TW201202390A - Membrane containing silver complex - Google Patents

Membrane containing silver complex Download PDF

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TW201202390A
TW201202390A TW100119089A TW100119089A TW201202390A TW 201202390 A TW201202390 A TW 201202390A TW 100119089 A TW100119089 A TW 100119089A TW 100119089 A TW100119089 A TW 100119089A TW 201202390 A TW201202390 A TW 201202390A
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atom
atoms
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heterocyclic compound
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TW100119089A
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Norifumi Kobayashi
Hideyuki Higashimura
Takashi Kaikoh
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Sumitomo Chemical Co
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Abstract

Provided is a membrane using a silver complex which is inexpensive compared to a platinum group metal complex and which exhibits excellent durability in the presence of oxygen when used as a light-emitting material. Specifically provided is a membrane containing a silver complex represented by the following compositional formula (1): (Ag+)(L1)a(L2)b(L3)c(X1)d. (L1 represents a molecule having a total of 3 to 6 of the following atoms and/or ions: at least one phosphorus atom and at least one nitrogen atom, oxygen atom, sulfur atom, arsenic atom, oxygen anion and/or sulfur anion. L2 represents a molecule having a total of two atoms and/or ions selected from among the aforementioned atoms and ions. L3 represents a molecule having one of the aforementioned atoms or ions. X1 represents an anion, a represents a number greater than 0.5, and b, c, and d each independently represent a number greater than or equal to 0.)

Description

201202390 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種含銀錯合物之膜。 【先前技術】 作為用於有機電致發光元件中之發光材料，以銥錯合物 為代表之使用鉑族金屬之磷光發光錯合物被視為有前途。 然而’銥於鉑族金屬中亦稀少，非常昂貴。因此，正在對 使用在成本方面有利的廉價金屬之錯合物進行各種研究 (非專利文獻1)。 [先前技術文獻] [非專利文獻] [非專利文獻 1] Coord. Chem. Rev. 250, 2093-2126 (2006) 【發明内容】 [發明所欲解決之問題] 作為用於有機電致發光元件中之發光材料，以膜之形狀 穩定地發光較為重要。 然而’使用公知之廉價金屬之錯合物的膜作為發光材料 於氧存在下之耐久性並不充分。 因此’本發明之目的在於提供—種使用與鈾族金屬之錯 合物相比較為廉價、且料發光㈣於氧存在下之耐久性 優異之錯合物的膜。 [解決問題之技術手段] 本發明第一提供 合物之膜， 一種含有下^切)所表 示之銀錯 156591.doc 201202390 (Ag )(L )a(L2)b(L3)c(x1)d ⑴ (組成式（1)中，L1為具有選自磷原子、氮原子、氧原子、 硫原子、砂原子、氧陰離子及硫陰離子中之原子或離子作 為可配位於Ag+之原子或離子的分子，Li所具有之可配位 於Ag+之原子及離子的總數為3個以上且6個以下，並且[丨 所具有之可配位於Ag+之原子中〖個以上為磷原子；L2為具 有選自碟原子、氮原子、氧原子 '硫原子、_原子、氧陰 離子及硫陰離子中之原子或離子作為可配位於Ag+之原: 或離子的分子，且L2所具有之可配位於Ag+之原子及離子 的總數為2個；L3為具有i個選自磷原子、氮原子、氧原 子I原子A申原子、氧陰離子及硫陰離子中之原子戋離 子作為可配位於Ag+之原子或離子的分子；χ丨為陰離子；a 為大於〇·5之數，b、c及d分別獨立為〇以上之數）。 本發明第二提供一種含有上述膜之發光元件。 本發明第三提供-種下述組成式⑺所表示之銀錯合 物。 (Ag )(L4)e(L5)f(L6)g(X2)h (3) (組成式（3)中，L4為 具有4個以上且6個以下之可配位於Ag+之磷原子的分 子，或者 具有1個以上之磷原子以及選自氮原子、氧原子、硫原 子、砷原子、氧陰離子及硫陰離子中之“固以上作為可配 位於Ag+之原子、或原子及離子 於Ag之原子及離子的總數為3個 ’並且L4所具有之可配位 以上且6個以下的分子； 156591.doc 201202390 L5為具有選自磷原子、氮原子 '氧原子、硫原子、砷原 子、氧陰離子及硫陰離子令之原子或離子作為可配位於201202390 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a film containing a silver complex. [Prior Art] As a luminescent material used in an organic electroluminescence device, a phosphorescent luminescent complex using a platinum group metal typified by a ruthenium complex is considered to be promising. However, it is also rare in the platinum group metals and is very expensive. Therefore, various studies have been conducted on the use of a complex of inexpensive metals which is advantageous in terms of cost (Non-Patent Document 1). [Prior Art Document] [Non-Patent Document 1] [Non-Patent Document 1] Coord. Chem. Rev. 250, 2093-2126 (2006) [Disclosure] [Problems to be Solved by the Invention] As an organic electroluminescence device Among the luminescent materials, it is important to stably emit light in the shape of a film. However, the use of a film of a complex of a known inexpensive metal as a light-emitting material is not sufficient in the presence of oxygen. Accordingly, it is an object of the present invention to provide a film which is less expensive than a uranium metal complex and which is excellent in durability when exposed to light (4) in the presence of oxygen. [Technical means for solving the problem] The film of the first providing compound of the present invention, one containing the silver 156591.doc 201202390 (Ag ) (L ) a (L2) b (L3) c (x1) d (1) (In the composition formula (1), L1 is an atom or ion having a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, a sand atom, an oxyanion, and a sulfur anion as an atom or ion which can be coordinated to Ag+ a molecule, Li has a total number of atoms and ions which can be coordinated to Ag+ of 3 or more and 6 or less, and [wherein the atom which can be assigned to Ag+ is more than one of phosphorus atoms; L2 is selected from the group consisting of An atom or ion in a dish atom, a nitrogen atom, an oxygen atom, a sulfur atom, an atom, an oxyanion, and a sulfur anion, as a molecule that can be coordinated to an Ag+: or an ion, and the L2 has an atom that can be coordinated to Ag+ and The total number of ions is two; L3 is an atom having at least one atom selected from a phosphorus atom, a nitrogen atom, an oxygen atom I atom, an oxyanion, and a sulfur anion as a molecule or ion that can be coordinated to Ag+; χ丨 is an anion; a is greater than 〇·5, b, c, and d Independent billion less than the number). A second aspect of the invention provides a light-emitting element comprising the above film. The third invention of the present invention provides a silver complex represented by the following composition formula (7). (Ag )(L4)e(L5)f(L6)g(X2)h (3) (In the composition formula (3), L4 is a molecule having 4 or more and 6 or less phosphorus atoms which can be coordinated to Ag+ Or one or more phosphorus atoms and one selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxyanion, and a sulfur anion, "a molecule that can be coordinated to an atom of Ag+, or an atom of an atom and an atom of Ag" And the total number of ions is 3 ' and L4 has more than 6 molecules below the coordination; 156591.doc 201202390 L5 is selected from phosphorus atom, nitrogen atom 'oxygen atom, sulfur atom, arsenic atom, oxygen anion And sulfur anions make the atoms or ions available as a match

Ag+之原子或離子的分子，且L5所具有之可配位於Ag+之原 子及離子的總數為2個，· L6為具有！個選自磷原子、氮原 子、氧原子、硫原子、砷原子、氧陰離子及硫陰離子中之 原子或離子作為可配位於Ag+之原子或離子的分子；X2為 陰離子；e為大於0.5之數，f、g&h分別獨立為〇以上之 數）。 本發明第四提供一種分子，其含有2個以上之二芳基膦 基，且含有1個或2個之選自從含氮原子之雜環式化合物中 去掉1個〜3個氫原子而成之基.、_〇-、_c(=〇)〇-&_s•中的 基，並且係以下述式（Aa)、（Ab)、（Ba，）、（Bb)、（Bc)或 (Bd)所表示。 [發明之效果] 本發明之膜與使用鉑族金屬之錯合物的膜相比較為廉 價，且作為發光材料於氧存在下之耐久性較高。即，本發 明之膜可表現出持續性優異之發光特性。 【實施方式】 以下對本發明加以說明。 於本說明書中，所謂「可經取代」，包括構成下文即將 記載之化合物或基的氫原子未經取代的情形、及氫原子之 一部分或全部經取代基所取代之情形兩者。作為經取代基 所取代之情形時的取代基，只要無特別說明，則例如可列 舉鹵素原子、碳原子數丨〜3〇之烴基及碳原子數丨〜3〇之烴氧 156591.doc 201202390 基，S亥等中較佳為鹵素原子 '碳原子數卜丨8之烴基及碳原 子數1〜18之烴氧基’更佳為鹵素原子、碳原子數丨〜12之烴 基及碳原子數1〜12之烴氧基，進而較佳為鹵素原子及碳原 子數1〜12之烴基’尤佳為鹵素原子及碳原子數之烴 基。再者，於本說明書_，「可經取代」可換言之為「可 具有取代基」。 於本說明書中，Me表示甲基，n-Bu表示正丁基，t-Bu表 示第二丁基，Ph表示苯基，n_Hex表示正己基。 於本說明書中，於記載為丙基、丁基、戊基、己基、庚 基、辛基、壬基、癸基、十一烷基、十二烷基、十五烷 基、十八烷基、二十二烷基之情形時，該等可為直鏈狀亦 可具有分支結構，較佳為直鍵狀。 本發明之膜含有下述組成式（1)所表示之銀錯合物。 (Ag )(L )a(L2)b(L3)c(X,)d ⑴ (組成式（1)中， L1為具有選自碟原子、氮原子、氧原子、硫原子、石申原 子+、氧陰離子及硫陰離子中之原子或離子作為可配位於 Ag之原子/或離子的*子，L,所具有之可配位於之原 子及離子的總數為3個以上且6個以下，並且Ll所具有之可 配位於Ag+之原子中“固以上為磷原子。。為具有選自磷原 子 '氮原子、氧原子、硫原子、坤原子、氧陰離子及硫陰 =子中之2原子及/或離子作為可配位於Ag+之原子或離子的 分子’ L2所具有之可配位於Ag+之原子及離子的總數為] 個。L3為具有！個選自磷原子、氮原子、氧原子、硫原 156591.doc 201202390 子珅原子、氧陰離子及硫陰離子中之原子或離子作為可 配位於Ag之原子或離子的分子。χ1為陰離子。&為大於 〇’5之數，b、c&d分別獨立為〇以上之數） # ; ’成式⑴中’ L、L2及L3為分子，但分別可具有帶電 荷之B肊基。L、L2及L3於分別具有帶電荷之官能基之情 形時，亦可為離子之狀態。 於組成式(1)中，Li為具有選自磷原子、氮原子、氧原 子、硫原子、砷原子、氧陰離子及硫陰離子中之原子或離 子作為可配位於Ag+之原子或離子的分子。 作為可配位於Ag+之磷原子之例，可列舉3價之磷原子。 作為可配位於Ag+之氮原子之例，可列舉：可經取代之含 氮原子之雜環式化合物中的氮原子（將該含氮原子之雜環 式化合物1個中所含的可配位之氮原子計數為丨個）、自可 經取代之含氮原子之雜環式化合物令去掉丨個〜5個氫原子 而成的基中之氮原子（將該自含氮原子之雜環式化合物令 去掉1個〜5個氫原子而成的基中所含的可配位之氮原子計 數為1個）、可經取代之二烷基胺基中的氮原子、可經取代 之二烷基胺基十的氮原子、可經取代之芳基胺基中的氮原 子、可經取代之烷基芳基胺基中的氮原子、可經取代之亞 胺基中的氮原子、及腈基中的氮原子。作為可配位之氧原 子之例，可列舉氫原子所鍵結之氧原子及第丨5族元素所鍵 結之氧原子》作為可配位於Ag+之硫原子之例，可列舉氣 原子所鍵結之硫原子、烷基巯基中之硫原子、及第15族元 素所鍵結之硫原子。作為可配位於Ag+之神原子之例，可 156591.doc 201202390 列舉3價之砰原子。作為可配位於Ag+之氧陰離子之例，可 列舉〇 Μ乍為可配位於Ag+之硫陰離子之例，可列舉§_。 所-有之可配位於Ag+之原子及離子的總數為3個以上 且6個以1^’並且L,所具有之可配位原子中1個以上為鱗原 子。即，L丨可為具有3個以上且6個以下之僅磷原子作為可 配位於Ag+之原子的分子，亦可為具有共計3個以上且“固 以下之1個以上的可配位於Ag+之磷原子以及選自可配位於The atom of atom or ion of Ag+, and the total number of atoms and ions that L5 can have in Ag+ is 2, · L6 is! An atom or ion selected from the group consisting of a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxyanion, and a sulfur anion as a molecule that can be coordinated to an atom or ion of Ag+; X2 is an anion; and e is a number greater than 0.5 , f, g & h are independent of the above number). The fourth invention provides a molecule comprising two or more diarylphosphino groups, and one or two of them are selected from the group consisting of one to three hydrogen atoms removed from a heterocyclic compound containing a nitrogen atom. a group in the base, _〇-, _c(=〇)〇-&_s•, and is represented by the following formula (Aa), (Ab), (Ba,), (Bb), (Bc) or (Bd) ) said. [Effects of the Invention] The film of the present invention is less expensive than a film using a complex of a platinum group metal, and has high durability as a light-emitting material in the presence of oxygen. That is, the film of the present invention can exhibit luminescent properties excellent in durability. [Embodiment] Hereinafter, the present invention will be described. In the present specification, the term "substitutable" includes both a case where a hydrogen atom constituting a compound or a group to be described later is unsubstituted, and a case where a part or all of a hydrogen atom is substituted with a substituent. The substituent in the case of being substituted with a substituent is, for example, a halogen atom, a hydrocarbon group having a carbon number of 丨3 to 3, and a hydrocarbon oxygen having a carbon number of 丨3 to 3, unless otherwise specified. In the case of S, etc., a halogen atom, a hydrocarbon group having a carbon number of 8 and a hydrocarbon group having 1 to 18 carbon atoms are more preferably a halogen atom, a hydrocarbon group having a carbon number of 丨12, and a carbon number of 1. The alkoxy group of ～12, more preferably a halogen atom and a hydrocarbon group having 1 to 12 carbon atoms are particularly preferably a halogen atom and a hydrocarbon group having a carbon number. Furthermore, in the present specification, "substitutable" may be referred to as "may have a substituent". In the present specification, Me represents a methyl group, n-Bu represents n-butyl group, t-Bu represents a second butyl group, Ph represents a phenyl group, and n_Hex represents a n-hexyl group. In the present specification, it is described as propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, pentadecyl, octadecyl. In the case of a behenyl group, the group may have a linear structure or a branched structure, and is preferably a straight bond. The film of the present invention contains the silver complex represented by the following composition formula (1). (Ag ) ( L ) a ( L 2 ) b ( L 3 ) c (X,) d (1) (In the composition formula (1), L 1 has a selected from the group consisting of a dish atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a stone atom + The atom or ion in the oxyanion and the sulfide anion is used as a *, L, which can be assigned to the atom/or ion of Ag, and the total number of atoms and ions which can be coordinated is 3 or more and 6 or less, and L1 It has a phosphorus atom which can be coordinated to the atom of Ag+. It has 2 atoms selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, a Kun atom, an oxygen anion, and a sulfur atom. Or the ion as a molecule which can be assigned to an atom or ion of Ag+ 'L2 has a total number of atoms and ions which can be coordinated to Ag+. L3 has a selected from phosphorus atom, nitrogen atom, oxygen atom, sulfurogen 156591.doc 201202390 Atom or ion in a helium atom, an oxyanion, and a sulfur anion is a molecule that can be assigned to an atom or ion of Ag. χ1 is an anion. & is greater than 〇'5, b, c&d respectively Independently above 〇)); 'Formula (1) 'L, L2 and L3 are molecules, but each can have The B group of the charge. L, L2 and L3 may also be in the state of ions when they have a charged functional group, respectively. In the composition formula (1), Li is selected from the group consisting of phosphorus atom, nitrogen atom and oxygen. The atom or ion in the atom, the sulfur atom, the arsenic atom, the oxyanion, and the sulfide anion is a molecule that can be coordinated to an atom or ion of Ag+. Examples of the phosphorus atom that can be coordinated to Ag+ include a trivalent phosphorus atom. Examples of the nitrogen atom which may be coordinated to Ag+ include a nitrogen atom in a heterocyclic compound which may be substituted with a nitrogen atom (coordination contained in one of the heterocyclic compounds containing a nitrogen atom) a nitrogen atom in which a nitrogen atom is counted as a heterocyclic compound in which a heterocyclic compound having a nitrogen atom which may be substituted is substituted to remove one to five hydrogen atoms (the heterocyclic compound derived from the nitrogen atom) The number of coordinable nitrogen atoms contained in the group in which one to five hydrogen atoms are removed is one), the nitrogen atom in the substituted dialkylamine group, and the dialkyl group which may be substituted a nitrogen atom of an amine group, a nitrogen atom in a substituted arylamine group, a nitrogen atom in the substituted alkylarylamine group, a nitrogen atom in the substituted imine group, and a nitrogen atom in the nitrile group. Examples of the oxygen atom to be coordinated include a hydrogen atom bond. The oxygen atom bonded to the oxygen atom and the oxygen atom bonded to the group 丨5 element is exemplified as a sulfur atom which can be coordinated to Ag+, and a sulfur atom bonded to a gas atom, a sulfur atom in an alkyl group, and a fifteenth A sulfur atom to which a group element is bonded. As an example of a atom that can be assigned to Ag+, 156591.doc 201202390 exemplifies a trivalent ruthenium atom. As an example of an oxygen anion that can be coordinated to Ag+, 〇Μ乍 can be cited as An example of a sulfur anion disposed in Ag+ can be cited as §_. The total number of atoms and ions that can be assigned to Ag+ is three or more, and six of them are 1^' and L, and one or more of the coordinable atoms are scaly atoms. In other words, L丨 may be a molecule having three or more and only six or less phosphorus atoms as atoms which can be coordinated to Ag+, or may have a total of three or more and one or more of the following may be assigned to Ag+. Phosphorus atoms and selected from

