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

200946537 六、發明說明： 【發明所屬之技術領域】 本發明係關於作為電場發光元件（有機電激發光元件） 用發光材料料有用之取代乙块金1狀絲胺基礙稀錯 合物。 【先前技術】 近年來，有機電激發光元件係 顯示器用顯示裝置而受到注目％為同U面和色 從發光分子之激發單態發光、，光材料主要是使用利用 效率，現今正熱烈進行開發利光#料，為了追求更高之 光材料。然而，在磷光性古I用激發三重態發光的磷光發 有機雷ϋ， 製成在為了完成全彩顯示器、藏發光元件中，已知難以 色區域中實現電激發光所造而為重要之440ηΐίΐ以下之深藍 光色就CIE(國際照明委$之發光波峰極大值，並且發 0.18的元件（例如參照後述<)表色系而言其y座標未達 又，至今仍完全未知本案砟專利文獻1)。 胺基碳歸錯合物、及彳M 代乙驗-環狀坑基 之有機電激發光元件。 冑合物作為發光材料 [非專利文獻1]社團决人言八 討會演講要旨集第7頁^子學會2_年財機虹 【發明内容】 研 (發明欲解決之課題） 本發明之課題係提供〜 有機電激發光S件用發激發光元件及作為該 、用之化合物，該有機 200946537 激發光元件為磷光性有機電激發光元件，且為在為了完成 全彩顯示器而為重要之440nm以下之深藍色區域中具有電 Λ 激發光所造成之發光波峰極大值，並且發光色就CIE(國際 . 照明委員會）表色系而言其y座標未達0· 18的元件。 (解決課題之方法） 本發明之課題可藉由通式（丨）所示之取代乙炔金—環狀 烷基胺基碳烯錯合物而獲得解決： X·~ΞΞ= AuL (1) Ο 式中， L表示環狀烷基胺基碳烯配位子； X表示院基、環烷基、芳基、芳烷基或雜環基；此處，X之 碳原子上之1個或數個氫原子可獨立地被鹵原子、烷基、 環烷基、烯基、芳基、芳烷基、烷氧基、芳氧基、經相同 或不同之烷基取代而成之二烷基胺基、烷基羰基、芳基羰 基、烧基巯基、芳基巯基、烷基磺醯基或芳基磺醯基所取 © 代；當X之碳原子上之數個氫原子係獨立地被烷基、烯基、 芳基、芳烧基、烷氧基、芳氧基、經相同或不同之烷基取 代而成之二烷基胺基、烷基羰基、芳基羰基、烷基巯基、 芳基魏基、烧基磺醯基或芳基磺醯基所取代時，鄰接之基 可互相結合而形成環。 (發明之效果） 依據本發明’可實現在440nm以下之深藍色區域（410 至440nm)具有構光電激發光之發光波峰極大值，且發光色 就CIE(國際照明委員會）表色系而言其y座標未達w的 321109 200946537 有機電激發光元件，並可提供作為該有機電激發光元件 發光材料等為有用之取代乙炔金-環狀烷基胺基碳埽錯1 物。 σ 【實施方式】 本發明之取代乙炔金-環狀院基胺基碳烯錯合物係如 前述通式（1)所示。在該通式（1)中，L表示環狀烷基胺義 碳烯配位子。X表示烷基、環烷基、芳基、芳烷基或雜二 基。 長 前述烷基係以碳原子數1至10之烷基為佳，可列舉如 甲基、乙基、丙基、丁基、戊基、已基、庚基、辛基、壬 基、癸基等。尤以碳原子數1至6之烷基為特佳。又，此 等基係包括其異構物。 前述環烷基係以碳原子數3至12之環烷基為佳，可列 舉如環丙基、環丁基、環戊基、環己基、環庚基、環辛基、 環壬基、環癸基、環十一碳烷基、環十二碳烧基等。 前述芳基係以碳原子數6至18之芳基為佳，可列舉如 本基、甲笨基、二曱苯基.、聯苯基、節基、蔡基、二甲基 萘基、蒽基、菲基、苐基、芘基（pyrenyl)、2-苯并菲基 (chrysenyl)、稠四苯基（naphthacenyl)等。尤以碳原子數 6至14之芳基為特佳。又，此等基係包括其異構物。 前述芳烧基係以碳原子數7至2 0之芳烧基為佳，可列 舉如苯曱基、萘曱基、茚曱基、聯苯甲基（biphenylmethyl) 等。 前述雜環基係以含有選自N、0或S之至少1個雜原子 6 321109 200946537 的由3至l〇之環員所構成的飽和或不飽和之環式基為佳， I列舉如吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基、 * 苯并噻吩基、吡啶基、吡哄基、嘧啶基、嗒啡基、喹啉基、 . 異喹啉基、喹唑啉基（quinazolinyl)、喹喔嘴基 (quinoxalinyl)等。 X之碳原子上之1個或數個氫原子可獨立地被鹵原 子、垸基、環烷基、烯基、芳基、芳烷基、烷氧基、芳氧 ❹基、二烷基胺基、烷基羰基、芳基羰基、烷基巯基、芳基 毓基、烷基磺醯基或芳基磺醯基所取代。 前述鹵原子可列舉如氟原子、氯原子、溴原子、碘原 子。 