemental analysis Observation C: 56.63, H: 5.90, N: 4.20
Theoretical value C: 57.05, H: 6.02, N: 4.29

Example 3 (Synthesis of benzoylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (BzE)])
The obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1 to 3/1) after the same operation as in Example 2 except that benzoylethine (21 mg, 0.158 mmol) was used instead of acetylethine. Then, the product was washed with hexane and filtered to obtain 0.098 g of the desired product as a white solid (yield 91%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.71-7.25 (m, 11H), 7.14 (s, 2H), 2.65-2.50 (sept, 4H), 1.33 (d, 12H), 1.22 (d, 12H)
CI-MS (M / Z): 715 (MH) ⁺
Luminescent analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 474
Thermal analysis: Melting point: 280 ° C
Elemental analysis Observation C: 60.63, H: 5.80, N: 3.90
Theoretical value C: 60.50, H: 5.78, N: 3.92

Reference Example 1 (Synthesis of acetylethynyl (triphenylphosphine) gold [Au (PPh ₃ ) (AcE)])
Under an argon atmosphere, Au (PPh ₃ ) Cl (247 mg, 0.50 mmol), 3-butyn-2-one (59 μL, 0.75 mmol) and ethanol (10 ml) were added to a 30 ml Schlenk tube, and then sodium ethoxide ( 208 μl, 0.53 mmol: ethanol solution having a concentration of 2.55 mol / L (liter)) was added dropwise and stirred at room temperature for 17 hours. After the reaction, ethanol was distilled off under reduced pressure, and the resulting residue was dissolved in methylene chloride and washed with water. After drying with sodium sulfate, the solvent was distilled off under reduced pressure using an evaporator. The obtained solid was washed with hexane and vacuum-dried to obtain 0.25 g of the target compound as a brown powder. (Yield 95%)

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.56-7.43 (m, 15H), 2.35 (s, 3H)

  When the emission spectrum of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex synthesized in Examples 1 to 3 was measured with a phosphorescence fluorometer (in chloroform, at a temperature of 77 K (Kelvin), under ultraviolet irradiation), the emission maximum was obtained. Blue phosphorescence was emitted at wavelengths of 431 nm to 475 nm and CIE chromaticity coordinates (0.166, 0.121) to (0.152, 0.342).

  Moreover, as a result of thermal analysis, the melting points of the substituted phenylethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention are all 200 ° C. or higher, suggesting that it is suitably used as an organic electroluminescence device.

  The present invention provides a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex useful as a light-emitting material for an electroluminescent device (organic electroluminescence device).

Claims (14)

General formula (1)

(In the formula, L represents a nitrogen-containing heterocyclic carbene ligand. R represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. Multiple hydrogen atoms are halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, dialkylamino groups, alkylcarbonyl groups, arylcarbonyl groups, alkyl mercapto groups, aryl mercapto groups. A plurality of hydrogen atoms on the carbon atom of R may be substituted with an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or an aryloxy group. , Dialkylamino group, formyl group, alkylcarbonyl group, arylcarbonyl Group, alkylmercapto group, arylmercapto group, an alkylsulfonyl group, or when they are substituted with an arylsulfonyl group, may form a ring by bonding groups to each other are adjacent.)
A substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the formula: L is the general formula (2) or (3)

(In the formula, R ¹ and R ² may be the same or different, and each represents an alkyl group, a cycloalkyl group, a polycycloalkyl group, or an aryl group, and R ³ , R ⁴ , R ^5, and R ⁶ are Each may be the same or different and represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, aryloxyl group, nitro group, cyano group or dialkylamino group, and is adjacent The groups may be bonded to each other to form a ring; the arbitrary hydrogen atoms of R ^{1 to} R ⁶ are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxyl group. Alternatively, it may be substituted with an aryloxyl group.)
The substituted ethynylgold-nitrogen-containing heterocyclic carbene complex according to claim 1, which is a nitrogen-containing heterocyclic carbene ligand represented by the formula: R ¹ and R ² are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a polycycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryloxyl group having 6 to 14 carbon atoms, a nitro group, a cyano group, or a dialkylamino group having 2 to 10 carbon atoms. 3. A substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to 2.   The polycycloalkyl group is a bicyclo- [2.1.1] -hexyl group, a bicyclo- [2.2.1] -heptyl group, a bicyclo- [2.2.2] -octyl group, or a bicyclo- [3. The substituted ethynyl gold-nitrogen-containing group according to claim 3, which is a 3.0] -octyl group, a bicyclo- [4.3.0] -nonyl group, a bicyclo- [4.4.0] -octyl group or an adamantyl group. A telocyclic carbene complex. R ¹ and R ² are tert-butyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group or adamantyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms Or a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 2, which is a chlorine atom. R ¹ and R ² are tert-butyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group or adamantyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 2.   The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to any one of claims 1 to 6, wherein R is a methyl group or a phenyl group.   The method for producing a substituted ethynylgold-nitrogen-containing heterocyclic carbene complex according to any one of claims 1 to 7, wherein the substituted ethynylgold-phosphine complex is reacted with a nitrogen-containing heterocyclic carbene ligand.   The process according to claim 8, wherein the nitrogen-containing heterocyclic carbene ligand is obtained by reaction of a nitrogen heterocyclic hydrohalide with a base.   The process according to claim 8 or 9, wherein the reaction uses 1 to 3 moles of a nitrogen-containing heterocyclic carbene ligand per mole of the substituted ethynylgold phosphine complex.   The reaction is carried out by mixing a substituted ethynylgold phosphine complex and a nitrogen-containing heterocyclic carbene ligand, and stirring at a temperature of 0 to 120 ° C in the presence of a solvent. The manufacturing method.   The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to any one of claims 1 to 7, wherein a gold (I) halide-nitrogen-containing heterocyclic carbene complex and a substituted ethyne are reacted in the presence of a base in an organic solvent. The manufacturing method. The method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 13, wherein the base is an alkali metal alcoholate. The method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 13 or 14, wherein the organic solvent is an alcohol.