Ag+之碟原子以外之原子（氮原子、氧原子、硫原子、及石申 原子）及可配位於Ag+之離子（氧陰離子及硫陰離子）中之^固 以上的分子。 作為上述L1之較佳態樣之―，可列舉具有4個以上且6個 以下之可配位於Ag+之磷原子的分子。作為Li之其他較佳 態樣之一，可列舉以下分子：具有丨個以上之可配位於Ag+ 之磷原子以及選自可配位於Ag+之氮原子、可配位於Ag+之 氧原子、可配位於Ag+之硫原子、可配位於Ag+之砷原子、 可配位於Ag之氧陰離子及可配位於Ag+之硫陰離子中的上 個以上，且可配位於Ag+之原子及離子共計為3個以上且6 個以下。上述較佳兩例中更佳為後者。 上述L1中所含之可配位於Ag+之磷原子之數為丨個以上， 較佳為2個以上。於L所具有之可配位於Ag+之麟原子之數 為2個以上之情形時’膜對於氧之耐久性更為提高，故較 佳為該2個以上之磷原子均未鍵結sp3碳原子。 於L可具有之可配位於Ag之碟原子、可配位於Ag+之氮 原子、可配位於Ag+之氧原子、可配位於Ag+之硫原子、可 156591.docAn atom other than the atom of the atom of Ag+ (a nitrogen atom, an oxygen atom, a sulfur atom, and a Shishen atom) and a molecule which can be coordinated with an ion of an Ag+ (an oxo anion and a sulfur anion). As a preferred aspect of the above L1, a molecule having four or more and six or less phosphorus atoms which can be coordinated to Ag+ can be cited. As one of other preferred aspects of Li, the following molecules may be mentioned: one or more phosphorus atoms which may be coordinated to Ag+ and one selected from a nitrogen atom which may be coordinated to Ag+, may be coordinated to an oxygen atom of Ag+, and may be coordinated. A sulfur atom of Ag+, an arsenic atom which can be coordinated to Ag+, an oxyanion which can be coordinated to Ag, and a sulfan anion which can be coordinated with Ag+, and a total of 3 or more atoms and ions which can be coordinated with Ag+ Below. More preferably, the latter of the above two preferred examples. The number of phosphorus atoms which can be coordinated to Ag+ contained in the above L1 is one or more, and preferably two or more. When the number of the arsenic atoms which can be assigned to the Ag+ in L is two or more, the durability of the film to oxygen is further improved. Therefore, it is preferred that the two or more phosphorus atoms are not bonded to the sp3 carbon atom. . L may have a fluorine atom which can be assigned to Ag, a nitrogen atom which can be coordinated to Ag+, an oxygen atom which can be coordinated to Ag+, a sulfur atom which can be coordinated to Ag+, and can be 156591.doc

S 201202390 配位於Ag+之石t原子、可配位於Ag+之氧陰離子及可配位於 Ag+之疏陰離子中，除鱗原子以外較佳者為氧陰離子及硫 陰離子，較佳為Li含有丨個氧陰離子或硫陰離子。 L1所具有之可配位於Ag+之原子及離子的總數為3個以上 且6個以下，較佳為3個或4個。再者，於L1所具有之可配 位於Ag+之原子及離子中，可含有複數個相同之原子及離 子’亦可含有不同之原子與離子之組合。S 201202390 is a rock atom of Ag+, an oxygen anion which can be coordinated with Ag+ and an anion which can be coordinated with Ag+. Preferably, the descaling atom is an oxyanion and a sulfur anion, preferably Li contains an oxygen anion. Or sulfur anions. The total number of atoms and ions which can be assigned to Ag+ in L1 is 3 or more and 6 or less, preferably 3 or 4. Furthermore, the atoms and ions which may be assigned to Ag+ in L1 may contain a plurality of identical atoms and ions, and may also contain different combinations of atoms and ions.

Ll較佳為配位於Α§+，作為單牙配位基而配位於Ag+、作 為雙牙配位基而配位KAg+、作為三牙以上之配位基而配 位於Ag均可，更佳為作為雙牙以上之配位基而配位於 Ag進而較佳為作為三牙以上之配位基而配位於Ag+。 L1之碳原子數通常為12〜3〇〇，較佳為22〜25〇 ,更佳為 25〜200，進而較佳為28〜150，尤佳為30-125。 作為L1之例’可列舉下述式（Aa)、（Ab)、（Ba)〜(Bd)、 (Ca) (Ci)、及（Da)〜(Dt)所表示之分子，由於錯合物之成膜 性優異’故更佳為下述式（Aa)、（Ab)、（Ba)〜(Bd)所表示之 分子，進而較佳為下述式（Ba)、（Bc)所表示之分子，尤佳 為下述式（Be)所表示之分子。 [化1] p2Aa D2Aa Q1A’ \Q2Aa〆 \Q1Aa Q1^ .Q1Ab \R3Af I (Aa) i1Ab U (Ab) p2Ba p2Ba p2Ba Q1Ba \〇2Ba 、1Ba (Ba) 156591.doc 201202390Ll is preferably located in Α§+, is assigned to Ag+ as a monodentate ligand, is coordinated to KAg+ as a bidentate ligand, and is coordinated to Ag as a ligand of three or more teeth, more preferably It is coordinated to Ag as a ligand of a double tooth or more, and is preferably a ligand of three or more teeth and is coordinated to Ag+. The number of carbon atoms of L1 is usually 12 to 3 Å, preferably 22 to 25 Å, more preferably 25 to 200, still more preferably 28 to 150, still more preferably 30 to 125. Examples of the L1 include molecules represented by the following formulas (Aa), (Ab), (Ba) to (Bd), (Ca) (Ci), and (Da) to (Dt), due to the complex compound. It is more preferably a molecule represented by the following formulas (Aa), (Ab), (Ba) to (Bd), and more preferably represented by the following formulas (Ba) and (Bc). The molecule is particularly preferably a molecule represented by the following formula (Be). p2Aa D2Aa Q1A' \Q2Aa〆 \Q1Aa Q1^ .Q1Ab \R3Af I (Aa) i1Ab U (Ab) p2Ba p2Ba p2Ba Q1Ba \〇2Ba , 1Ba (Ba) 156591.doc 201202390

b / 1BV 1Qb / 1BV 1Q

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h 1C Q12 \ h R Q 2ch4c/2ch/h) R——Q——R c ( 2C Q /h h c c chh 1C Q12 \ h R Q 2ch4c/2ch/h) R——Q——R c ( 2C Q /h h c c ch

1ci~Q Q/5ci1ci 1ci\l Q1ci 1Q 式（Aa)中，Q1Aa&-P(R11Aa)2、-As(R12Aa)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Aa)(R14Aa)、-0、-S_、-S(=0)2〇-、-C(=0)0·、-P(=0) (R15Aa)2、-As(=0)(R丨6Aa)2、-P(=S)(R17Aa)2、-As(=S)(R18Aa)2、 -CN、-OH、-SH、-C(=0)0H、-S(=0)20H、-SR19Aa、或 _C(=〇)N(R21Aa)2。R11Aa、R12Aa、R13Aa、R15Aa、R16Aa、 R17Aa、RlSAa及R2lAa分別獨立為氫原子或可經取代之碳原 -10- I5659l.doc s 201202390 子數^50的烴基，及Riw分別獨立為可經取代之碳 原子數 1〜30之烷基，R11Aa、R12Aa、RuAa、Ri4Aa、Rl5Aa、 、d R21Aa可分別相同亦可不同/ Q2Aa為-P(R2，-、-As(R，_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Aa)_、 -P(=〇)(R25Aa)-、-As(=0)(R26A>、_p(=s)(R27Aa)、或-As⑼ (R，_。R22Aa、R23Aa、R25Aa、R26Aa、〇R28Aa分別獨 立為氫原子或可經取代之碳原子數i〜5〇之烴基，R24Aa為可 經取代之碳原子數1〜30之烷基，R22Aa、R23Aa、R24Aa、 R25Aa、R26Aa、R27Aa 菸 八 ^ 叫 K Κ 及R 可分別相同亦可不同。 R2Aa為碳原子數50以下之2價基，然而，於所鍵結之QlAa 為自含氮原子之雜環式化合物中去掉1個氫原子而成的基 之情形’或所鍵結之QW為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。1ci~QQ/5ci1ci 1ci\l Q1ci 1Q In the formula (Aa), Q1Aa&-P(R11Aa)2, -As(R12Aa)2, one hydrogen is removed from the heterocyclic compound having a nitrogen atom which may be substituted The base of the atom, -N(R13Aa)(R14Aa), -0, -S_, -S(=0)2〇-, -C(=0)0·, -P(=0) (R15Aa)2 , -As(=0)(R丨6Aa)2, -P(=S)(R17Aa)2, -As(=S)(R18Aa)2, -CN, -OH, -SH, -C(=0 ) 0H, -S(=0)20H, -SR19Aa, or _C(=〇)N(R21Aa)2. R11Aa, R12Aa, R13Aa, R15Aa, R16Aa, R17Aa, RlSAa and R2lAa are each independently a hydrogen atom or a substituted carbonogen-10-I5659l.doc s 201202390 subunit number 50, and Riw is independently substituted The alkyl group having 1 to 30 carbon atoms, R11Aa, R12Aa, RuAa, Ri4Aa, Rl5Aa, and dR21Aa may be the same or different / Q2Aa is -P(R2, -, -As(R, _, self-conductible) A group in which two hydrogen atoms are removed from a heterocyclic compound substituted with a nitrogen atom, _N(R24Aa)_, -P(=〇)(R25Aa)-, -As(=0)(R26A>, _p( = s) (R27Aa), or -As (9) (R, _. R22Aa, R23Aa, R25Aa, R26Aa, 〇R28Aa are each independently a hydrogen atom or a hydrocarbyl group having a substituted number of carbon atoms i~5〇, and R24Aa is a substitutable The alkyl group having 1 to 30 carbon atoms, R22Aa, R23Aa, R24Aa, R25Aa, R26Aa, R27Aa, and the like, may be the same or different. R2Aa is a divalent group having 50 or less carbon atoms. In the case where the bonded QlAa is a group in which one hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded QW is a heterocyclic compound derived from a nitrogen atom. When the base of two hydrogen atoms is removed, it may be a direct bond.

R 1 6AaR 1 6Aa

R 17AaR 17Aa

選自 R11Aa、Rl2Aa、Rl3Aa、Rl4Aa、r15/U RUAa、RlW、R21Aa、R22Aa、R23Aa、R24Aa、、κ·、 e及自可經取代之含氮原子之雜環式化合 $中去掉1個〜2個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 作為式（Aa)所表示之分子之各取代基的較佳態樣， 舉： Q1A、-P(R11Aa)2、_A<5n?12Aa、 A Λ- )2 AS(R )2自可經取代之含氮原子 之雜環式化合物中去掉1個氫原子而成的基、_〇-、_S-、 -s(=〇)2〇·、或-c(=o)〇-， 156591.doc 201202390 Q為-p(R22Aa)-、_As(R23Aa)-、或自可經取代之含氮原 子之雜環式化合物中去掉2個氫原子而成的基， R 、Rl2Aa、R22Aa&R23Aa分別獨立為可經取代之苯 式（Aa)所表示之分子含有i個以上之_p(Rlu、、或 'P(R22Aa)·的態樣；其中’較佳為R2Aa為直接鍵結或可經取 代之下述式rl〜r12中之任一個所表示之基。 式⑽中，dP(R"Ab)2、_As(Rl2Ab)2、自可經取代 之含氮原子之雜環式化合物中去掉i個氫原子而成的基、 •N(R，3Ab)(Rl4Ab> ' -°· ' ' -S(=〇)2〇- ^ -0(=〇)〇- . .P(=0) (R，5Ab)2 ^ -As(=0)(R—)2 , -P(=S)(R-Ab)2 ^ _As(=S)(Rl8Ab)2 . •CN、-0H、_SH、_c(=〇)〇H、_s(=〇)2〇h、、或 •c(=〇)N(R_)2。R⑽、Rl2Ab、Rl3Ab、Rl5Ab、r_、 R^Ab、p 18Ab β D21Ab 八 刀別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，Rl4Ab及R19Ab八 刀另!獨立為可經取代之碳 原子數 i〜30之烧基 ’ 、Rl2Ab、Rl3Ab、Rl4Ab、Ri5Ab、 R16Ab、Rl7Ab、Rl8Ab、r19 及R 可分別相同亦可不同。 R3Ab為碳原子數5〇以下之3價基。One selected from the group consisting of R11Aa, Rl2Aa, Rl3Aa, Rl4Aa, r15/U RUAa, RlW, R21Aa, R22Aa, R23Aa, R24Aa, κ·, e and a heterocyclic compound of a nitrogen atom which may be substituted is removed. Two or more of the two hydrogen atoms may be bonded to each other to form a ring. As a preferred aspect of each substituent of the molecule represented by the formula (Aa), Q1A, -P(R11Aa)2, _A<5n?12Aa, A Λ- )2 AS(R )2 are self-substitutable a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, _〇-, _S-, -s(=〇)2〇·, or -c(=o)〇-, 156591.doc 201202390 Q is -p(R22Aa)-, _As(R23Aa)-, or a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, and R, Rl2Aa, R22Aa&R23Aa are each independently The molecule represented by the phenyl group (Aa) which may be substituted may contain more than one _p(Rlu, or 'P(R22Aa)·); wherein 'preferably R2Aa is a direct bond or may be substituted a group represented by any one of the following formulas rl to r12. In the formula (10), dP(R"Ab)2, _As(Rl2Ab)2, and a heterocyclic compound having a nitrogen atom which may be substituted are removed. a group of hydrogen atoms, •N(R,3Ab)(Rl4Ab> '-°· ' ' -S(=〇)2〇- ^ -0(=〇)〇- . .P(=0) ( R,5Ab)2 ^ -As(=0)(R—)2 , -P(=S)(R-Ab)2 ^ _As(=S)(Rl8Ab)2 . •CN,-0H, _SH, _c (=〇)〇H, _s(=〇)2〇h,, or •c(= N(R_)2. R(10), Rl2Ab, Rl3Ab, Rl5Ab, r_, R^Ab, p 18Ab β D21Ab are independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, Rl4Ab and R19Ab eight Further, the alkyl group, Rl2Ab, Rl3Ab, Rl4Ab, Ri5Ab, R16Ab, Rl7Ab, Rl8Ab, r19 and R which are independently substituted carbon atoms i to 30 may be the same or different. R3Ab is 5 carbon atoms. 〇 The following 3 valence base.