前述烷基係以碳原子數1至2〇，尤以碳原子數1至12 之烧基為佳，可列舉如甲基、乙基、丙基、丁基、戊基、 己基、庚基、辛基、壬基、癸基、十一碳烷基、十二碳烷 基等。尤以碳原子數1至6之烷基為特佳。又，此等取代 ❹ 基係包括其異構物。 前述環烷基係以碳原子數3至7之環烷基為佳，可列 舉如環丙基、環丁基、環戊基、環已基、環庚基等。 前述烯基係以碳原子數2至20’尤以碳原子數2至12 之烯基為佳，可列舉如乙烯基、丙烯基、丁烯基、戊烯基、 己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、 十二碳烯基等。又，此等取代基係包括其異構物。 則述芳基係以碳原子數6至2〇，尤以碳原子數6至16 之芳基為佳.，可列舉如苯基、甲苯基、二曱苯基、聯苯基、 321109 200946537 節基、萘基、2甲基萘基、蒽基、菲基、第基 又’此等取代基係包括其異構物。 土寻 前述芳烧基係以碳原子數7至20之芳垸 舉如笨甲基、苯乙基、萘甲基、節甲基、聯苯甲基等1 前述烷氧基係以碳原子數丨至10之燒 = =氧基、乙氧基、丙氧基、丁氧基、戊氧::氧可基列 :::異::基、壬氧基、癸氧基等。又，此等取代基係 前述芳氧基係以碳原子數6至14之芳氧基為佳，可列 :如苯氧基、曱苯氧基、二甲苯氧基、萘氧基、二甲基茶 乳基等。又’此等取代基係包括其異構物。 刖述二烷基胺基較佳為.經選自碳原子數1至6之烷基 之相同或不同之2個基取代而成的二烷基胺基。尤其可列 舉如二曱基胺基、二乙基胺基、二丙基胺基等。又，此等 取代基係包括其異構物。 則述烷基羰基係以碳原子數2至10之烷基羰基為佳， 可列舉如乙醯基、丙醯基、丁醯基等。又，此等取代基係 包括其異構物。 土 前述芳基羰基係以碳原子數7至11之芳基羰基為佳， 可列舉如笨甲醯基、氟苯曱醯基、萘曱醯基等。又，此等 取代基係包括其異構物。 前述烷基巯基係以碳原子數1至6之烷基巯基為佳， 可列舉如甲基巯基、乙基髄基、丙基巯基、丁基毓基、戊 基親基、己基酼基。又，此等取代基係包括其異構物。 8 321109 200946537 可列係以碳原子數6至14之芳紐為佳， =舉：本基疏基、甲笨基疏基、二甲菜基縣、萘基魏 基等。又，此等取代基係包括其異構物。 佳 ==錄以瑗原子數1至12之烧基樹為 了歹J舉如甲基補基、乙基賴基 佳 前述芳基績醒基係以碳原子數6至18之土 為 Ο 可列舉如苯基石黃醯基、甲苯基績醯基n 土為 从當χ之:炭原子上之數個氫原子被燒基^基 方烧基、以基、芳氧基、二絲絲 ^ ，絲《、芳基疏基、燒 取代時，鄰接之基可互相結合而形成環。醯基所 例如，可列舉如下述情形：去 個氫原子分別獨立地經前述取代：：原子上鄰接之2 彼此可與該等所結合之碳原子 、，鄰接之取代基 或是8、9或10員二環式之飽和5、6或？員單環式 形而含有取代基所包含之選自〇5 #環（其亦可依據情 前述由鄰接之基互相結合及^雜原子）。 環戊烯環、環己稀環、環庚烯/成環時之環，可列舉如 環、苯并》料、萘環、四氫料 此等中，較佳之例為：x為^ N'甲絲咬環等。 基、碳原子數6至18之芳基者，"ζ ★原子數〗至6之院 或數個氬原子可獨立地被選自㈣f X之碳原子上之1個 硬原子、、二甲基胺基、二乙：：子、氯原子、漠原子、 基、丙酿基、丁酿基、苯甲―私胺基、二丙基胺基、乙酿 土、鼠笨甲醯基、萘甲醯基、 321109 200946537 甲基酼基、乙基巯基、丙基毓基、曱基磺醯基、乙基磺醯 基、丙基磺醯基之基所取代。 .環狀烷基胺基碳烯配位子係如下述通式（2)所示：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):

式中，η表示1至3之整數； R1表示烷基、環烷基、聚環烷基或芳基； R2、R3、R4及R5分別可為相同或不同，表示氫原子、鹵原子、 烷基、烯基、芳基、芳烷基、烷氧基、芳氧基、硝基、氰 基、或經相同或不同之烷基取代而成之二烷基胺基，或是 R2、R3、R4及R5之鄰接之基彼此可與該等所結合之碳原子一 起形成環；當R1至R5表示含有碳原子之基時，其碳原子上 之1個或數個氫原子可被鹵原子、烷基、環烷基、烯基、 芳基、芳烷基、烷氧基或芳氧基所取代。 此處，R1表示烷基、環烷基、聚環烷基或芳基，該烷 基、環烷基、芳基係與前述X之碳原子上之取代基所定義 者為相同意義。 前述聚環烷基係以碳原子數6至10之聚環烷基為佳， 可列舉如雙環-[2. 1. 1]-己基、雙環-[2. 2. 1]-庚基、雙環-[2. 2. 2]-辛基、雙環-[3. 3. 