選自R llAb R 、Rl4Ab、R15Ab、Rl6Ab、R17Ab、 R2!Ab、R3Ab目了纟k取代之含氮原子之雜 環式化合物中去掉1個氫原子而占从*丄風原于而成的基中的2個以上之基亦可任意鍵結而形成環。 式（Ba)中，Q1B^-P(RMBa)AS(^R )2、自可經取代之含氣原子之雜％式化合物中+娃、加甲去掉1個氡原子而成的基、A compound selected from the group consisting of R llAb R , Rl4Ab , R15Ab , Rl6Ab , R17Ab , R 2 ! Ab , R 3 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Two or more groups in the group may be bonded arbitrarily to form a ring. In the formula (Ba), Q1B^-P(RMBa)AS(^R)2, a base of a heteropoly compound of a gas atom which can be substituted, + a base, a base obtained by removing one helium atom,

R 12AbR 12Ab

R 18AbR 18Ab

R l9Ab -12· 156591.doc 201202390 -N(严)(R_)、-◦·、_S·、骨〇)2〇.、_c(=〇)◦•件〇) (R15Ba)2、-蛛〇)(R_)2、_P(=s)(Rl7Ba)2、A—.，、 -CN、-0H、-SH、_C(=0)〇H、_s(=〇)2〇h、抓⑽、或-C(=0)N(R21Ba)2。RHBa、Rl2Ba、Rl3Ba、尺咖、、 R”Ba、RlSBa及 R2 丨 Ba 分 倒马虱原子或可經取代之碳原 子數卜50之烴基’ Ri、r，分別獨立為可經取代之碳 原子數1〜30之院基，R"Ba、尺丨瓜 R13BiR l9Ab -12· 156591.doc 201202390 -N (strict) (R_), -◦·, _S·, osteophyte) 2〇., _c(=〇)◦•件〇) (R15Ba)2, - spider 〇 )(R_)2, _P(=s)(Rl7Ba)2, A-.,, -CN, -0H, -SH, _C(=0)〇H, _s(=〇)2〇h, grab (10), Or -C(=0)N(R21Ba)2. RHBa, Rl2Ba, Rl3Ba, ruthenium, R"Ba, RlSBa, and R2 丨Ba are inverted equimolar atoms or a substitutable carbon atom number 50 of the hydrocarbon group ' Ri, r, respectively, which are independently substituted carbon atoms Number 1~30 of the yard base, R"Ba, ruler melon R13Bi

Rl6Ba、R"BaRl6Ba, R"Ba

R 18Bi R19Ba» R21Ba-p ' 及R 可分別相同亦可不同 Q⑴為-P(R，_、_As(R23Ba)·、自可經取代之含氣原子 之雜環式化合物中去掉2個氫原子而成的基、_n(r施)_、 外〇)(严)_、_As(=0)(R26Ba)_、.p(=s)(R27Ba)、或 _as(=s) (R28Ba)-°R22Ba、R23Ba、R25Ba、R26Ba、dR2、„ 立為氫原子或可經取代之碳原子數N50 Ba R22Ba；Rl\24：" R-a、R26Ba、R27Ba及r28〜分別相同亦可不同。 碳原子數50以下之2價基 '然而，於所鍵結之QiBa 為自含氣原子之雜環式化合物中去W個氫原子而成的基 之情形，或所鍵結之f為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。R 18Bi R19Ba» R21Ba-p ' and R may be the same or different Q(1) is -P(R, _, _As(R23Ba)·, 2 hydrogen atoms are removed from the heterocyclic compound containing a gas atom which may be substituted The base, _n(r), outer 〇(strict)_, _As(=0)(R26Ba)_, .p(=s)(R27Ba), or _as(=s) (R28Ba) -R22Ba, R23Ba, R25Ba, R26Ba, dR2, „ a hydrogen atom or a carbon atom which may be substituted, N50 Ba R22Ba; Rl\24:" Ra, R26Ba, R27Ba and r28~ may be the same or different. a divalent group having an atomic number of 50 or less ' However, in the case where the bonded QiBa is a group obtained by removing a hydrogen atom from a heterocyclic compound containing a gas atom, or the bonded f is a self-containing nitrogen In the case where a hydrogen atom is removed from a heterocyclic compound of an atom, it may be a direct bond.

選自R llBaFrom R llBa

R 12BsR 12Bs

R 13BaR 13Ba

R 14Ba 5Βί j^24Bi j^l 6Ba j^25BaR 14Ba 5Βί j^24Bi j^l 6Ba j^25Ba

R 17BaR 17Ba

RlSBa、R!9Ba、R2lBa、R22Ba、R23Bi R27Ba x 〇28Ba ri2Ba~ , 上、 可經取代之含氮原子之雜環式化合 :中去掉1個〜2個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。RlSBa, R!9Ba, R2lBa, R22Ba, R23Bi R27Ba x 〇28Ba ri2Ba~ , a heterocyclic compound of a substituted nitrogen atom; two of the groups obtained by removing one to two hydrogen atoms The above groups may also be bonded to form a ring.

R 26Bi 15659l.doc •13· 201202390 作為式（Ba)所表示之分子之各取代基的較佳態樣可列 舉以下態樣： 、自可經取代之含氮原子之雜環式化合 物中去掉1個氫原子而成的基、_〇-、_c(=〇)〇-、或—S.， 0283為彳(尺22^)-或自可經取代之含氮原子之雜環式化合 物中去掉2個氫原子而成的基， 尺1】^及!122^分別獨立為可經取代之苯基，…以為直接鍵 結或可經取代之下述式rl〜rl2中之任一個所表示之基。 式（Bb)中，自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基 -Ν^，(κ_)、_〇-、_s· ' -S(=〇)2〇· ' c(=〇)〇.、p(=〇) (R15Bb)2 ' -As(=0)(R,6Bb)2 . -P(=S)(R17Bb)2 . -As(=S)(R,8Bb)2 . -CN、-〇H、-SH、-C(=0)0H、-S(=0)2〇H、-SR丨9Bb、戋 -C(=0)N(R21Bb)2。R_、以⑽、RnBb、R,5Bb、R】6Bb、 R 、R18Bb& R21Bb*別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R丨4Bb&R〗9Bb分別獨立為可經取代之碳 原子數1〜30之烧基，R丨丨Bb、R丨2Bb、R13Bb、Rl4Bb丨5Bb d Rl7Bb、Rl8Bb、r19、r21b^分別相同亦可不同。 Q2、-P(R，…As(R23Bb)_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Bby、 -P(=〇)(R25Bb)-、·Α3(=〇)(ΐι26Βΐ3)_、·ppsxR^Bb)·、或 _As卜s) (R28Bb)_。R22Bb、R23Bb、R25Bb、R26Bb、R27Bl^R28Bb分別獨 立為氫原子或可經取代之碳原子數丨〜”之烴基，R：UBb為可 經取代之碳原子數^30之烷基，R22Bb、R23Bb、R24Bb、 156591.doc • 14· 201202390 严、R26Bb、R2及R騰可分別相同亦可不同。 R2、碳原子數50以下之2價基，然而，於所鍵结之QiBb 為自含氮原子之雜環式化合物中去W個氣原子而成的基 之情形，或所鍵結之Q挪為自含氮原子之雜環式化合物中 • 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 . R3Bb為碳原子數50以下之3價基。 選自R11Bb、 Rl2Bb、 1 3 B b R18Bb、 j^l9Bb ^21Bb r2 2 B b R27Bb、 j^28Bb R2Bb、 R3Bb 及 R_、R_、Ri4Bb、Ri5Bb、Ri6Bb、Ri7Bb、 …咖、、R23Bb、R24Bb、、 ο 2 B b t> 3 B b -rr - 可經取代之含氮原子之雜環 式化合物中去掉！個~2個氫原子而成的基中的玲以上之基 亦可任意鍵結而形成環。 式（Bc)中，Q1BC為-p(R"Bf (R1、、自可經取代 之含氮原子之雜環式化合物中去掉㈣氫原子 -N(R13Bc)(R—) , -ο-. .s-. _S(=〇. 〇. 战的土 y。)2〇、-C(=0)0-、_P(=〇) (R15%、-As(=〇)(R’2、_P(=s)(Rl7Be)2、_坪戰i8%、 -CN、·ΟΗ、-SH、_C(=0)0H、_s(=〇)2〇h、⑽他 C(=0)N(R，。、ruBc、Rl3Be、r15b^ ^_及广分„立為氫原子或可經取代之碳片 子數WG之烴基’ 分別獨立為可經取代之碳原 子數1〜30之烷基，R"Be、Rl2Be、R]3Bc、以丨他、汉丨5Bc、 R〜一、R’、R，及R21BC可分別相同亦可不同^ ^ Q-為P、As、自可經取代之含說原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As(=〇)、p(=s)、 或 As(=S) 〇 156591.doc •15· 201202390 R 為碳原子數50以下之2價基，然而，於所鍵結之q丨Be 為自含氣原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之Q3BC為自含氮原子之雜環式化合物中 去掉3個氫原子而成的基之情形時，亦可為直接鍵結。 選自 RnBc、Rl2Bc、Rl3Bc、Rl4Bc、Rl5Bc、r丨6Bc、r17Bc、 R18Bc . ϋ 19Bc p21Bc τ» 2Bc β ώ 人总 ， κ R 、R及自含氮原子之雜環式化合物中 去掉1個或3個氫原子而成的基中的2個以上之基亦可任意 鍵結而形成環。 作為上述式（Be)所表示之分子之各取代基的較佳態樣， 可列舉以下態樣： Q1BU(R11Be)2、自可經取代之含氮原子之雜環式化合 物中去掉1個氫原子而成的基、_〇-、_c(=〇)〇-、戋_s·, (^以為卩或自可經取代之含氮原子之雜環式化合物_去 掉3個氫原子而成的基， R11Be為可經取代之苯基， R2Be為直接鍵結或可經取代之下述式rl〜rl2中之任一個 所表示之基。 自可經取代 式（Bd)中，Q1Bd為 _P(R"Bd)2、_As(Rl2Bd)2 之含氮原子之雜環式化合物中去掉i個 -CN、-OH、-SH、-C(=〇)〇h、 -C(=0)N(R21Bd)2。R"Bd、Ri2Bd 分別獨立為氫原 -p(=S)(R,7Bd)2 > -As(=S)(R,8Bd)2 > -N(R,3Bd)(R丨4Bd)、-〇·、_s-(R15Bd)2、-As(=0)(R16Bd)2、 r17B<)、Rl8Bd及 R2IBd 虱原子而成的基、 S(=0)20' ' -〇(=〇)〇- ^ -P(=〇) -S(=〇)2〇H、-SR19Bd、或 、R13Bd、、Rl6Bd、 子或可經取代之碳原 -16- 15659丨.docR 26Bi 15659l.doc • 13· 201202390 As a preferred aspect of each substituent of the molecule represented by the formula (Ba), the following aspects can be exemplified: From the heterocyclic compound having a nitrogen atom which can be substituted, 1 is removed. a group of hydrogen atoms, _〇-, _c(=〇)〇-, or -S., 0283 is 彳 (foot 22^)- or removed from a heterocyclic compound containing a nitrogen atom which may be substituted a base of two hydrogen atoms, each of which is independently a phenyl group which can be substituted, and which is represented by any of the following formulas rl to rl2 which may be substituted or substituted. base. In the formula (Bb), a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, (κ_), _〇-, _s· ' -S (=〇) 2〇· ' c(=〇)〇., p(=〇) (R15Bb)2 ' -As(=0)(R,6Bb)2 . -P(=S)(R17Bb)2 . -As(= S)(R,8Bb)2 . -CN, -〇H, -SH, -C(=0)0H, -S(=0)2〇H, -SR丨9Bb, 戋-C(=0)N (R21Bb) 2. R_, (10), RnBb, R, 5Bb, R] 6Bb, R, R18Bb& R21Bb* are independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R丨4Bb&R9bb are independently The substituted carbon atom having 1 to 30 carbon atoms may be the same or different from R丨丨Bb, R丨2Bb, R13Bb, Rl4Bb丨5Bb d Rl7Bb, Rl8Bb, r19 and r21b^. Q2, -P(R,...As(R23Bb)_, a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _N(R24Bby, -P(=〇)(R25Bb )-,·Α3(=〇)(ΐι26Βΐ3)_,·ppsxR^Bb)·, or _As s) (R28Bb)_. R22Bb, R23Bb, R25Bb, R26Bb, R27Bl^R28Bb are each independently a hydrogen atom or a hydrocarbon group having a carbon number of 丨~", and R:UBb is a substitutable alkyl group having a carbon number of 30, R22Bb, R23Bb , R24Bb, 156591.doc • 14· 201202390 Strict, R26Bb, R2 and Rteng may be the same or different. R2, a valence of 50 or less carbon atoms, however, the bonded QiBb is a self-containing nitrogen atom In the case where a heterocyclic compound is substituted with a gas atom, or the bonded Q is a heterocyclic compound derived from a nitrogen atom; when a base of two hydrogen atoms is removed, It may also be a direct bond. R3Bb is a trivalent group having a carbon number of 50 or less. It is selected from the group consisting of R11Bb, Rl2Bb, 1 3 B b R18Bb, j^l9Bb ^21Bb r2 2 B b R27Bb, j^28Bb R2Bb, R3Bb and R_, R_, Ri4Bb, Ri5Bb, Ri6Bb, Ri7Bb, ..., coffee, R23Bb, R24Bb, ο 2 B b t> 3 B b - rr - a substituted heterocyclic compound containing a nitrogen atom is removed! The group in which the two hydrogen atoms are formed may be arbitrarily bonded to form a ring. In the formula (Bc), Q1BC is -p (R" Bf (R1) Remove the (iv) hydrogen atom -N(R13Bc)(R-) from the substitutable nitrogen-containing heterocyclic compound, -ο-. .s-. _S(=〇. 〇. Battle of soil y.) 2 〇, -C(=0)0-, _P(=〇) (R15%, -As(=〇)(R'2, _P(=s)(Rl7Be)2, _ping battle i8%, -CN, ·ΟΗ, -SH, _C(=0)0H, _s(=〇)2〇h, (10)He C(=0)N(R,., ruBc, Rl3Be, r15b^^_, and widely divided into hydrogen The atomic or substituted carbon number WG of the hydrocarbon group 'is independently a substituted alkyl group having 1 to 30 carbon atoms, R"Be, Rl2Be, R]3Bc, 丨他, 汉丨5Bc, R~ 1. R', R, and R21BC may be the same or different. ^ Q- is P, As, a radical formed by removing three hydrogen atoms from a heterocyclic compound containing a substituted atom, N, p(=〇), As(=〇), p(=s), or As(=S) 〇156591.doc •15· 201202390 R is a divalent group having 50 or less carbon atoms, however, q丨Be is a case in which a hydrogen atom is removed from a heterocyclic compound containing a gas atom, or the bonded Q3BC is a three-hydrogen atom removed from a heterocyclic compound containing a nitrogen atom. Base situation , May also be a direct bond. It is selected from the group consisting of RnBc, Rl2Bc, Rl3Bc, Rl4Bc, Rl5Bc, r丨6Bc, r17Bc, R18Bc. ϋ 19Bc p21Bc τ» 2Bc β ώ total, κ R , R and one of the heterocyclic compounds from the nitrogen atom are removed or Two or more of the three hydrogen atoms may be bonded to each other to form a ring. Preferred examples of the respective substituents of the molecule represented by the above formula (Be) include the following: Q1BU(R11Be)2, and one hydrogen is removed from the heterocyclic compound having a nitrogen atom which may be substituted A radical, _〇-, _c(=〇)〇-, 戋_s·, (^ is a heterocyclic compound containing a nitrogen atom that can be replaced by a hydrogen atom. R11Be is a phenyl group which may be substituted, and R2Be is a group which is directly bonded or substituted by any one of the following formulas rl to rl2. In the substitutable formula (Bd), Q1Bd is _P (R"Bd)2, _As(Rl2Bd)2, the nitrogen-containing heterocyclic compound is removed from -CH, -OH, -SH, -C(=〇)〇h, -C(=0)N (R21Bd) 2. R"Bd, Ri2Bd are independently hydrogenogen-p(=S)(R,7Bd)2 > -As(=S)(R,8Bd)2 > -N(R,3Bd) (R丨4Bd), -〇·, _s-(R15Bd)2, -As(=0)(R16Bd)2, r17B<), Rl8Bd and R2IBd bases of 虱 atoms, S(=0)20' ' -〇(=〇)〇- ^ -P(=〇) -S(=〇)2〇H, -SR19Bd, or, R13Bd,, Rl6Bd, sub or substituted carbonogen-16- 15659丨.doc

S 201202390 子數1〜50之烴基，R丨似及尺丨9Bd分別獨 刀乃J倜立為可經取代之碳 原子數1〜30之烷基，R丨丨Bd、R丨2Bd、Rl3Bd、Rl4Bd、 R1…、R圖、Rl8Bd、R隨及R21Bd可分別相同亦可：同。、 R4Bd為碳原子數70以下之4價基。 選自 RllBd、Rl2Bd、Rl3Bd、Rl4Bd、Rl5Bd、Ri6Bd、尺17^ R_、R_、R謂、，及自可經取代之含氮原子之雜環 式化合物中去掉1個氫原子而成的基中的2個以上之基亦可 任意鍵結而形成環。 式（Ca)中，Q心為-P(RHCa)2、-As(RuCa)2、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -N(R13Ca)(R丨4Ca)、〇-、_s-、_s(=〇)2〇-、_c(=〇)〇_、_p(=〇) (R，5Ca)2 > -As(=0)(R16Ca)2 . -P(=S)(R17Ca)2 . -As(=S)(R,8Ca)2 . -CN、-OH、-SH、-C(=〇)〇H、-S(=0)2〇H、-SR19Ca、或 -C( = 〇)N(R21Ca)2。R 丨丨Ca、R12Ca、Rl3Ca、Rl5Ca、R〖6Ca、 R17Ca、R18Ca& R21Ca分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，尺丨心及…心分別獨立為可經取代之碳 原子數 1〜30之烧基，R"Ca、R12Ca、R】3Ca、R14Ca、Rl5Ca、 R 6ea' Rl7ea' Rl8ea、Rl9elR2iea可分別相同亦可不同。 Q2Ca& -P(R22Ca)-、-As(R23Ca)·、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Ca)_、 -P(=0)(R25Ca)-、_As(=〇)(R26Ca)_、_p(=s)(R27Ca)_、或 _As(=s) (R28Ca)-。R”Ca、R23Ca、R25Ca、R26Ca、R27CiR28Ca分別獨 立為氫原子或可經取代之碳原子數卜％之烴基，R24Ca為可 經取代之碳原子數1〜3〇之烷基，R22Ca、R23Ca、R24Ca、 156591 .doc -17- 201202390 p25Ca、〇26Ca、u27Cart ij28Ca八 σ 1 R 、R 、R 及R 可分別相同亦可不同。 R2Ca為碳原子數50以下之2價基，然而，於所鍵結之QlCa 為自含氮原子之雜環式化合物中去掉1個氫原子而成的基 之情形，或所鍵結之Q2Ca為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 選自 R11Ca、R12Ca、R13Ca、R丨4Ca、R丨 5Ca、R16Ca、R17Ca、 R18Ca、R19Ca、R21Ca、R22Ca、R23Ca、R24Ca、R25Ca、R26Ca、 R 、R 、R及自可經取代之含氮原子之雜環式化合 物中去掉1個〜2個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 式（Cb)中，Q丨Cb為-P(R丨心)2、_As(Rl2Cb)2、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -n(r丨，㊉丨，、_〇·、_s-、_s(=0)2〇·、_c(=〇)〇·、p㈣ (R15Cb)2、-As(=0)(R_)2、-P(=S)(RnCb)2、-As(=s)(Rl8Cb)2、 -CN、-〇H、-SH、-C(=0)0H、-S(=〇)2〇h、_SR丨9Cb、或 -C( = 〇)N(R21Cb)2。R11Cb、R12Cb、R丨 3Cb、Ri5Cb、Rl6Cb、 、RUCb及RhCb分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R14Cb&R19Cb分別獨立為可經取代之碳 原子數 1〜30之烷基，R"Cb、R12Cb、Rncb、Rl4Cb、Rl5Cb、 R16Cb 17Cb、R18Cb、R 19Cb „ VICb-r \ , R R R 及R 可分別相同亦可不同。 Q2C1 -P(R22Cb)-、-As(R23cb)·、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Cb)_、 _P(=〇)(R25Cb)-、-As(=0)(R26Cb)·、_P(=s)(R27Cb)·、 (R2SCb). 〇 R22Cb . R23Cb . R25Cb ^ R26Cb ^ •18· 156591.doc s 201202390 立為氫原子或可經取代之碳原子數…之烴基，R24cb為可 經取代之奴原子數^30之烷基，R22Cb、、R24Cb、 R25Cb、R26Cb、r27c c Mb、 了刀別相同亦可不同。 R2Cb為碳原子數5(m下之2價基，“，於所鍵結之QlCb 為自含氮原子之雜環式化合物中去個氮原子而成的基 之情形，或所鍵結之Q-為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 R eb為碳原子數5〇以下之3價基。 選自R"Cb、R⑽、严、Rl4Cb、R】5Cb、尺⑽、尺⑽ R-b、R⑽、R21Cb、R22Cb、R23Cb、R24cb、、r薦、S 201202390 Hydrocarbyl group of 1 to 50, R 丨 like and 丨 9Bd respectively, is a substituted alkyl group having 1 to 30 carbon atoms, R丨丨Bd, R丨2Bd, Rl3Bd, Rl4Bd, R1, R, Rl8Bd, R and R21Bd may be the same or the same: same. R4Bd is a tetravalent group having 70 or less carbon atoms. It is selected from the group consisting of RllBd, Rl2Bd, Rl3Bd, Rl4Bd, Rl5Bd, Ri6Bd, ruthenium 17^R_, R_, R, and a group of one hydrogen atom removed from a heterocyclic compound having a nitrogen atom which may be substituted. Two or more groups may be bonded to each other to form a ring. In the formula (Ca), the Q core is -P(RHCa)2, -As(RuCa)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N( R13Ca)(R丨4Ca), 〇-, _s-, _s(=〇)2〇-, _c(=〇)〇_, _p(=〇) (R,5Ca)2 > -As(=0) (R16Ca)2 . -P(=S)(R17Ca)2 . -As(=S)(R,8Ca)2 . -CN, -OH, -SH, -C(=〇)〇H, -S( =0) 2〇H, -SR19Ca, or -C( = 〇)N(R21Ca)2. R 丨丨Ca, R12Ca, Rl3Ca, Rl5Ca, R 〖6Ca, R17Ca, R18Ca& R21Ca are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and the core and the heart are independently The substituted alkyl group having 1 to 30 carbon atoms may be the same or different in R"Ca, R12Ca, R]3Ca, R14Ca, Rl5Ca, R 6ea' Rl7ea' Rl8ea and Rl9elR2iea. Q2Ca&-P(R22Ca)-, -As(R23Ca)·, a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _N(R24Ca)_, -P(= 0) (R25Ca)-, _As(=〇)(R26Ca)_, _p(=s)(R27Ca)_, or _As(=s)(R28Ca)-. R"Ca, R23Ca, R25Ca, R26Ca, R27CiR28Ca are each independently a hydrogen atom or a hydrocarbon group which may be substituted by a number of carbon atoms, and R24Ca is a substituted alkyl group having 1 to 3 carbon atoms, R22Ca, R23Ca, R24Ca, 156591 .doc -17- 201202390 p25Ca, 〇26Ca, u27Cart ij28Ca 八σ 1 R , R , R and R may be the same or different. R 2 Ca is a divalent group having 50 or less carbon atoms, however, The Q1Ca is a group in which one hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q2Ca is obtained by removing two hydrogen atoms from a heterocyclic compound containing a nitrogen atom. In the case of a base, it may be a direct bond. It is selected from the group consisting of R11Ca, R12Ca, R13Ca, R丨4Ca, R丨5Ca, R16Ca, R17Ca, R18Ca, R19Ca, R21Ca, R22Ca, R23Ca, R24Ca, R25Ca, R26Ca, R. Further, two or more groups of R, R and a heterocyclic compound having a nitrogen atom which may be substituted with one or two hydrogen atoms may be bonded to each other to form a ring. In the formula, Q丨Cb is -P(R丨2)2, _As(Rl2Cb)2, and heterocyclic ringing of a nitrogen atom which can be substituted The base from which a hydrogen atom is removed, -n(r丨, 十丨, _〇·, _s-, _s(=0)2〇·, _c(=〇)〇·, p(4) (R15Cb) 2. -As(=0)(R_)2, -P(=S)(RnCb)2, -As(=s)(Rl8Cb)2, -CN, -〇H, -SH, -C(=0 ) 0H, -S(=〇)2〇h, _SR丨9Cb, or -C(=〇)N(R21Cb)2. R11Cb, R12Cb, R丨3Cb, Ri5Cb, Rl6Cb, , RUCb, and RhCb are each independently hydrogen An atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R14Cb&R19Cb are independently a substituted alkyl group having 1 to 30 carbon atoms, and R"Cb, R12Cb, Rncb, Rl4Cb, Rl5Cb, R16Cb 17Cb, R18Cb, R 19Cb „ VICb-r \ , RRR and R may be the same or different. Q2C1 -P(R22Cb)-, -As(R23cb)·, removed from a heterocyclic compound containing a nitrogen atom which may be substituted a group of two hydrogen atoms, _N(R24Cb)_, _P(=〇)(R25Cb)-, -As(=0)(R26Cb)·, _P(=s)(R27Cb)·, (R2SCb). 〇R22Cb . R23Cb . R25Cb ^ R26Cb ^ •18· 156591.doc s 201202390 A hydrocarbon group which is a hydrogen atom or a carbon atom which may be substituted, R24cb is a substitutable atomic number of alkyl group of 30, R22Cb, , R24Cb, R25Cb, R26Cb, r27c c Mb, and the same can be different. R2Cb is a carbon number of 5 (a divalent group at m, ", in the case where the bonded QlCb is a group derived from a nitrogen atom in a heterocyclic compound containing a nitrogen atom, or a bonded Q - In the case where a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R eb is a trivalent group having 5 or less carbon atoms. From R" Cb, R (10), Yan, Rl4Cb, R] 5Cb, ruler (10), ruler (10) Rb, R (10), R21Cb, R22Cb, R23Cb, R24cb, r recommended,

R 27Cb 28Cb 、R 、R Cb及自可經取代之含氮原子之雜環 式化合物中去W個〜2個氫原子而成的基中的⑽以上之基 亦可任意鍵結而形成環。 式（Cc)中，（^為_P(Rnce)2、·_12、2、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -N(R，(R，、_〇、_S-、评〇)2〇•、㈣^ (R15Ce)2、-As(=0)(R，2、_P(=s)(Rl7Cc)2、_As(=s)(Ri8、、 -CN、-OH、-SH、-C(=0)〇H、-S(=〇)2〇h、-SRi9Cc、或The group of (10) or more in which R 27Cb 28Cb , R , R Cb and a heterocyclic compound having a nitrogen atom which may be substituted may have W to 2 hydrogen atoms may be arbitrarily bonded to form a ring. In the formula (Cc), (^ is _P(Rnce) 2, ·_12, 2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R, (R,, _〇, _S-, evaluation) 2〇•, (4)^ (R15Ce)2, -As(=0)(R,2, _P(=s)(Rl7Cc)2, _As(=s) (Ri8, -CN, -OH, -SH, -C(=0)〇H, -S(=〇)2〇h, -SRi9Cc, or

R -C(=〇)N(R21Cc)2。R11Cc、Ri2Cc、RRnce、Rl8Ce及R21Ce分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，WARi9Ce分別獨立為可經取代之碳 原子數 1〜30之烷基，R11Cc、R12CC、Ri3Ce、Rl4Cc、Ri5CeR 、R 、R 、R及R21。可分別相同亦可不同。 Q2Ccg -P(R22Cc)-、-As(R23Ce)_、自可經取代之含氮原子 13CcR - C (= 〇) N (R21Cc) 2. R11Cc, Ri2Cc, RRnce, Rl8Ce and R21Ce are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and WARa9Ce is independently a substituted alkyl group having 1 to 30 carbon atoms, R11Cc, R12CC, Ri3Ce, Rl4Cc, Ri5CeR, R, R, R and R21. They can be the same or different. Q2Ccg -P(R22Cc)-, -As(R23Ce)_, self-substitutable nitrogen-containing atom 13Cc

R l5CcR l5Cc

R 16Cc 156591.doc •19· 201202390 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Cc)_、R 16Cc 156591.doc •19· 201202390 A heterocyclic compound in which two hydrogen atoms are removed, _N(R24Cc)_,

-P(=〇)(R25Cc)-、-As(=〇)(R26Cc)_、 27C 立為氫原子或可經取代之碳原子數】〜50之烴基，R24C。為可 經取代之碳原子數1〜30之烧基，r22Cc、r23Cc、r24Cc、 R 、R 、R27Ce及1128(：<:可分別相同亦可不同。 Q3Ce為P、As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As(=0)、p(=s)、 或 As(=S)。 R2Cc為碳原子數50以下之2價基，然而，於所鍵結之qicc 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，所鍵結之Q2Cc為自含氮原子之雜環式化合物中去 掉2個氫原子而成的基之情形，或所鍵結之…以為自含氮 原子之雜環式化合物中去掉3個氫原子而成的基之情形 時，亦可為直接鍵結。 選自 R11Cc、R12Cc、R13CC、rI4Cc、rI5Cc、r16Cc、r17Cc、 r18Cc、Rl9Ce、r21Cg、r22Cg、r23Cc、、r25Cc、r26Cc、 r 、R28Ce、R2Ce及自可經取代之含氮原子之雜環式化合 物中去掉1〜3個氫原子而成的基中的2個以上之基亦可任意 鍵結而形成環。 式（Cd)中 ’ QlCd 為 _P(RHCd)2、_As(Rl2Cd)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Cd)(R14Cd)、_〇.、、_s(=〇)2〇.、_c(=〇)〇.、_p(=〇) (R15Cd)2、_As(=0)(R16Cd)2、-P(=s)(R17Cd)2、_As(=S)(R18Cd)2、 156591.doc .20- s 201202390 -cN、_OH、-SH、-C(=0)0H、_s(=〇)2〇h、sRi9cd、或 -C(=〇)N(R21Cd)2。R11Cd ' R以d、Rl3Cd、Rl5Cd、Ri6cd、 RUCd、RWCd 及 R21Cd 分別 ~乳屌于或可經取代之碳原 子數1〜50之烴基’ R14Cd&R19Cd分 刀別獨立為可經取代之碳-P(=〇)(R25Cc)-, -As(=〇)(R26Cc)_, 27C is a hydrogen atom or a carbon atom which may be substituted] to 50, a hydrocarbon group, R24C. R12Cc, r23Cc, r24Cc, R, R, R27Ce and 1128(:<: may be the same or different, respectively, which may be substituted with a carbon atom having 1 to 30 carbon atoms. Q3Ce is P, As, self-substitutable a group in which three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, N, p(=〇), As(=0), p(=s), or As(=S). R2Cc is carbon a divalent group having an atomic number of 50 or less. However, in the case where the bonded qicc is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, the bonded Q2Cc is a self-containing nitrogen atom. In the case where the two hydrogen atoms are removed from the heterocyclic compound, or the bonded group is considered to be a group in which three hydrogen atoms are removed from the heterocyclic compound containing a nitrogen atom, For direct bonding, selected from R11Cc, R12Cc, R13CC, rI4Cc, rI5Cc, r16Cc, r17Cc, r18Cc, Rl9Ce, r21Cg, r22Cg, r23Cc, r25Cc, r26Cc, r, R28Ce, R2Ce and self-substitutable nitrogen-containing atoms In the heterocyclic compound, two or more groups in which one or three hydrogen atoms are removed may be bonded to each other to form a ring. In the formula (Cd), 'QlCd is _ P(RHCd)2, _As(Rl2Cd)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R13Cd)(R14Cd), _〇., _s(=〇)2〇., _c(=〇)〇., _p(=〇) (R15Cd)2, _As(=0)(R16Cd)2, -P(=s)(R17Cd)2, _As( =S)(R18Cd)2, 156591.doc .20- s 201202390 -cN, _OH, -SH, -C(=0)0H, _s(=〇)2〇h, sRi9cd, or -C(=〇) N(R21Cd)2. R11Cd 'R is d, Rl3Cd, Rl5Cd, Ri6cd, RUCd, RWCd and R21Cd respectively ~ chylo- or substituted hydrocarbyl groups of 1~50 carbon atoms' R14Cd&R19Cd Substitutable carbon