0]-辛基、雙環-[4. 3. 0]-壬基、 雙環-[4.4. 0]-辛基、金剛烷基等。 R2、R3、R4及R5表示鹵原子、烷基、烯基、芳基、芳烷 200946537 基純基、芳氧基、硝基、氮基、或經相同或不 基取代而成之二垸基絲，此等基係與前述X之碳^ •之取代基所定義者為相同意義。 、 . 此外，R2、R3nR5之鄰接之基彼此可與該等所处人 之碳原子—起形成環。在通式⑵中，由以以/及^ 與該等所結合之碳原子一起形成環時之環，可列舉如 稀環、環己烯環、環庚烯環、環戊烧環、環己燒環、j ❹烧環、苯，、萘環等碳原子數5至14之碳環。 讀 又，當R1至R5表示含有碳原子之基時，其碳原子 1個，數個氫原子可被自原子、縣、環絲、烯基、芳 基、方烷基、烷氧基或芳氧基所取代，此等基係與前述X 之碳原子上之取代基所定義者為相同意義。 此等中’較佳之例為：R1為選自碳原子數1至20之烷 基、碳原子數3 JL 7之環烧基、碳原子數6至10之聚環燒 基或碳原子數6至20之芳基，R2、R3、^及R5猶立地為氫 ❹原子、㈣子、碳原子數丨至2Q種基、碳原子數2至 20之烯基、碳原子數6至2〇之芳基、碳原子數7至2〇之 芳烧基、碳原子數1至10之烧氧基、碳原子數6至14之 方氧基、硝基、氰基、或經相同或不同之2個碳原子數1 至6之院基取代而成之二烧基胺基。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尤以第三丁基、2, 6-二異丙基苯基、2, 4, 6-三甲基 苯基或金剛烧基為佳。另夕卜，r2、r3、r4 & r5尤以氮原子或 石反原子數1至6之烷基為佳，當R2、R3、^及R5之鄰接夂 基彼此與該等所結合之碳原子一起形成環時，以形成環已 11 321109 200946537 烷環者為佳，且以形成環己烷環、卜甲基-4-丙基己烷環為 佳。 本發明之含氮雜環碳烯配位子（L)之具體例可列舉如 式（3)至（18)所示之化合物。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 本發明之通式（1)所示之取代乙炔金-環狀烷基胺基碳 稀錯合物，例如可如反應步驟式[1 ]所示，藉由使取代乙块 • 金膦錯合物與環狀烷基胺基碳烯配位子（L)進行反應而獲 - 得： [反應步驟式（1)]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_ L

X--一ΑυΡ -► X-===一AuLX--一ΑυΡ -► X-===一uL

-P (3) (1) 0 式中，X及L係與前述同義，P表示單牙膦配位子。 前述單牙膦配位子可列舉如雙（五氟苯基）苯基膦、（4-溴苯基）二苯基膦、二烯丙基苯基膦、二環己基苯基膦、二 乙基苯基膦、4-(二曱基胺基）苯基二苯基膦、二曱基苯基 膦、二苯基（2-甲氧基苯基）膦、二苯基（五氟苯基）膦、二 苯基丙基膦、二苯基-2-°比啶基膦、二苯基（對甲苯基）膦、 二苯基乙烯基膦、乙基二苯基膦、異丙基二苯基膦、曱基 二苯基膦、三苯曱基膦、三丁基膦、三-第三丁基膦、三環 Ο 己基膦、三環戊基膦、三乙基膦、三-2-呋喃基膦、三異丁 基膦、三異丙基膦、三丙基膦、三曱基膦、三辛基膦、三 苯基膦、三（4-氯苯基）膦、三（3-氯苯基）膦、三（2, 6-二曱 氧基苯基）膦、三（4-氟苯基）膦、三（3-氟苯基）膦、三（4-甲氧基苯基）膦、三（3-曱氧基苯基）膦、三（2-曱氧基苯基） 膦、三（4-三氟曱基苯基）膦、三（五氟苯基）膦、三（2, 4, 6-三曱氧基苯基）膦、三（2, 4, 6-三曱基苯基）膦、三間甲苯基 膦、三鄰甲苯基膦、三對甲苯基膦、苯甲基二苯基膦、雙 (2-曱氧基苯基）苯基膦、二苯基環己基膦、2-(二-第三丁 13 321109 200946537 基膦基）聯苯、2-(二環己基膦基）聯苯、新盖基二苯基膦 (neomenthyl diphenyl phosphine)、對甲苯基二苯基膦、 二稀丙基麟、二（2，4，4_二曱基戊基）麟、三（1_蔡基）鱗、 三（羥基曱基）膦、三（羥基丙基）膦等。此等可直接使用市 售品。 前述取代乙炔金膦錯合物’例如可如反應步驟式[2] 所示’藉由在鹼之存在下使金鹵化膦錯合物與取代乙炔進 行反應而獲得： [反應步驟式（2)] 鹼-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" + Υ一AuP -► X- ~·ί· —AuP (4) (5) (6) 式中’ X及P係與前述同義’ Y表示鹵原子（例如參照journa 1 of Chemical Society, Dalton Trans.