原子數1〜30之烷基，R"Cd、R12Cd、R 13CdAlkyl group with an atomic number of 1 to 30, R"Cd, R12Cd, R 13Cd

R 14CdR 14Cd

R 15CdR 15Cd

R 16CdR 16Cd

R 17CdR 17Cd

R 18Cd R19Cc^R21Cd可分別相同亦可不同 Q⑽為-P(R，-、-As(R，.、自可經取代之含氛原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Cd)_、 -P㈣(R25,、_As(=〇)(R26Cd)…·p(=s)(R27Cd)、或 a㈣(R，W ' R23Cd、R25Cd、R26Cd、R27、R28Cd分別獨 立為氫原子或可經取代之碳原子數丨〜5〇之烴基，R24Cd為可 經取代之碳原子數1〜30之烷基，RUCd、R23Cd、r24C<j、 R25Cd、R26Cd R27Cd β 八如 士 K 及R 可分別相同亦可不同。 2 C d R 為碳原子數50以下之2價基，然而，於所鍵結之QlCd 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之Q2Cd為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時’亦可為直接鍵結。 R3Cd為碳原子數50以下之3價基。 選自 R11Cd、Rl2Cd、R"cd、Rl4Cd、Rl5Cd、RUCd、尺⑽、 R 、Rl9Cd、R2lCd、R22Cd、R23Cd、R24C；d、r25C(J、R26(：d、 R27ed、、心、R3Cd及自可經取代之含氮原子之雜環 式化合物中去掉1個〜2個氫原子而成的基中的2個以上之基 亦可任意鍵結而形成環。 式（Ce)中，q丨ce 為 _p(Rnce)2、·Α5(κι2(：β)2、自可經取代 156591.doc • 21- 201202390 之含^原子之雜環式化合物中去掉+ •T： )(RMCC)'·0^ (R )2 > -As(=〇)(R-Ce)2 . .p(=S)(Rl7Ce)2 ^ .As(=S)(Rl8Ce)2 ^ -CN、-0H、_SH、-C(=〇)〇H、_s(=〇)2〇h、、或 •C( = 〇)N(R2 丨％。R丨丨。、R〗2Ce、RUCe、尺15。、严、 R^e、Rl8Ce及尺2心分別獨立 ~氧项于或可經取代之碳原 子數1〜50之烴基，Rl4Ce及丨9C ^ 刀別獨立為可經取代之 原子數1〜30之烷基，R"Ce、R12Ce、 13Ce 碳 、R1 R’、Rl7Ce、Rl8Ce、r19、r21、分別相同亦可不同。 Q心為-P(R，·、-As〇自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Ce)_、 . .As(=〇)(R26ce). . .P(=S)(R27ce). ^ ^ _As(=s) (R —)- 〇 R-Ce . R23Ce , R25Ce . R26Ce ^ R27CeaR28Ce^^^ 立為風原子或可經取代之碳原子數1〜5〇之烴基，R24Ce為可 經取代之碳原子數1〜30之烷基，R22Ce、R23Ce、R24Ce、 R25Ce、R26Ce、以心及以…可分別相同亦可不同。 R2(：e為碳原子數5〇以下之2價基，然而，於所鍵結之QiCe 為自含氮原子之雜環式化合物中去掉1個氩原子而成的基 之情形，或所鍵結之Q2Ce為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 R4。為碳原子數70以下之4價基。R 18Cd R19Cc^R21Cd may be the same or different Q(10) is -P(R,-, -As(R,., a group obtained by removing two hydrogen atoms from a heterocyclic compound having a substituted atomic group) , _N(R24Cd)_, -P(4)(R25,, _As(=〇)(R26Cd)...·p(=s)(R27Cd), or a(four)(R,W ' R23Cd, R25Cd, R26Cd, R27, R28Cd are independent a hydrogen atom or a hydrocarbon group having a carbon number of 丨~5〇, R24Cd is a substitutable alkyl group having 1 to 30 carbon atoms, and RUCd, R23Cd, r24C<j, R25Cd, R26Cd R27Cd β K and R may be the same or different. 2 C d R is a divalent group having 50 or less carbon atoms, however, the bonded QlCd is one in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom. In the case of a group, or when the bonded Q2Cd is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R3Cd is 50 or less carbon atoms. a trivalent group selected from the group consisting of R11Cd, Rl2Cd, R"cd, Rl4Cd, Rl5Cd, RUCd, ruler (10), R, Rl9Cd, R2lCd, R22Cd, R23Cd, R24C; d, r25C (J, R26(:d, R27ed, heart, Two or more groups of R3Cd and a group obtained by removing one to two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted may be arbitrarily bonded to form a ring. In the formula (Ce), Q丨ce is _p(Rnce)2,·Α5(κι2(:β)2, and can be removed by the substitution of 156591.doc • 21-201202390 of the heterocyclic compound containing ^ atom: + • T: ) (RMCC )'·0^ (R )2 > -As(=〇)(R-Ce)2 . .p(=S)(Rl7Ce)2 ^ .As(=S)(Rl8Ce)2 ^ -CN,- 0H, _SH, -C(=〇)〇H, _s(=〇)2〇h, or •C(=〇)N(R2 丨%. R丨丨., R〗 2Ce, RUCe, ruler 15. , R, e, Rl8Ce and 尺2 core are respectively independent ~ oxygen or substituted carbon atom with 1 to 50 carbon atoms, Rl4Ce and 丨9C ^ are independent of the number of atoms that can be substituted 1~30 The alkyl group, R"Ce, R12Ce, 13Ce carbon, R1 R', Rl7Ce, Rl8Ce, r19, r21, respectively, may be different. Q core is -P(R, ·, -As〇 can be substituted A group in which a hydrogen atom is removed from a heterocyclic compound of a nitrogen atom, _N(R24Ce)_, . . . (=〇)(R26ce). . .P(=S)(R27ce). ^ ^ _As( =s) (R —)- 〇R-Ce . R23Ce , R25Ce R26Ce ^ R27CeaR28Ce^^^ is a hydrocarbon atom or a substituted hydrocarbon group having 1 to 5 carbon atoms, R24Ce is a substituted alkyl group having 1 to 30 carbon atoms, R22Ce, R23Ce, R24Ce, R25Ce, R26Ce, heart and ... can be the same or different. R2(:e is a divalent group having a carbon number of 5 Å or less, however, the bonded QiCe is a group in which one argon atom is removed from a heterocyclic compound containing a nitrogen atom, or a bond When Q2Ce is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R4 is a tetravalent group having 70 or less carbon atoms.

選自 R11Ce、R12Ce、R13Ce、R !4CeFrom R11Ce, R12Ce, R13Ce, R !4Ce

RlSCe、j^i9CeRlSCe, j^i9Ce

R 27C(R 27C(

Rl5Ce R21Ce、R22Ce、R23Ce、R24Ce R&e、R4Ce及自可經取代之含氮原子之雜環 R28Ce、t>2Ce r. 4CeRl5Ce R21Ce, R22Ce, R23Ce, R24Ce R&e, R4Ce and a heterocyclic ring containing a nitrogen atom which may be substituted R28Ce, t> 2Ce r. 4Ce

Rl6Ce、Rl7Ce R25Ce、R26Ce 156591.doc -22- s 201202390 式化合物中去掉1個〜2個氫原子而成的基中的2個以上之基 亦可任意鍵結而形成環。 式（Cf)中，Q旧為-P(RllCf)2、_As(Rl2Cf)2、自可經取代之 含氮原子之雜環式化合物中去掉i個氫原子而成的基、 _N(Rl3Cf)(Rl4Cf)、-〇-、_s·、s( = 〇)2〇.、c(=⑺〇、p卜⑺ (R15Cf)2、-As(=0)(R16Cf)2、-P(=S)(Ri7cf)2、As(=s)(Rl8Cf)2、 -CN、-〇H、-SH、-C(=〇)〇H、-S(=〇)2〇h、-SR19Cf、或 -C( = 〇)N(R21Cf)2。R"Cf、R12Cf、 P 17Cf ^ „ i»rf__” nRl6Ce, Rl7Ce R25Ce, R26Ce 156591.doc -22- s 201202390 Two or more groups in which one to two hydrogen atoms are removed from the compound of the formula may be arbitrarily bonded to form a ring. In the formula (Cf), Q is -P(RllCf)2, _As(Rl2Cf)2, a group obtained by removing i hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, and _N(Rl3Cf) (Rl4Cf), -〇-, _s·, s( = 〇)2〇., c(=(7)〇, p(7) (R15Cf)2, -As(=0)(R16Cf)2, -P(=S )(Ri7cf)2, As(=s)(Rl8Cf)2, -CN, -〇H, -SH, -C(=〇)〇H, -S(=〇)2〇h, -SR19Cf, or - C( = 〇)N(R21Cf)2. R"Cf, R12Cf, P 17Cf ^ „ i»rf__” n

R 13CfR 13Cf

R 15CfR 15Cf

R 16Cf R 7Cf、R⑽及R而分別獨立錢原子或可經取代之碳原子 數1〜5〇之烴基’ Rl^R⑽分別獨立為可經取代之碳原子 叙 Dni u _ 1 1 r-r ____ 數1〜30之烷基”认、k—、r™、Ri r\^Cf ^ * 1 J j M'AS'自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As㈣ 或 As(=S)。 ::為碳原子數5。以下之2價基，然而，於所鍵結之^ 二心T之雜環式化合物中去掉1個氨原子而成的基 疋滑形，或所鍵結之Q3Cf為自 去掉3個㈣子w㈤氮原子之雜環式化合物中 R3CfA而成的基之情形時’亦可為直接鍵結。 為石反原子數50以下之3價基。R 16Cf R 7Cf, R(10) and R, respectively, independently a carbon atom or a substituted hydrocarbon group having 1 to 5 moles of a hydrocarbon group 'Rl^R(10), respectively, independently a carbon atom which can be substituted, Dni u _ 1 1 rr ____ number 1 〜30的 alkyl", k-, rTM, Ri r\^Cf ^ * 1 J j M'AS' is obtained by removing three hydrogen atoms from a heterocyclic compound containing a nitrogen atom which may be substituted Base, N, p (= 〇), As (four) or As (= S). :: is a carbon atom number of 5. The following two valent groups, however, removed from the bonded heterocyclic compound of the two-heart T The base slip formed by one ammonia atom, or the bonded Q3Cf is a group in which R3CfA in a heterocyclic compound of three (four) sub-w(f) nitrogen atoms is removed, and may be a direct bond. It is a trivalent group having a stone antiatomic number of 50 or less.

R I ICfR I ICf

R 12CfR 12Cf

R 13CfR 13Cf

R 14Cf 15Cf 選自R⑽、Rl2Cf、Rncf、尺贈 Ri8Cf 〗9C 、R 、R16Cf、R17Cf、 K ' R2，Cf . R^Cf , R3Cf _ 之雜環式& A & 17經取代之含氮原子 式化合物令去掉1個或3個氫片不1二 以上之其亦-τν色 飞原子而成的基申的2個 土 、可任思鍵結而形成環。 J 56591.d0) -23- 201202390 式（Cg)中 ’Q1Cga-P(RnCg)2、-As(R12Cg)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Cg)(R14Cg)、_〇、-S'、-S(=0)20.、·(：（=〇)〇、·ρ(=〇) (R15Cg)2 ' -As(=0)(R16Cg)2 ' -P(=S)(R17C^)2，-As(=S)(R,8cS)2 . -CN、-OH ' -SH、-C(=0)0H、-S(=0)2〇H、-SR19Cg、或 _C(=0)N(R21Cg)2 〇 R11Cg、R12Cg、R13Cg、Ri5Cg、Rl6Cg、 r g、R18Cg及R21Cg分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R14Cg&R19Cg分別獨立為可經取代之碳 原子數 1 〜30之烷基，R11Cg、R12Cg、R13Cg、R“cg、Rl5Cg、 R1^、Rwg、Rl8Cg、Rl9C^R21Cg可分別相同亦可不同。 Q2Cg為-P(R22Cg)-、-As(R23Cg)-、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、-N(R24cg>、 -P(=0)(R25Cg)-、-As(=0)(R26Cg)-、-P(=S)(R27Cg)-、或 _As(=s) (R28CS)-。R22Cg、R23Cg、R25Cg、R26Cg、R27Cg&R28Cg分別獨 立為氫原子或可經取代之碳原子數1〜50之烴基，R24Cg為可 經取代之碳原子數1〜30之烷基，R22cg、R23Cg、R24Cg、 R25Cg、R26C：g、R27Cg及R28Cg可分別相同亦可不同。 R3eg為碳原子數50以下之3價基。 選自 RllCg、R12Cg、R13Cg、R14Cg、R15Cg、R16Cg、R】7Cg、 R丨 8Cg、Rl9Cg、R21Cg、R22Cg、R23Cg、R24Cg、R25Cg、R26Cg、 R 7eg、R28eg、r3Cs及自可經取代之含氮原子之雜環式化合 物中去掉1個〜2個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 式（Ch)中，Q丨ηΛ_ρ(κηα)2、_As(R〗2Ch)2 '自可經取代 15659丨.doc -24· 201202390 之含氛原子之雜環式化合物中去掉1 γ -N(R13Ch)(R14Ch)、·〇_、_S·、_s 〇 固氧原子而成的基、 (R15Ch)2 ^ -As(=0)(R-h)2 . ,P(=S)(r127 ' 'C(=〇)〇' ' -P(=〇) -CN、-OH、-SH、-C(=0)0H、_s 、X )2 十0)2〇H、-SR19Ch、哎 -C(=0)N(R21Ch)2。R"ch、r12c 汊 K > J>*5Ch ^ p]6Ch pl7Ch T>18Chrt r»21Ch,x rt. ^ ^ R 'R及及分別獨立為氫眉 L席子或可經取代之碳原 子數1~50之烴基’ R丨似及汉丨似公 刀別獨立為可經取代之碳 原子數1~30之烷基，R1丨Ch、Rl2Ch Λ 、R Lh、Rl4Ch、R 15Ch、 -16Ch …· ---- ^R 14Cf 15Cf is selected from the group consisting of R(10), Rl2Cf, Rncf, R8, R8, R16, R16, C16, R1Cf, R3Cf, R3Cf_, heterocyclic formula & A & 17 substituted nitrogen The atomic compound is such that two or three hydrogen sheets are removed, and the two soils, which are also formed by the -τν color flying atom, can be bonded to form a ring. J 56591.d0) -23- 201202390 In the formula (Cg), 'Q1Cga-P(RnCg)2, -As(R12Cg)2, one hydrogen atom is removed from the heterocyclic compound having a nitrogen atom which may be substituted The group formed, -N(R13Cg)(R14Cg), _〇, -S', -S(=0)20.,·(:(=〇)〇,·ρ(=〇) (R15Cg)2 ' - As(=0)(R16Cg)2 ' -P(=S)(R17C^)2, -As(=S)(R,8cS)2 . -CN, -OH ' -SH, -C(=0) 0H, -S(=0)2〇H, -SR19Cg, or _C(=0)N(R21Cg)2 〇R11Cg, R12Cg, R13Cg, Ri5Cg, Rl6Cg, rg, R18Cg and R21Cg are each independently a hydrogen atom or may be The substituted hydrocarbon group having 1 to 50 carbon atoms, R14Cg&R19Cg are each independently a substituted alkyl group having 1 to 30 carbon atoms, R11Cg, R12Cg, R13Cg, R"cg, Rl5Cg, R1^, Rwg, Rl8Cg Rl9C^R21Cg may be the same or different. Q2Cg is -P(R22Cg)-, -As(R23Cg)-, a base obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted , -N(R24cg>, -P(=0)(R25Cg)-, -As(=0)(R26Cg)-, -P(=S)(R27Cg)-, or _As(=s) (R28CS) - R22Cg, R23Cg, R25Cg, R26Cg, R27Cg& R28Cg are each independently a hydrogen atom or may be substituted a hydrocarbon group having 1 to 50 atoms, R24Cg being a substitutable alkyl group having 1 to 30 carbon atoms, and R22cg, R23Cg, R24Cg, R25Cg, R26C:g, R27Cg and R28Cg may be the same or different. R3eg is a carbon atom. a trivalent group having a number of 50 or less. From R11Cg, R12Cg, R13Cg, R14Cg, R15Cg, R16Cg, R7Cg, R丨8Cg, Rl9Cg, R21Cg, R22Cg, R23Cg, R24Cg, R25Cg, R26Cg, R 7eg, R28eg, r3Cs And two or more groups in which the one or two hydrogen atoms are removed from the heterocyclic compound having a nitrogen atom which may be substituted may be arbitrarily bonded to form a ring. In the formula (Ch), Q丨ηΛ_ρ(κηα)2, _As(R]2Ch)2 'Removal of 1 γ -N(R13Ch)(R14Ch) from a heterocyclic compound containing an aromatic atom of 15659丨.doc -24· 201202390 〇_, _S·, _s The base of the enthalpy oxygen atom, (R15Ch)2 ^ -As(=0)(Rh)2 . , P(=S)(r127 ' 'C(=〇)〇' ' -P(=〇) -CN, -OH, -SH, -C(=0)0H, _s, X)2 Ten 0) 2〇H, -SR19Ch, 哎-C(=0)N(R21Ch)2 . R"ch,r12c 汊K >J>*5Ch ^ p]6Ch pl7Ch T>18Chrt r»21Ch,x rt. ^ ^ R 'R and the number of carbon atoms independently of hydrogen eyebrows or substituted 1~50 hydrocarbon group 'R丨like and Han 丨like public knives are independent of the alkyl group with 1~30 carbon atoms which can be substituted, R1丨Ch, Rl2Ch Λ, R Lh, Rl4Ch, R 15Ch, -16Ch ... · ---- ^