，411(1986))。 又，前述金i化膦錯合物可依據周知之方法而合成（例 如參照實驗化學講座第4版，丸善社，第455頁，18卷（1991 年））。 前述取代乙炔可直接使用市售品，亦可依據周知之方 法由取代芳香族漠化物來合成（例如參照journal 〇fX-:·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, 1985，50 卷，1763.)。 前述環狀烷基胺基碳烯配位子係藉由以周知之方法使 對應之環狀亞胺鐵鹽（cyclic iminium salt)與驗（例如二 異丙基醯胺鋰等）進行反應而獲得（例如參照國際公開第 2006/138166 號手冊）。 在本發明之取代乙炔金-環狀烷基胺基碳烯錯合物之 14 321109 200946537 合成中，相對於取代乙块金膦錯合物j莫耳，環狀燒基胺 基碳細配位子之使用量細丨至1G料為佳，尤 莫耳為更佳。 4 在本發明之取代乙块金一環狀垸基胺基碳歸錯合 Γ=Γ溶媒，只要是不會阻礙反應者即無特別限 制，例如使用：四心夫喃、四4吨_二 ❹ ❹ 乙基醚、二異丙基醚、二丁基驗等驗類；戍燒、己燒 烷、辛烷等脂肪族烴類；苯、甲苯、_ HP —〜 τ本一甲本等方香族烴類； 一 I甲烧、—乳乙炫、二氯丙燒㈣化脂肪族烴類 等齒化芳香族烴類。又，此等溶媒可使用！種或混合2 2種以上。 π用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

前述溶媒之使用量係依據反應液之均-性和授拌性而 適當調節，相對於取代乙炔金膦錯合物1莫耳，以丨至3〇1 為佳，尤以5至20L為更佳。 J 本發明之取代乙块金-環狀烧基胺基碳稀錯合物之合 成’可藉㈣如將取紅块金膦錯合物、躲縣胺基碳 烯配位子及溶媒混合，一邊賴一邊使其反應等方法而進 行。此時之反應溫度較佳為〇至12(rc，更佳為2〇至1〇〇 °C ’反應壓力則並無特別限制。 本發明之取代㈣金—環㈣基胺基料錯合物，係在 反應結束後藉由中和、萃取、過濾、濃縮、蒸餾、再結晶、 昇華、層析等周知之方法而單離、生成。 本發明之取代乙块金—環狀跪基胺基碳缚錯合物，可列 舉如式（19)至（49)所示之化合物。 15 321109 200946537The 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(31) (32) (33) (34) ❹

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

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

依據本發明之取代乙炔金-環狀烷基胺基碳烯錯合 物，可實現在氯仿中、在溫度77K(kelvin，亦即絕對溫度）、 © 紫外線照射下，於440nm以下之深藍色區域（410至440mn) 具有電激發光元件所造成之發光波峰極大值，且發光色就 CIE(國際照明委員會）表色系而言其y座標未達0. 18的元 件，顯示該錯合物可適用於有機電激發光元件。 其次，針對本發明之有機電激發光元件，說明其實施 型態。 本發明之有機電激發光元件，係藉由使有機化合物薄 層中之至少一層含有該取代乙炔金-環狀烷基胺基碳烯錯 合物而成者，較佳為在一對之電極間具有單層或多層之有 17 321109 200946537 機化合物層的有機電激發光元件。 合物驗—雜縣胺基麵錯合物對於有機化 二ΓΓ雖無特別限制，但相對於有機化合物層 〇〇1^ 其他電激發光元件中，亦可組合使用發光材料、 電^雜材料、電洞注人材料或電子注人材料。更進一步， /入層、發光層、電子注入層可分別藉由二層以上之 曰構造而形成。此時’當形成電洞 “電洞之層稱為電.躲人層，====從電極 ^電洞到發光層之層稱為電洞輸送層。同樣地，當形 厚電子注入層時，將從電極注入電子之層稱為電子注入 ^將從電子注人層接受電子並輪送電子到發光層之層稱 子輸送層。此等各層係依據材料之能量位準、雜性、 田、有機化合物層較屬電極之密著性等各要因而選擇使 用。 