RR

R 17ChR 17Ch

R 18ChR 18Ch

Rl9、R21Ch可分別相同亦可不同 Q4Ch為含有可配位於Ag、P、含氮原子之雜環式化合物 中之N、0_、或S.t之任-個的碳原子數7()以下之4價基。 R2Ch為碳原子數50以下之2價|，然而，於所鍵結之Qich 為自含氮原子之雜環式化合物中去㈤個氫原子而成的基 之情形時，亦可為直接鍵結。 選自 R丨丨Ch、RUCh、R13Ch、Rl4Ch、Rl5Ch、Rl6Ch、Ri7ch、 RlSCh、Rl9Ch、R21Ch 2Ch R Q及自可經取代之含氮原子 之雜環式化合物中去掉丨個氫原子而成的基中的2個以上之 基亦可任意鍵結而形成環。 式（Ci)中，QlCi 為 _p(RllCi)2、_As(Ri2Ci)2、自可經取代之 3氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(Rl3Cl)(Rl4Cl)、-0、-S·、-S(=0)20·、-C(=〇)〇-、·ρ(=0) (R15C,)2 ' -As(=〇)(Ri6Ci)2 ^ _p(=S)(R17Ci)2 ^ -As(=S)(R18Ci)2 > -CN、-OH、-SH、-C(=0)0H、-S(=0)20H、-SR19Ci、或 _C( = 0)N(R2ICi)2。RllCi、R12Ci、R13Ci、Rl5Ci、Rl6Ci、 156591.doc -25- 201202390 R '、Rm別獨立為氫原子或可經取代 數卜50之録，、可經取代之碳原子數^ 抄 r, 1 ICi ^ l^r； ^ I ir- ： ____ ^ 烷基，R—、、w、RuCi、Rl5Ci、Rl6Ci、Ri7ci、 R18ei、R19c^R21Ci可分別相同亦可不同e R5Gi為碳原子數100以下之5價基。Rl9 and R21Ch may be the same or different, and Q4Ch is a valence of 4 or less carbon atoms having 7 or more carbon atoms of N, 0, or St which may be coordinated to a heterocyclic compound of Ag, P or a nitrogen atom. base. R2Ch is a valence of 50 or less carbon atoms; however, in the case where the bonded Qich is a group of (f) hydrogen atoms from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. . a group selected from the group consisting of R丨丨Ch, RUCh, R13Ch, Rl4Ch, Rl5Ch, Rl6Ch, Ri7ch, RlSCh, Rl9Ch, R21Ch 2Ch RQ and a heterocyclic compound having a nitrogen atom which may be substituted, wherein one hydrogen atom is removed Two or more of the groups may be arbitrarily bonded to form a ring. In the formula (Ci), QlCi is _p(RllCi)2, _As(Ri2Ci)2, a group obtained by removing one hydrogen atom from a heterocyclic compound of a nitrogen atom which may be substituted, -N(Rl3Cl) (Rl4Cl), -0, -S·, -S(=0)20·, -C(=〇)〇-,·ρ(=0) (R15C,)2 ' -As(=〇)(Ri6Ci) 2 ^ _p(=S)(R17Ci)2 ^ -As(=S)(R18Ci)2 > -CN, -OH, -SH, -C(=0)0H, -S(=0)20H,- SR19Ci, or _C( = 0)N(R2ICi)2. RllCi, R12Ci, R13Ci, Rl5Ci, Rl6Ci, 156591.doc -25- 201202390 R ', Rm is independently hydrogen atom or can be substituted by number 50, the number of carbon atoms which can be substituted ^ copy r, 1 ICi ^ l^r; ^ I ir- : ____ ^ alkyl, R—, w, RuCi, Rl5Ci, Rl6Ci, Ri7ci, R18ei, R19c^R21Ci may be the same or different e R5Gi is 5 or less of carbon atoms Price base.

選自R HCiFrom R HCi

R 12Ci _ R13Ci、Rl4Ci、Rl5Ci、尺16。R 12Ci _ R13Ci, Rl4Ci, Rl5Ci, ruler 16.

R l7Ci RUCi、R^i、RhCi、R5Ci及自可經取代之含氮原子之雜環 式化合物中去掉1個氫原子而成的基中的2個以上之基亦可 任意鍵結而形成環。 [化 2-1] Q1 20a/ R or 2 OVQ 2 N R 2 -0> ,Rl、Da 〆，0 < 20% R /3R l7Ci RUCi, R^i, RhCi, R5Ci and two or more groups in which a hydrogen atom is removed from a heterocyclic compound having a nitrogen atom which may be substituted may be arbitrarily bonded to form a ring. . [Chem. 2-1] Q1 20a/ R or 2 OVQ 2 N R 2 -0> , Rl, Da 〆, 0 < 20% R /3

Da 1 ΌDa 1 Ό

b / 1DS 1Qb / 1DS 1Q

υ 3Dυ 3D

Db R—1QDb R-1Q

RR

H •t R20H •t R20

RR

Db 1 QDb 1 Q

(D(D

Dc/ 1 QDc/ 1 Q

q1dc2DC Qrc/R 2RIQIq1dc2DC Qrc/R 2RIQI

〆0 2D R QlDC〆0 2D R QlDC

Rz,Rz,

Dc 1 QDc 1 Q

DdDdDd q1i4r—q1 g- 1 Q 一一 iDd)DdDdDd q1i4r—q1 g- 1 Q one by one iDd)

sR2DsR2D

Dd 1 QDd 1 Q

s、 1 Qs, 1 Q

RR

2D f R 2D/ 9 Df S/R 1 ^ Q% 2De/R% 2re) 2De/(D Q 'DeDe 3 1 e RIQ2D f R 2D/ 9 Df S/R 1 ^ Q% 2De/R% 2re) 2De/(D Q 'DeDe 3 1 e RIQ

2 R R IQ° #(\ -qD,2 R R IQ° #(\ -qD,

R -26· 15659丨.doc 201202390R -26· 15659丨.doc 201202390

〇iDg R2DfQ | 〇'<气2〇，气硝 Q1Dg q1Cr3D〆之hR2Dh - | Q1Dg (Dg) Q1Dh (Dh) Q1Di n1Di 〇2Di_p4Di_ 2Di 1Di Q、R2Di'Q 7 Q、R2DrQ Q1Di Q1〇j ， 、R3Dj (JjIDj djIDj (Di) (Dj) 〇1叫 〇1Dk _2DK，U „2Dk"U n1DI R2Dr〇 I 〇1Dh 之 2Dh’U I 、3Dh ^IDh 3\R2Dh，Q I I n1Dk n3Dk n3Dk n1Dk U、R2Dk'U、R2Dk'U\R2DliU 〇1DI 〇3DI 〇2DI 〇1 υ \R2Dru\R3Dru\R2DrQ (Dk) q1di (Dl) [化 2-2]〇iDg R2DfQ | 〇 '< gas 2 〇, gas nitrous oxide Q1Dg q1Cr3D 〆 hR2Dh - | Q1Dg (Dg) Q1Dh (Dh) Q1Di n1Di 〇2Di_p4Di_ 2Di 1Di Q, R2Di'Q 7 Q, R2DrQ Q1Di Q1〇j , , R3Dj (JjIDj djIDj (Di) (Dj) 〇1 is called 1Dk _2DK, U „2Dk"U n1DI R2Dr〇I 〇1Dh 2Dh'UI, 3Dh ^IDh 3\R2Dh, QII n1Dk n3Dk n3Dk n1Dk U, R2Dk'U , R2Dk'U\R2DliU 〇1DI 〇3DI 〇2DI 〇1 υ \R2Dru\R3Dru\R2DrQ (Dk) q1di (Dl) [Chem. 2-2]

m D1Qm D1Q

KK

TR 2 R m m ) DDP 2 1 ir -m e /R e /Q(D D Q / D / 2 4 / 2 R丨iTR 2 R m m ) DDP 2 1 ir -m e /R e /Q(D D Q / D / 2 4 / 2 R丨i

Dn 2 RDn 2 R

m D1Qm D1Q

D、 1Q 3R—Q10D, 1Q 3R-Q10

DnDn

D1QD1Q

Q 3DQ 3D

:lQ1D:lQ1D

DoDo/ 2RI3Q I DODODO 14 1 Q— R——Q i D0 01DDoDo / 2RI3Q I DODODO 14 1 Q— R——Q i D0 01D

D0 1 Q Q ° D 2 D0 2IN Q I p p p D D D 14 1 Q— R—Q i Dp q1dD0 1 Q Q ° D 2 D0 2IN Q I p p p D D D 14 1 Q— R—Q i Dp q1d

§Dp 3 1 R— Q§Dp 3 1 R— Q

Dp 1 QDp 1 Q

1Dq/ 1Q1Dq/ 1Q

2 R——Q2 R——Q

Dq 1Q 〆Dq 1Q 〆

(D(D

RDq Dq^ T1QRDq Dq^ T1Q

Dq1Q V q D D 2 1 R Q 4Dq/2Dq/Dq1Q V q D D 2 1 R Q 4Dq/2Dq/

Dr/ 1QDr/ 1Q

DrDr

Dr/ 1 QDr/ 1 Q

RR

Dr )〆r vr D D 2D2r 1q DrR$ 叫 2R\ / ( Q/DSDs \/5r—q1 1DSDS- a 10Dr )〆r vr D D 2D2r 1q DrR$ is called 2R\ / ( Q/DSDs \/5r—q1 1DSDS- a 10

DsDs

2 R2 R

Ds 1 QDs 1 Q

s) (Ds) (D

s-q1ds x6Dt\Q o 1Dt1Q QS-q1ds x6Dt\Q o 1Dt1Q Q

Q I5659l.doc •27 201202390 式（Da)中，Qi、_P(R"Da)2、_As(Rl2Da)2、自可經取代 之含策原子之雜環式化合物中去掉！個氫原子而成的基、 娜、_σ、_s·、_s(=q)2。·、·㈣)。·、_p㈣ (R1,2、_As(=〇)(Rl6Da)2、_p(=s)(Rl7Da)2、_As(=s)(Ri8Da)2、 -CN、-〇H、-SH、-C(=〇)〇H、_S(=〇)2〇H、_SRl9Da、或 •C( = 0)N(R21Da)2。RHDa、Rl2Da、、以以、 R R及R分別獨立為氫原子或可經取代之碳原Q I5659l.doc •27 201202390 In the formula (Da), Qi, _P (R" Da) 2, _As (Rl2Da) 2, are removed from the heterocyclic compound containing a substituted atom! A group of hydrogen atoms, Na, _σ, _s·, _s(=q)2. ·, · (4)). ·, _p (four) (R1, 2, _As (= 〇) (Rl6Da) 2, _p (= s) (Rl7Da) 2, _As (= s) (Ri8Da) 2, -CN, -〇H, -SH, -C (=〇)〇H, _S(=〇)2〇H, _SRl9Da, or •C(= 0)N(R21Da)2. RHDa, Rl2Da, and Y, RR and R are each independently a hydrogen atom or can be Substituted carbon

R16Da、R…a、R 子數1〜50之烴基，Rl4、R19Da分別獨立為可經取代之碳 原子數1〜30之炫1基，RUDa、Rl2Da、Rl3Da、^仙、尺丨❿、 18Da p 20Da η n 2 1 Da R 及R 1Da可分別相同亦可不同e •As(R23Da)_、自可經取代之含氮原子 7Da Q2D4 -P(R22Da)· 之雜環式化合物中去掉2個氫原子而成的*、-N(R24Da)· -P(=〇XR2，-、-As(=0)(r2，_、作咖，、或 _As㈣R16Da, R...a, R group of hydrocarbons of 1 to 50, Rl4 and R19Da are each independently a substitutable carbon atom having 1 to 30 carbon atoms, RUDa, Rl2Da, Rl3Da, ^xian, 丨❿, 18Da p 20Da η n 2 1 Da R and R 1Da may be the same or different e • As(R23Da)_, and 2 of the heterocyclic compounds of the nitrogen-containing atom 7Da Q2D4 -P(R22Da)· which may be substituted *, -N(R24Da)· -P(=〇XR2,-, -As(=0)(r2,_, 咖,, or _As(4))

R 24Di (R’“严、R23Da、R25Da、R26Da、严及严分別獨 立為氫原子或可經取代之碳原子數^50之烴基，R24Da為可 經取代之碳原子數1〜3〇之烷基，R22〇a、r23d π: R26Da、R27、R28Da可分別相同亦可不同 R2Da為碳原子數50以下之2價基u，於所鍵結之QlDa 為自含氮原子之雜環式化合物中去掉i個氯原子而成的基 之情形，或所鍵結之Q2Da為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 選自 R丨丨Da、Rl2Da、RnDa、R〗4Da、R,5Da、Ri6Da、Ri7Da、 R 丨咖、严、R2】Da、R22Da、R23Da、R24Da、严、^ R2-、R狐、R2、自可經取代之含氮原子之雜環式化合 15659 丨.docR 24Di (R'", R23Da, R25Da, R26Da, strictly and strictly independently a hydrogen atom or a substituted hydrocarbon group having a carbon number of 50, and R24Da is a substitutable carbon atom having 1 to 3 Å. R22〇a, r23d π: R26Da, R27, R28Da may be the same or different, R2Da is a divalent group u having a carbon number of 50 or less, and the bonded QlDa is a heterocyclic compound derived from a nitrogen atom. In the case where a group of i chlorine atoms is removed, or the bonded Q2Da is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. From R丨丨Da, Rl2Da, RnDa, R〗 4Da, R, 5Da, Ri6Da, Ri7Da, R 丨, 、, R2]Da, R22Da, R23Da, R24Da, Yan, ^ R2-, R fox, R2, from Heterocyclic compound of substituted nitrogen atom 15659 丨.doc

S •28· 201202390 物中去掉1個〜2個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 式_中，Q心為-P(R_)2、_As(R⑽)2、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 娜13Db)(Rl4Db)、-〇·、、·δ(=0)2σ、♦〇)〇·、_p(=〇) (R15Db)2、-as(=o)(r_)2、_P(=s)(Rl7Db)2、_As(=s)(r18d、 CN、-〇H、-SH、-C(=〇)〇H、-S(=〇)2〇H、_SRi9Db、或 -C(=0)N(R腦）2。R_、R⑽、Rl3Db、Rl5Db、r16d/、 R_ ' R_及R21Db分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R⑽^及…似分別獨立為可經取代之碳 原子數 1 〜30 之烷基，RHDb、Rl2Db、Rl3Db、Ri4Db、R丨 5Db R_、Rl7Db、Rl8Db、dR_可分別相同亦可不同 Q為-P(R )_、、自可經取代之含氣原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Db)_、 、-As㈣(R_)_、·ρ㈣(R27Db)·、或 A㈣ (R_)-。r，、R_、R25Db、R26Db、r27〜r腿分別 獨立為氫原子或可經取代之碳原子數^50之烴基，尺^^為 可經取代之碳原子數1〜30之烷基，R22〇b、R23Db、R24Db、 π:: 、产及π、分別相同亦可不同。 R2Db為碳原子數50以下之2價基’ _，於所鍵結之QlDb 為自含氮原子之雜環式化合物中去⑴個氫原子而成的基 之清幵V *所鍵結之Q Db為自含氮原子之雜環式化合物中 去掉:固氫原子而成的基之情形時，亦可為直接鍵結。 R 為碳原子數5 0以下之3價基。 15659J.doc -29- 201202390 選自 R"Db、Rl2Db、y、Rl4Db、&_、汉16的、汉憑、 R ⑽、Rl9Db、R2lDb、R22Db、R23Db、R24Db、R25Db、 R26Db、R27Db、汉28Db R2Db、R3Db B ώ K 、R R及自可經取代之含氮原子 之雜環式化合物中去…個〜2個氫原子而成的基中的之個以 上之基亦可任意鍵結而形成環。 式㈣中，dP(R_)2、_As(Rl2Dc)2、自可經取代 之含氮原子之雜環式化合物中去掉i個氮原子而成的基、 _s·、_s(=_·、_c㈣)σ、·ρ㈣ (R15%、-As(=0)(Rl，2、·Ρ(=δ)(κ"%、_As(=s)(r18Dc)2、 _CN、-0H、.SH、_c(=〇)〇H、_s㈣）2〇h、_sr19d、或 -C(=0)N(R隱）2。RnDc、Rl2Dc、r13Dc、汉咖、汉账、 r17Dc、r18Dc及r21Dc分別獨立為氦庙工斗、 j ^马氫原子或可經取代之碳原 子數1〜50之烴基’ R，及R，分別獨立為可經取代之碳 原子數 1 〜30之院基，Rn〇C、R〗2De、Rl3Dc、Rl4Dc、Ri5Dc、 R_、严、RuDe、严及R21De可分別相同亦可不同。、 Q2DU(R22Dc)-、_As(R23Dc)·、 }自可經取代之自氮原子 之雜環式化合物令去掉2個氫原子而成的基、_n(r24Dc) …0)〇、·_=0)〇_、.p(=s)(r2，、或_ (R28De)·。R22De、R23De、R25De e 耻 K 、：R27De 及 r28Dc分別獨 立為氫原子或可經取代之碳原子數丨〜％之烴 να。 經取代之碳原子數丨〜⑽之烷基，R22〇c、W r2仙0 R，、严、严及严可分別相同亦可不同。、 Q 為P、As、自可經取代之冬备 代之3氮原子之雜環式化合物 中去掉3個氫原子而成的基、n、p(=〇)、As㈣叫 15659J.docTwo or more of the groups in which one to two hydrogen atoms are removed from S.28.201202390 may be bonded to form a ring. In the formula _, Q is -P(R_)2, _As(R(10))2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, Na 13Db) (Rl4Db) , -〇·,··δ(=0)2σ, ♦〇)〇·, _p(=〇) (R15Db)2, -as(=o)(r_)2, _P(=s)(Rl7Db)2 , _As(=s)(r18d, CN, -〇H, -SH, -C(=〇)〇H, -S(=〇)2〇H, _SRi9Db, or -C(=0)N(R brain 2) R_, R(10), Rl3Db, Rl5Db, r16d/, R_'R_ and R21Db are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R(10)^ and ... are each independently substituted. The alkyl group having 1 to 30 carbon atoms, RHDb, Rl2Db, Rl3Db, Ri4Db, R丨5Db R_, Rl7Db, Rl8Db, dR_ may be the same or different Q is -P(R)_, self-substitutable a group in which two hydrogen atoms are removed from a heterocyclic compound containing a gas atom, _N(R24Db)_, , -As(tetra)(R_)_, ·ρ(tetra)(R27Db)·, or A(tetra)(R_)-.r, , R_, R25Db, R26Db, r27~r legs are each independently a hydrogen atom or a substituted hydrocarbon group having a carbon number of 50, and the substituent is a substituted alkyl group having 1 to 30 carbon atoms, R22〇b , R23Db, R24Db, ::, and π, respectively, may be different. R2Db is a divalent group having a carbon number of 50 or less ' _, and the bonded QlDb is a (1) hydrogen atom from a heterocyclic compound containing a nitrogen atom. The Q Db bonded to the group V* is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, and may also be a direct bond. R is a carbon number. 3 valence base below 50. 15659J.doc -29- 201202390 From R"Db, Rl2Db, y, Rl4Db, &_, Han 16, Han, R (10), Rl9Db, R2lDb, R22Db, R23Db, R24Db , R25Db, R26Db, R27Db, Han 28Db R2Db, R3Db B ώ K , RR and more than one of the substituents of the nitrogen-containing heterocyclic compound which can be substituted with ~2 hydrogen atoms The group may be bonded to form a ring by any bonding. In the formula (IV), dP(R_)2, _As(Rl2Dc)2, a group obtained by removing i nitrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _s·, _s(=_·, _c(4)) σ,·ρ(4) (R15%, -As(=0)(Rl,2,·Ρ(=δ)(κ"%, _As(=s)(r18Dc)2 , _CN, -0H, .SH, _c(=〇)〇H, _s(four))2〇h, _s R19d, or -C(=0)N(R)2. RnDc, Rl2Dc, r13Dc, Hanka, Han account, r17Dc, r18Dc and r21Dc are respectively independent of the temple, j ^ horse hydrogen atom or a substituted hydrocarbon group of 1 to 50 'R, and R, respectively Independently a substitutable carbon atom number of 1 to 30, Rn〇C, R 2De, Rl3Dc, Rl4Dc, Ri5Dc, R_, Yan, RuDe, Yan and R21De may be the same or different. , Q2DU(R22Dc)-, _As(R23Dc)·, } A radical formed by a heterocyclic compound which can be substituted from a nitrogen atom, such that two hydrogen atoms are removed, _n(r24Dc) ... 0) 〇, ·_= 0) 〇_,.p(=s)(r2,, or _(R28De)·. R22De, R23De, R25De e shame K, : R27De and r28Dc are each independently a hydrogen atom or a carbon atom which can be substituted 丨~ % of hydrocarbon να. Substituted carbon atom 丨~(10) alkyl group, R22〇c, W r2仙0 R, strict, strict and strict may be the same or different, Q is P, As, self-could In the substituted heterocyclic compound of the nitrogen atom of the substituted 3, the base of the three hydrogen atoms is removed, n, p (= 〇), As (four) is called 15659J.doc

S •30- 201202390 或 As(=S) 〇 R2Dc為碳原子數50以下之2價基，然*，於所鍵結之q1D< 為自含氮原子之雜環式化合物中去⑹個氫原子而成的基 之情形，所鍵結之Q-為自含氮原子之雜環式化合物中去 掉2個氫原子而成的基之情形，或所鍵 原子之雜環式化合物中去掉3個氯原子而：的基為二 時，亦可為直接鍵結。 選 i rIIDc、 R 18Dc R19Dc 、 R 27Dc 、 r28Dc 、 R 12Dc 21Dc 2D< .R13Dc % RUDc ^ R15Dc ^ Rl6Dc λ r17Dc %S •30- 201202390 or As(=S) 〇R2Dc is a divalent group having 50 or less carbon atoms, and *, in the bonded q1D< is a (6) hydrogen atom from a heterocyclic compound containing a nitrogen atom In the case of a group, the bonded Q- is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, or three chlorine atoms are removed from a heterocyclic compound of a bonded atom. When the base of the atom is two, it can also be a direct bond. Select i rIIDc, R 18Dc R19Dc , R 27Dc , r28Dc , R 12Dc 21Dc 2D< .R13Dc % RUDc ^ R15Dc ^ Rl6Dc λ r17Dc %

Rl8DC、W、R21DC、r22Dc、r23Dc、V、pc、W、 R 、R 、R A自可經取代之含氮原子之雜環式化合 物中去掉丨個〜3個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 式(Dd)中 ’Q，-P(R"，2、_As(Rl2Dd)2、k_ 之含氮原子之雜環式化合物中去掉i個氫原子而成的基、 -N(Rl3Dd)(R,4Dd)、·〇·、_s·、|〇)2。·' _c(,〇.、_p㈣ (R—)2 , -As(=0)(R—)2 . -P(=S)(R-d)2 , .As(=S)(R—)2 . -CN、-0H、-SH、_C(=0)0H、_s(=〇)2〇h sRi9Dd、或 -C( = 0)N(R2 ⑽）2。R⑽、Rl2Dd、Rl3Dd、…叫、Ri6/ R17Dd、Rl⑽及R21Dd分別獨立為 、 乳你十或可經取代之碳原 子數1〜50之烴基，R〜19、別獨立為可經取代之碳 原子數 1 〜30之烧基，RiiDd、Ri2Dd、Rl3Dd、Ri4Dd ^_、广、^及，可分別相同亦可不同/ Q-為-P(R，、-As(R，、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Dd)_、 156591.doc •31 · 201202390 -P(=0)(R25Dd). . -As(=〇)(R26Dd)- ^ -P(=S)(R27Dd). . ^ _As(=S) (R28Dd)-。RUDd、R23Dd、R25Dd、R26Dd、&27叫及汉_ 分別 獨立為氫原子或可經取代之碳原子數之烴基，尺以加為 可經取代之碳原子數1〜30之烧基，R22Dd、R23Dd、R24〇d、 R25= R26Dd、可分別相同亦可不同》 R2Dd為碳原子數50以下之2價基，然而，於所鍵結之QlDd 為自含氮原？之雜環式化合物中去掉！個氣原子而成的基 之If形，或所鍵結之Q2Dd為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 R4Dd為碳原子數70以下之4價基。Rl8DC, W, R21DC, r22Dc, r23Dc, V, pc, W, R, R, and RA are 2 of the bases of the heterocyclic compound having a nitrogen atom which may be substituted by removing one to three hydrogen atoms. More than one of the groups may be bonded to form a ring. a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom of 'Q,-P(R", 2, _As(Rl2Dd) 2, k_ in the formula (Dd), -N(Rl3Dd)(R , 4Dd), ·〇·, _s·,|〇)2. · ' _c (, 〇., _p (four) (R-) 2 , -As(=0)(R-)2 . -P(=S)(Rd)2 , .As(=S)(R-)2 . -CN, -0H, -SH, _C(=0)0H, _s(=〇)2〇h sRi9Dd, or -C( = 0)N(R2 (10))2. R(10), Rl2Dd, Rl3Dd,...called, Ri6 / R17Dd, Rl (10) and R21Dd are each independently, a ten or a substituted hydrocarbon group having 1 to 50 carbon atoms, R to 19, independently a substitutable carbon atom having a carbon number of 1 to 30, RiiDd, Ri2Dd, Rl3Dd, Ri4Dd ^_, 广, ^ and , respectively, may be the same or different / Q- is -P(R,, -As(R,, removed from the heterocyclic compound containing a nitrogen atom which may be substituted) a group of two hydrogen atoms, _N(R24Dd)_, 156591.doc •31 · 201202390 -P(=0)(R25Dd). . -As(=〇)(R26Dd)- ^ -P(=S) (R27Dd). . ^ _As(=S) (R28Dd)-.RUDd, R23Dd, R25Dd, R26Dd, &27 and Han_ are each independently a hydrogen atom or a hydrocarbon group with a substituted number of carbon atoms. R12Dd, R23Dd, R24〇d, R25= R26Dd may be the same or different, and R2Dd is a divalent group having 50 or less carbon atoms. However, in the case of a substitutable carbon atom having 1 to 30 carbon atoms, R22Dd, R23Dd, R24〇d, and R25=R26Dd may be used. Bonded QlDd is self-contained In the case of the original heterocyclic compound, the base form of the gas atom is removed, or the bonded Q2Dd is a group in which two hydrogen atoms are removed from the heterocyclic compound containing a nitrogen atom. It may also be a direct bond. R4Dd is a tetravalent group having a carbon number of 70 or less.

R 選自 R11Dd、RUDd、Rl3Dd、Rl4Dd、R】5Dd R16Dd、R17Dd、 18DdR is selected from R11Dd, RUDd, Rl3Dd, Rl4Dd, R] 5Dd R16Dd, R17Dd, 18Dd

R 19DdR 19Dd

R 21DdR 21Dd

R 22Dd R23Dd Λ R24DdR 22Dd R23Dd Λ R24Dd

R 25Dd R26Dd、R27Dd、R28Dd、R2Dd、R4Dd及 之雜環式化合物中去掉1個〜2個氫原 自可經取代之含氮原子 子而成的基中的2個以 上之基亦可任意鍵結而形成環。 式（De)中 ’ Q1DU(RHDe)2、_As(r12d)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 娜_)(严）、_σ、-s·、_s(=0)2〇·、_c(=〇)〇.、_p(=〇) (R15%、-As(=0)(R職)2、·ρ(=3)(ιι17%、_As(=s你臟、 -CN、-OH、-SH、-C(=0)0H、_S(=〇)2〇H、_SRl9De、或 -C(=〇)N(R21De)2。RHDe、Rl2De、Rl3De、Ri5De R]6De R17De、dR21De分別獨立為氮原子或可經取代之石炭原 子數1〜50之烴基，R14、R19De分別獨立為可經取代之碳 原子數 1 〜30 之烷基，R"De 及 R12De、Rl3De、RUDe、Ri5De、 ·32· 156591.doc s 201202390 R16De、Rl7De、Rl8De、…心及…心可分別相同亦可不同。 Q為_p(R22De)-、-As(R23De)-、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24De>_、 -P(=〇)(R25De)-、-As(=0)(R驗)…·Ρ(=3)(Κ2，_、或 _As卜 (R28De)_。R22De、R23De、R25De、R26De、尺’及尺狐分別獨 立為氫原子或可經取代之碳原子數卜⑽之烴基，R24De為可 經取代之碳原子數1~30之烧基，R22De、R23De、R24De、 R25De、、R27^以❿可分別相同亦可不同。 R2De為碳原子數50以下之2價基，然而，於所鍵結之QlDe 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形’或所鍵結之Q2De為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 R3De為碳原子數5 0以下之3價基。 R27De、R28De、R2De、R3De及自 式化合物中去掉1個〜2個氫原 R17De、 R26De、 選自 R11De、R12De、R13De、 R18De、Rl9De、R21De、R22De、 亦可任意鍵結而形成環。 RWDe、Rl5De、Rl6De、 R23De、R24De、R25De、 可經取代之含氮原子之雜環 子而成的基中的2個以上之基 式⑽中，Q⑼為-P(R_)2、_As(Rl2Df)2、自可經取代 之含氮原子之雜環式化合物中去掉i個氫原子而成的基、 -N(Rl3Df)(Rl4Df)、m(=〇)2a、命〇)σ、_P(=0) (Ri5Df)2、·Μ=〇)η _P(=s)(Rl7Df)2、_As(=s)(Ri8Df)2、 _C(=〇)N(R2,Df)2。R"Df、Rl2Df、Rl3Df、尺⑽、 -CN、-0H、-SH、-C(=〇)〇H、·δ(=〇)2〇Η、-SR應、或R 25Dd R26Dd, R27Dd, R28Dd, R2Dd, R4Dd and a heterocyclic compound in which one or two hydrogen atoms are removed from a substitutable nitrogen-containing atom may have two or more groups. Knot to form a ring. In the formula (De), Q1DU(RHDe)2, _As(r12d)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, and Na (), _σ , -s·, _s(=0)2〇·, _c(=〇)〇., _p(=〇) (R15%, -As(=0)(R jobs)2,·ρ(=3)( Ιι17%, _As(=s you dirty, -CN, -OH, -SH, -C(=0)0H, _S(=〇)2〇H, _SRl9De, or -C(=〇)N(R21De)2 RHDe, Rl2De, Rl3De, Ri5De R]6De R17De, dR21De are each independently a nitrogen atom or a substituted hydrocarbon group having a carbon number of 1 to 50, and R14 and R19De are independently substituted carbon atoms of 1 to 30, respectively. Alkyl, R"De and R12De, Rl3De, RUDe, Ri5De, ·32· 156591.doc s 201202390 R16De, Rl7De, Rl8De, ... heart and ... heart can be the same or different. Q is _p(R22De)-, -As(R23De)-, a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _N(R24De>_, -P(=〇)(R25De)-, -As (=0)(R test)...·Ρ(=3)(Κ2,_, or _As(R28De)_. R22De, R23De, R25De, R26De, ruler and ruler fox are each independently a hydrogen atom or can pass Substituted carbon atom The hydrocarbon group of (10), R24De is a substitutable carbon atom having 1 to 30 carbon atoms, and R22De, R23De, R24De, R25De, and R27^ may be the same or different, respectively. R2De is a carbon number of 50 or less. a valence group, however, where the bonded QlDe is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q2De is a heterocyclic compound derived from a nitrogen atom. In the case where a base of two hydrogen atoms is removed, it may be a direct bond. R3De is a trivalent group having a carbon number of 50 or less. One of R27De, R28De, R2De, R3De and a self-compound is removed. Two hydrogen atoms R17De, R26De, selected from R11De, R12De, R13De, R18De, Rl9De, R21De, R22De, may also be arbitrarily bonded to form a ring. RWDe, Rl5De, Rl6De, R23De, R24De, R25De, may be substituted In the formula (10) of two or more groups of the heterocyclic ring of a nitrogen atom, Q(9) is -P(R_)2, _As(Rl2Df)2, and a heterocyclic compound derived from a nitrogen atom which may be substituted A group obtained by removing i hydrogen atoms, -N(Rl3Df)(Rl4Df), m(=〇)2a, 〇)σ, _P(=0) (Ri5Df)2, ·Μ=〇)η _P(=s)(Rl7Df)2, _As(=s)(Ri8Df)2, _C(=〇)N(R2, Df)2. R"Df, Rl2Df, Rl3Df, ruler (10), -CN, -0H, -SH, -C(=〇)〇H,·δ(=〇)2〇Η, -SR should, or