可與該取代乙炔金-環狀院基胺基碳烯錯合物一起使 用於有機化合物層之發光材料或主體材料，係可列舉如各 種’唾衍生物、縮合多環芳香族（例如蒽、萘、菲、祐、稠 四笨、稠五苯、蔻（coronene)、苯并菲（chrysene)、螢光 素（fluorescein)、茈（perylene)、紅螢烯（rubrene)及該 等之街生物）、献茈（phthaloperylene)、萘駄茈、紫環_ (Perinone)、酞紫環酮、萘酞紫環酮、二苯基丁二烯、四 笨基丁二烯、香豆素、噚二唑、醛連氮（aldazine)、雙苯 18 321109 200946537 并噚唑啉、二苯乙烯基、吡畊、環戊二烯、喹啉金屬錯合 物、二苯基乙細、乙稀基恩、二胺基味唾、η比喃、π塞喃 ' · ("thiopyran)、聚次甲基（polymethine)、部花青素 ' (merocyanine)、咪唾螯合化類曙辛化合物（imidazole chelated oxinoid compound)、喹吖咬酮（quinacridone)、 紅螢烯、二苯乙烯系衍生物、芳香族矽化合物、芳香族鍺 化合物等。 在本發明之有機電激發光元件中可使用之周知之電洞 ❹注入材料中，有效果之電洞注入材料為芳香族三級胺衍生 物、欧菁衍生物或聯伸三苯（triphenylene)衍生物。芳香 族三級胺衍生物之具體態樣為三苯基胺、三甲苯基胺、甲 苯基二苯基胺、Ν，Ν’ -二苯基-N，Ν’ -(3-甲基苯基）-1，1’ -聯苯-4, 4’-二胺（以下記載為TPD)、11^1，，犷-(4-甲基苯 基）-1，Γ-苯基-4, 4’-二胺、1^，1'^’，]^-(4-甲基苯基） -1，Γ-聯苯-4,4’_二胺、Ν，Ν’-二苯基-Ν，Ν’二萘基-1，Γ-❹聯苯-4, 4’ -二胺、Ν，Ν’ -(甲基苯基）-Ν，Ν’ -(4-正丁基苯基） -菲-9,10-二胺、1,1-雙[4-(二-4-甲苯基胺基）苯基]環己 烷等、或是具有此等芳香族三級胺骨架之寡聚物或聚合 物，但不限定於此等。 酞菁（phthalocyanine，亦即Pc)衍生物之具體態樣為 H2Pc、CuPc、CoPc、NiPc、ZnPc、PdPc、FePc、MnPc、ClAlPc、 CIGaPc、Cl InPc、CISnPc、ChSiPc、（HO)AlPc、（HO)GaPc、 VOPc、TiOPc、MoOPc、GaPc-O-GaPc 等酞菁衍生物及萘酞 菁衍生物，但不限定於此等。 19 321109 200946537 聯伸三苯衍生物之具體態樣係表示如下式。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) 式中，Z表示1個或複數個之烷基、環烷基、芳基、 芳烧基或雜環基，Z之碳原子上之1個或複數個氫原子可 被齒原子、燒基、環燒基、稀基、芳基、芳烧基、燒氧基、 ❹ 芳氧基、經相同或不同之烷基取代而成之二烷基胺基、院 基幾基、芳基羰基、有機矽烷基所取代。有機矽烷基以外 之取代基係與前述X之碳原子上之可取代之基所定義者為 相同意義。 前述有機矽烷基可列舉如三曱基矽烷基、三乙基石夕烧 基、第三丁基二曱基矽烷基、三異丙基矽烷基、第三丁基 二笨基石夕燒基等。 ,〇 在本發明之有機電激發光元件中，更有效之周知之電 子注入材料為金屬錯合物化合物或含氮五員環衍生物。金 屬錯5物化合物之具體態樣可列舉如經基喧嘛鋰、雙（8一 鉍基喹啉）鋅、雙（8-羥基喹啉）銅、雙（8-羥基喹啉）錳、三 (8-羥基喹啉）鋁（以下，記載為AlQ3)、三（2_曱基_8_羥基 喹啉）鋁、三（8_羥基喹啉）鎵、雙（10-羥基苯并[h]喹啉） 鈹、雙（10-羥基苯并[h]喹啉）鋅、雙（2_曱基_8_喹啉）氯 鎵、雙（2-甲基—8-喹啉）（鄰曱酚）鎵、雙（2_曱基_8_喹啉） 321109 20 200946537 .(1_蔡紛）銘、雙（2-曱基-8-喹啉）（2-萘酚）鎵等，但不限定 於此等。 此外’含氮五員環衍生物係以噚唑、噻峻、噚二唑、 ' 噻一唑或二唑衍生物為佳。具體而言，可列舉如2, 5-雙（1- 苯基）-1，3’4-暇唾、二甲基p〇p〇p(此處，p〇p〇p表示Γ,4一 雙（5-苯基曙哇-2-基）笨）、2, 5—雙（1_笨基）]，3, 4_射、 2,5-雙（1-笨基）-1，3,4一噚二唑、2_(4，_第三丁基苯基）_5_ ❹（4 _聯苯）-1，3, 4-噚二唑、2, 5-雙（卜苯基）―丨，3, 4_噚二 唑、1,4-雙[2-(5-苯基噚二唑基）]苯、丨，4—雙[2_(5_苯基 曙二唑基）-4-第三丁基苯]、2—(4，_第三丁基苯基）_5_ (4 聯苯）-1，3, 4-噻二唑、2, 5-雙（1-萘基）-1,3,4-噻二 唑、1,4-雙[2-(5-苯基噻二唑基）]苯、2_(4, _第三丁基苯 基）-5-(4’ 聯笨）-1 3, 4_***、3_(4_聯苯基）_4_苯基一5_ 第三丁基苯基-1，2,4-***、2,5-雙（1-萘基）-1，3,4_三 唑、1,4-雙[2-(5-苯基***基）]苯等，但不限定於此等。 ❹ 本發明之有機電激發光元件中，為了提升電荷注入 性，亦可在發光層與電極之間設置無機化合物層。 該無機化合物層可列舉如UF、U2〇、Ra〇、SrO、、 Srh等鹼金屬或鹼土金屬之氟化物、氧化物等。 本發明之有機電激發光元件之陽極所使用之導電性材 料宜為具有大於4eV之功函數者，可使用碳原子、鋁、釩、 鐵、録、鎳、鎢、銀、金、鉑、鈀及該等之合金、IT〇(在 氧化銦中添加5至1〇%氧化錫而成之物質）基板、ΝΕ^基 板所使用之氧化錫、氧化銦等氧化金屬，更可使用聚嗟吩 321109 21 200946537 或聚。比咯等有機導電性樹脂。 陰極所使用之導電性物質宜為具有小於4eV之功函數 者，可使用鎮、#5、錫、錯、欽、妃、裡、釕、猛、銘等 該等之合金。此處，所謂合金係指鎂/銀、鎮/銦、經/铭等。 合金之比率係依據蒸鍍源之溫度、環境氣體、真空度等而 控制，並無特別限定。 陽極及陰極，若有需要，亦可藉由二層以上之積層構 造形成。 本發明之有機電激發光元件之較理想例，係其至少一 面在元件之發光波長區域中為透明。又，基板亦以透明者 為佳。 透明電極係藉由使用前述導電性材料，並以蒸鍍或濺 鍍等方法設定成可確保預定之透光性而獲得。 發光面之電極係以使光透過率成為10 %以上為佳。 基板只要是具有機械強度、熱強度且具有透明性者即 可，並無特別限制，可列舉如玻璃基板或透明性樹脂薄膜。 透明性樹脂薄膜可列舉如聚乙烯、乙烯-乙酸乙烯酯共 聚物、乙烯-乙烯醇共聚物、聚丙烯、聚苯乙烯、聚曱基丙 烯酸曱酯、聚氯化乙烯、聚乙烯醇、聚乙烯基縮丁醛 (polyvinyl butyral)、尼龍、聚醚醚酮、聚礙、聚醚石風、 四氟乙烯-全氟烷基乙烯基醚共聚物、聚氟化乙烯、四氟乙 浠-乙烯共聚物、四氟乙稀-六氟丙烯共聚物、聚氯三氟乙 烯、聚偏二氟乙烯、聚酯、聚碳酸酯、聚胺酯、聚醯亞胺、 聚醚醯亞胺、聚丙烯等。 22 321109 200946537 本發明之有機電激發光元件中，為了提升對於溫度、 濕度、環境氣體等之安定性，亦可在元件之表面設置保護 層，或亦可藉由矽油、樹脂等保護元件整體。 • 此外，有機電激發光元件之各層之形成，可適用真空 蒸鍍、濺鍍、電漿、離子鍍覆等乾式成膜法或旋塗法、浸 塗法、流塗法等濕式成膜法之任一種方法。膜厚雖無特別 限定，但通常之膜厚為5nm至10 // m之範圍，尤以10 mn 至0.2/zm之範圍為佳。 當使用濕式成膜法時，可在各層上，將前述通式（1) 所示之化合物溶解或分散於乙醇、氯仿、四氫吱喃、二卩萼 烷等溶媒中而調製薄膜。 乾式成膜法係以真空蒸鍍為佳，可藉由使用真空蒸鍍 裝置，使真空度成為2xlO_3Pa以下，使基板溫度為室溫， 將已置入蒸鍍槽之本發明之式（1)所示之取代乙炔金-環狀 烷基胺基碳烯錯合物予以加熱，使該材料蒸發而調製薄 Q 膜。此時，為了控制蒸鑛源之溫度，以接觸於蒸鑛槽之熱 電偶（thermocoup 1 e)或非接觸之紅外線溫度計等為適用。 此外，為了控制蒸鍍量，以蒸鍍膜厚計為適用。 蒸鍍膜厚計之較佳形式之例為使用面對於蒸鍍源而設 置之水晶振動子（crystal unit)，從該振動子之振盪頻率 之變化來計測附著於前述水晶振動子表面之蒸鍍膜之重 量’並即時從該計測重量求出膜厚。 前述通式（1)所示之取代乙炔金-環狀烷基胺基碳烯錯 合物與發光材料或其他主體材料之共蒸鍍，可藉由分別使 23 321109. 200946537 用各自^㈣，且分職立地控制各自之溫度而進行。 *處’為了提升成膜性、防止膜 =可使用例如聚笨乙稀、聚碳酸醋、聚丙』機 掄㈣’醯胺聚胺酯、聚砜、聚甲基丙烯酸甲酯、聚丙(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

:酉旨、纖維素等絕緣性樹脂及該等之共聚物·，聚I =基料、聚錢f光導錄龍；㈣吩、聚鱗等 =電)±樹I等樹脂；或抗氧化劑、紫外線 等添加劑。 、本發明之有機電激發光元件可利用於例如壁掛式電視 或手機電話之平面顯示器等平面發光體、影印機、印表機、 液B曰顯不裔之背光、或計量軸等之光源、顯示板、 燈等。 (實施例） 以下列舉實施例而具體說明本發明，但本發明之範圍 不限定於此等。 只轭例1 ([Ν一（2，6 -二異丙基苯基）一2, 2, 4, 4-四曱基亞 〇比咯啶基―4’ 氟苯基乙炔金（23)]之合成） 在氬氣環境下，於30mL之休雷克瓶（Schlenk flask) 中添加1~(2, 6-二異丙基苯基）__2, 2, 4, 4-四甲基-3, 4-二氫 2H二氟曱磺酸吡咯鏽鹽（261mg，〇. 6則^)、四氫呋喃 (6mL)，製成懸濁溶液。於-78°C下添加二異丙基醯胺鋰 (2. 〇M溶液，300//L，0. 6mmol)，攪拌5分鐘後，於室溫 攪拌45分鐘，然後減壓餾去四氫呋喃與副產物二異丙基 胺。添加四氫呋喃（8mL)並於70t：攪拌5分鐘後，過濾反 321109 24 200946537 . 應混合物，在濾液中添加4_氟苯基乙炔基（三苯基膦）金 (116mg ’ 0. 2mmol)後，於室溫攪拌2小時。減壓餾去四氫 °夫读後，添加二氯甲烷，進行水洗而使pH成為7。以硫酸 ‘ 納乾燥後’再以蒸發器將溶媒減壓餾去。將反應粗生成物 藉由使用石夕膠之管柱層析（己烷/Ac〇Et==6/1)進行精製，而 獲得白色固體之目的物62. 4mg(收率51%)。 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) E I -MS (M/Z) : 6 0 1 (M + ) , c I (m/z) : 6 〇 2 (MH + ) 發光分析（CHC13, 77K, Ex250nm)A(nm):412(max)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)

熱分析：熔點212°C 元素分析觀測值 C : 56. 0，Η : 5. 9，N : 2. 3 理論值 C : 55. 9，Η : 5. 9，Ν : 2. 3 實施例2 (有機電激發光元件之製作） ❹ 如下述，製作第2圖所示之電激發光元件。 使用EHC公司製之附有銦錫氧化物（以下簡稱為ΙΤ0) 被膜之玻璃作為透明電極基板，並使用ULVAC機工公司製 之真空蒸鍍裝置，在該基板上以2xlO-3Pa以下之真空度依 序真空蒸鍍下述者： 膜厚40nm之電洞輸送層3，其係由2-(4,-三甲基矽烷基苯 基）聯三伸苯所構成； 膜厚30nm之發光層4，其係在作為主體之2-甲基-1，4-雙 (三苯基鍺烷基）苯（以下簡稱為Me-p-BTPGB)中含有作為客 25 321109 200946537 體之磷光錯合物（N-(2’，6’_二異丙基笨基）-，2,2,4,4-四 甲基亞吡咯啶基-4’ 氟苯基乙炔金（以下簡稱為磷光錯合 物（23))5. 0重量％者； ’ 30nm之電洞阻擋層5，其係由3-(4-聯苯基）-4-苯基-5-第 . 三丁基苯基-1，2, 4-***（昇華精製品，以下簡稱為TAZ)所 構成； 0. 5nm之電子輸送層6，其係由氟化链（以下簡稱為LiF)所 構成， lOOnm之電極7，其係由鋁（以下簡稱為A1)所構成。 藉此而製成電激發光元件。 又，真空蒸鍍係藉由將原料饋入面對基板設置之坩堝 中，並連同坩堝一起加熱原料而進行。 比較例（有機電激發光元件之製作） 就比較例而言，除了使發光層4中不含有鱗光錯合物 (23)以外，其餘與實施例2進行同樣操作，而製成有機電 激發光元件。 〇 將實施例2之電激發光元件之IT0電極2作為正極、 將A1電極7作為負極而進行通電並提升電極間電壓時，元 件從+ 12V附近開始有可明顯以肉眼辨識之藍色發光，在 + 24V中以4. 6cd/m2發光。以下述式求出關於此元件之發 光的電流效率。 電流效率=(每單位面積之發光亮度）/(每單位面積之電流 密度） 如此所求得之電流效率在+ 21V中為0. 014cd/A。 26 321109 200946537 使用日本分光公司製的螢光光度計測定此元件之發光 色。依據在電極間電壓+ 19V中所得之光譜，並依據jis * Z8701所求出之色度座標之值為x=0.169，y=0.139。 ‘ 將實施例1所合成之碟光錯合物（2 3 )、實施例2及比 較例之有機電激發光元件以磷光螢光光度計測定發光光譜 (氯仿中，溫度77K(絕對溫度），紫外線照射下）。 如第1圖所示，實施例2之有機電激發光元件係在 440nm以下之深藍色區域（410至440nm)中具有發光波峰極 φ 大值。另一方面’在發光層中未含有磷光錯合物（23)之比 較例之有機電激發光元件則在深藍色區域外（紫外線區域） 之380mn附近顯示發光波峰極大值。又，關於比較例之電 激發光元件，雖然將ΙΤ0電極2作為正極、將M電極7作 為負極而進行通電並提升電極間電壓，但僅在％—之紫 外線區域觀測到微弱之發光。 (產業上之可利用性） ❹ 雜本發明’可實現-種元件，其_光性有機電激 發光兀件’且為在為了完成全彩顯示器而為重要之權⑽ 以下之深藍色區域⑷Q i 44〇ηιη)中具有電激發光所造成 之發光波峰極大值，並且發光色钟、 / 尤CIE(國際照明委員會） 表色糸而言其y座標未達〇. 180的元件。 【圖式簡單說明】 第1圖係實施例1之錯合物之罐光光譜、實施例2及 比較例之有機電激發光元件之EL先# 第2圖係實施例2之有機電敎發光元件之構造。 321109 27 200946537 【主要元件符號說明】 1 玻璃基板 2 ΙΤ0透明電極 3 電洞輸送層 4 發光層 5 電洞阻擋層 6 電子輸送層 7 鋁電極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• 28 321109

Claims (1)

200946537 ^ 七、申請專利範圍： 1· 一種取代乙炔金-環狀烧基胺基碳烯錯合物，其係如通 ‘式（1)所示： X —AuL (1) 式中， L表示環狀烷基胺基碳烯配位子； X表示烧基、環院基、芳基、芳烧基或雜環基；此 魯 處’ X之碳原子上之1個或數個氫原子可獨立地被鹵原 子'烷基、環烷基、烯基、芳基、芳烷基、烷氧基、芳 氧基、經相同或不同之烧基取代而成之二燒基胺基、烧 基羰基、芳基羰基、烷基巯基、芳基毓基、烷基磺醯基 或♦基確醯基所取代；當X之碳原子上之數個氫原子係 獨立地被烷基、烯基、芳基、芳烷基、烷氧基、芳氧基、 經相同或不同之烷基取代而成之二烷基胺基、烧基裁 基、芳基羰基、烷基酼基、芳基魏基、烷基磺醯基或芳 ® 基績醯基所取代時，鄰接之基可互相結合而形成環。 2·如申請專利範圍第j項之取代乙炔金_環狀烷基胺基碳 婦錯合物，其中 基碳晞配位子： R3 前述L為通式（2)所示之環狀烷基胺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) 式中，η表示1至3之整數； 321109 29 200946537 R1表示烷基、環烷基、聚環烷基或芳基； R2、R3、R4及R5分別可為相同或不同，表示氫原子、 鹵原子、烷基、烯基、芳基、芳烷基、烷氧基、芳氧基、 硝基、氰基、或經相同或不同之2個烷基取代而成之二 烷基胺基，或是R2、R3、R4及R5之鄰接之基彼此可與該 等所結合之碳原子一起形成環；當R1至R5表示含有碳 原子之基時，其碳原子上之1個或數個氫原子可被鹵原 子、烷基、環烷基、烯基、芳基、芳烷基、烷氧基或芳 氧基所取代。 3. 如申請專利範圍第2項之取代乙炔金-環狀烷基胺基碳 稀錯合物，其中’ R1為碳原子數1至20之烷基、碳原子數3至7之 環烷基、碳原子數6至i〇之聚環烷基、或碳原子數6 至20之芳基； R2、R3、R4及R5獨立地為氫原子、鹵原子、碳原子 數1至20之烧基、礙原子數2至20之烯基、碳原子數 6至20之芳基、碳原子數7至20之芳烷基、碳原子數 1至10之烷氧基、碳原子數6至14之芳氧基、硝基、 氰基、或經相同或不同之2個烷基取代而成之二烷基胺 基。 4. 如申請專利範圍第3項之取代乙炔金—環狀烷基胺基碳 烯錯合物’其中，前述聚環烷基係選自雙環_[2.1.1]-己基、雙環-[2· 2. 1]-庚基、雙環— [2. 2. 2]-辛基、雙環 -[3. 3. 0]-辛基、雙環-[4. 3· 0]-壬基、雙環-[4. 4. 0]- 30 321109 200946537 ~ 辛基及金剛烷基所成群組者。 5. —種申請專利範圍第1項之取代乙炔金-環狀烷基胺基 * 碳烯錯合物的製造方法，其係藉由使取代乙炔金膦錯合 w 物與環狀烷基胺基碳烯配位孑進行反應而實施。 6. 如申請專利範圍第5項之製造方法，其中’環狀炫基胺 基碳烯配位子係藉由使環狀爻胺鐵鹽與驗進行反應而 獲得者。 ^ 7.如申請專利範圍第5項或第6頊之製造方法，其中，反 應係相對於取代乙炔金膦錯合物1莫耳，使用環狀烷基 胺基碳烯配位子1至5莫耳者。 8. 如申請專利範圍第5項至第7項中任一項之製造方法， 其中，反應係藉由將取代乙炔金“錯合物與環狀烷基胺 基碳烯配位子混合，在溶媒之存在下’以〇至12(TC之 溫度攪拌而進行者。 9. 一種有機電激發光元件，其特徵係在一對電極間形成發 © 光層或包含發光層之複數層之有機化合物薄層，該有機 化合物薄層含有1種或2種以上之申請專利範圍第1 項之通式（1)所示之取代乙炔金-環狀烷基胺基碳烯錯 合物。 10. 如申請專利範圍第9項之有機電激發光元件，其在一對 電極間形成發光層或包含發光層之複數層之有機化合 物薄層，於440nm以下之深藍色區域中具有磷光電激發 光之發光波峰極大值，並且發光色就CIE(國際照明委 員會）表色系而言其y座標未達0. 18。 321109 31(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