R 16Df 156591.doc -33· 201202390 7Df、Rl8Df& R21Df分別獨立為氮原子或可經取代之碳原 子數1〜50之烴基，RMDf及Rl9〇f分別獨立為可經取代之碳原 子數 1〜30 之院基，R11Df、Rl2Df、Ri3Df、Ri4Df、Rl5Df、R 16Df 156591.doc -33· 201202390 7Df, Rl8Df& R21Df are each independently a nitrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and RMDf and Rl9〇f are each independently a carbon atom which can be substituted 1~ 30 yard base, R11Df, Rl2Df, Ri3Df, Ri4Df, Rl5Df,

Rl6Df、Ri7Df、Rl8Df、Ri9Df 21Df R 及R 可分別相同亦可不同。 Q2D、-P(R22Df)-、_As(R23Df)… 可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Df)_、 -P(=0)(R25Df)-、_As(=〇)(R·)…_p(=s)(R27Df)、或 _As(=s) (R2’_。R22Df、R23Df、R贿、R26Df、r而及尺讀分別獨 立為氫原子或可經取代之碳原子數丨〜5 〇之烴基，R24Df為可 經取代之碳原子數1〜30之烷基，R22Df、R23Df、R24Df、 R25Df、R26Df、R27、R28Df可分別相同亦可不同。 Q為Ρ、As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N ' p(=〇)、As(=〇)、p卜y、 或 As(=S)。 R2Df為碳原子數50以下之2價基，然而，於所鍵結之QlDf 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形’所鍵結之Q2D、自含氮原子之雜環式化合物中去 掉2個氫原子而成的基之情形，或所鍵結之屮^為自含氮 原子之雜環式化合物中去掉3個氫原子而成的基之情形 時’亦可為直接鍵結。 避目 κ.…、R1 …、Rl3Df、Rl4Df、Rl5Df、…咖、尺 R 丨 8〇f、R19Df、R21Df、R22Df、R23Df、R24Df、R25Df、尺 R、R28Df、R2Df及自可經取代之含氮原子之雜環$ 物中去掉1個〜3個氫原子而成的基中的2個以上之基功 156591.doc -34. 201202390 意鍵結而形成環。 式（Dg)中，Q1〇g為-P(R"Dg)2、_As(Ri2Dg)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Dg)(RI4Dg)、_〇·、-s·、_s(=〇)2〇-、_〇(=0)0·、·ρ(=〇) (R15Dg)2、-As(=0)(R16Dg)2、_P(=S)(Rmg)2、_As(=s)(Rl8Dg)2、 -CN、-〇H、-SH、_C(=0)0H、-S(=0)2〇H、-SR19Dg、或 -C( = 〇)N(R21Dg)2。R1 丨 Dg、RUDg、R13Dg、Rl5Dg、Rl6Dg、Rl6Df, Ri7Df, Rl8Df, Ri9Df 21Df R and R may be the same or different. Q2D, -P(R22Df)-, _As(R23Df)... A group obtained by removing two hydrogen atoms from a substituted heterocyclic compound containing a nitrogen atom, _N(R24Df)_, -P(=0) R25Df)-, _As(=〇)(R·)..._p(=s)(R27Df), or _As(=s) (R2'_. R22Df, R23Df, R bribe, R26Df, r and foot reading respectively Independently a hydrogen atom or a substituted hydrocarbon group having a carbon number of 丨~5 ,, R24Df is a substituted alkyl group having 1 to 30 carbon atoms, and R22Df, R23Df, R24Df, R25Df, R26Df, R27, R28Df may be respectively The same may be different. Q is a group of ruthenium, As, a heterocyclic compound containing a nitrogen atom which may be substituted by three hydrogen atoms, N ' p (= 〇), As (= 〇), p y, or As(=S) R2Df is a divalent group having 50 or less carbon atoms. However, the bonded QlDf is a group obtained by removing one hydrogen atom from a heterocyclic compound containing a nitrogen atom. In the case of Q2D bonded, a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, or the bond is removed from a heterocyclic compound containing a nitrogen atom. In the case of a base of three hydrogen atoms, it can also be a direct bond. 6-1., R1 ..., Rl3Df, Rl4Df, Rl5Df, ..., coffee, ruler R 丨8〇f, R19Df, R21Df, R22Df, R23Df, R24Df, R25Df, ruler R, R28Df, R2Df and self-substitutable In the heterocyclic ring containing a nitrogen atom, two or more bases in a group obtained by removing one to three hydrogen atoms are 156591.doc -34. 201202390 is bonded to form a ring. In the formula (Dg), Q1〇g is -P(R"Dg)2, _As(Ri2Dg)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R13Dg) (RI4Dg) ), _〇·, -s·, _s(=〇)2〇-, _〇(=0)0·,·ρ(=〇) (R15Dg)2, -As(=0)(R16Dg)2 _P(=S)(Rmg)2, _As(=s)(Rl8Dg)2, -CN, -〇H, -SH, _C(=0)0H, -S(=0)2〇H, -SR19Dg, Or -C( = 〇)N(R21Dg)2. R1 丨Dg, RUDg, R13Dg, Rl5Dg, Rl6Dg,

RlWg、RUDg及R21Dg分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R14〇g及r19〇s為可經取代之碳原子數 1 〜30 之烷基，R"Dg、R12Dg、R13Dg、Ri4Dg、Rl5Dg、Rl6Dg、RlWg, RUDg and R21Dg are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R14〇g and r19〇s are substituted alkyl groups having 1 to 30 carbon atoms, R"Dg, R12Dg, R13Dg, Ri4Dg, Rl5Dg, Rl6Dg,

Riw、RuDg、可分別相同亦可不同。 Q叫為-P(R2，_、_As(R23Dg)_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24〇g)_、 -p(=o)(r25DV、-As(=〇)(R26D”_、_P(=s)(R27Dg)·、或 _ (R’）-。、R23Dg、R25Dg、R26Dg、R27、R28Dg 分別 獨立為氫原子或可經取代之碳原子數丨〜”之烴基，R24Dgg 可經取代之碳原子數1〜30之烷基，R22Dg、R23Dg、R24Dg、 r25D3s、R2叫、R27h R28D4分別相同亦可不同。Riw and RuDg may be the same or different. Q is -P(R2, _, _As(R23Dg)_, a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _N(R24〇g)_, -p (=o)(r25DV, -As(=〇)(R26D"_, _P(=s)(R27Dg)·, or _(R')-., R23Dg, R25Dg, R26Dg, R27, R28Dg are each independently hydrogen Atom or a hydrocarbon group having a carbon number of 丨~", R24Dgg may be substituted with an alkyl group having 1 to 30 carbon atoms, and R22Dg, R23Dg, R24Dg, r25D3s, R2, and R27h R28D4 may be the same or different.

As'自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As(=⑺、p(=s)、 或 As(=S) 〇 R2Dg為碳原子數50以下之2價* ’然❼，於所鍵結之QlDg 為自含氮原子之雜環式化合物中去掉i個氫原子而成的基 之情形’所鍵結之Q、自含氮原子之雜環式化合物中去 156591.doc •35· 201202390 掉2個氫原子而成的基之情形，或所鍵結之Q3Dgg自含氮 原子之雜環式化合物中去掉3個氫原子而成的基之情形 時，亦可為直接鍵結。 R3Dg為碳原子數50以下之3價基。 選自 RiiDg、R12Dg、Ri3Dg、RUDg、Rl5Dg、Rl6Dg、Rl7Dg、 R18Dg、R19Dg、R2lDg、R22Dg、R23Dg、R24Dg、R25Dg、 R g ' R”Dg、R28Dg、R2Dg、心及自可經取代之含氣原子 之雜環式化合物中去掉〖個〜3個氫原子而成的基中的2個以 上之基亦可任意鍵結而形成環。 式（Dh)中，QlDh 為 _p(RllDh)2、_As(R) WJ理取f 之3氮原子之雜環式化合物中去掉丨個氫原子而成的基 n(r )(r Dh)、-0·、_S_、-S(=〇)2cr、_c(=0)0·、-p(=( (R )2、_As(=〇)(R16Dh)2、，P(=S)(R17Dh)2、_As(=S)(R18Dh)2 CN、_〇H、_SH、-C(=〇)OH、-S(=0)2〇H、-SR19Dh _C(-〇)N(R21Dh)2。RllDh、Ri2Dh、Ri3Dh、f,、R R17Dh、·ρ 18Dh n n2inh 及R 分別獨立為氫原子或可經取代之碳 子數1〜50之烴基’ RMDh&R〗9Dh分別獨立為可經取代之 原子數1〜30之院基，R11Dh、R丨2Dh、R13Dh、R14Dh、Rl5Dh R】6Dh、Rl7Dh 8 、R 及R 1Dh可分別相同亦可不同 Q2D、-P(R22Dh)_、A fR23Dh、. J _As(R )_、自可經取代之含氮原 之雜環式化合物中去掉2個氫原子而成的基、-N(R，· -ρ(=ο)〇·、_As(，(R26Dh)、_p(=s)(R27Dh)·、或，=(R28'。R22Dh、R23Dh、r25dh、、尺_及尺_分 獨立為氫原子或可經取代之碳原子數1〜5G之烴基，R_ 15Dh 16Dh *5659l.d〇c s ·36· 201202390 可經取代之碳原子數1〜30之烷基，R22Dh、R23Dh、R24Dh、 R25::R26Dh、π、112·可分別相同亦可不同。 Q3Dh為P、AS、自可經取代之含氮原子之雜環式化合物 中去掉3個氣原子而成的基、N、P(=〇)、As(=〇)、p(=s)、 或 As(=S)。 R2Dh為碳原子數50以下之2價基，然而，於所鍵結之QlDh 為自3氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形’所鍵結之C為自含氮原子之雜環式化合物中去 掉2個氫原子而成的基之情形’或所鍵結之Q3Dh為自含氮 原子之雜環式化合物中去掉3個氫原子而成的基之情形 時，亦可為直接鍵結。 R 為碳原子數5 0以下之3價基。As', a group of N, p(=〇), As(=(7), p(=s), or As(=S) obtained by removing three hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted. 〇R2Dg is a valence of 50 or less carbon atoms*', and the bonded Q1Dg is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom. Q. From a heterocyclic compound containing a nitrogen atom, 156591.doc •35· 201202390 A case where two hydrogen atoms are removed, or the bonded Q3Dgg is removed from a heterocyclic compound containing a nitrogen atom. In the case of a group of hydrogen atoms, it may be a direct bond. R3Dg is a trivalent group having 50 or less carbon atoms. It is selected from the group consisting of RiiDg, R12Dg, Ri3Dg, RUDg, Rl5Dg, Rl6Dg, Rl7Dg, R18Dg, R19Dg, R2lDg, R22Dg, R23Dg, R24Dg, R25Dg, Rg 'R"Dg, R28Dg, R2Dg, and a group of heterocyclic compounds containing a gas atom which may be substituted by a group of ~3 hydrogen atoms Two or more groups may be arbitrarily bonded to form a ring. In the formula (Dh), QlDh is _p(RllDh)2, _As(R) WJ is taken from the heterocyclic compound of the nitrogen atom of 3 The base n(r )(r Dh), -0·, _S_, -S(=〇)2cr, _c(=0)0·, -p(=( (R )2, _As) formed by one hydrogen atom (=〇)(R16Dh)2, P(=S)(R17Dh)2, _As(=S)(R18Dh)2 CN, _〇H, _SH, -C(=〇)OH, -S(=0 2〇H, -SR19Dh _C(-〇)N(R21Dh)2. RllDh, Ri2Dh, Ri3Dh, f, R R17Dh, ·ρ 18Dh n n2inh and R are each independently a hydrogen atom or a carbon number that can be substituted 1~50 hydrocarbon group ' RMDh & R〗 9Dh are independently substituted by the atomic number of 1~30, R11Dh, R丨2Dh, R13Dh, R14Dh, Rl5Dh R] 6Dh, Rl7Dh 8 , R and R 1Dh The same or different Q2D, -P(R22Dh)_, A fR23Dh, . J _As(R )_, a base obtained by removing two hydrogen atoms from a heterocyclic compound which can be substituted with a nitrogen atom, N(R,· -ρ(=ο)〇·, _As(,(R26Dh), _p(=s)(R27Dh)·, or,=(R28'.R22Dh, R23Dh, r25dh, ruler_and ruler_ a hydrogen atom or a substituted hydrocarbon group having 1 to 5 carbon atoms, R_ 15Dh 16Dh *5659l.d〇cs ·36· 201202390 A substituted alkyl group having 1 to 30 carbon atoms, R22Dh, R23Dh, R24Dh, R25::R26Dh, π, 112· can be the same respectively It can be different. Q3Dh is a group in which P, AS, and a heterocyclic compound containing a nitrogen atom which may be substituted, and three gas atoms are removed, N, P(=〇), As(=〇), p(=s), Or As(=S). R2Dh is a divalent group having a carbon number of 50 or less. However, in the case where the bonded QlDh is a group in which a hydrogen atom is removed from a heterocyclic compound of 3 nitrogen atoms, the bonded C is self. In the case where a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q3Dh is a group in which three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom. It can also be a direct bond. R is a trivalent group having a carbon number of 50 or less.

RR

選自R 18Dh 1 lDhFrom R 18Dh 1 lDh

R 12DhR 12Dh

R 13DhR 13Dh

R 19DhR 19Dh

R 21DhR 21Dh

R R 22Dh 14Dh、Rl5Dh、Ri6Dh、R17Dh R24Dh 、 R25Dh 、R 6Dh、R27Dh、R28Dh、R2Dh、R3Dh R及自可經取代之含氮原子 雜衣式化。物中去掉卜3個氣原子而成的基中的2個以上 之基亦可任意鍵結而形成環。 式㈣t，Q⑶為-P(R，2、_As(R⑽)2、自可經取代之 含氮原子之雜環式化合物中去掉i個氫原子而成的基、 N(RnDi)(Rl4Di)、_〇·、& ·R R 22Dh 14Dh, Rl5Dh, Ri6Dh, R17Dh R24Dh, R25Dh, R 6Dh, R27Dh, R28Dh, R2Dh, R3Dh R and from a substitutable nitrogen-containing atom. Two or more of the groups in which three gas atoms are removed from the material may be arbitrarily bonded to form a ring. (4) t, Q(3) is -P(R, 2, _As(R(10)) 2, a group obtained by removing i hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, N(RnDi)(Rl4Di), _〇·, & ·

R 23Dh 、-s(=〇)2〇·、-C(=〇)〇.、_P(=〇) 1)2、-AS(=〇)(Rl6Di)2、-p(=S)(R17Di)2、-As(=s)(Rl⑽)2、 -CN、-〇H、-SH、·π〇)〇Η、_s(=〇)2〇H、妞19 -c(=o)n(r，2。、R,2Di、R⑽、Ri5Di、Ri6Di 一分別獨立為氫原子或可經取代之碳原子R 23Dh , -s(=〇)2〇·, -C(=〇)〇., _P(=〇) 1)2, -AS(=〇)(Rl6Di)2, -p(=S)(R17Di 2, -As(=s)(Rl(10))2, -CN, -〇H, -SH, ·π〇)〇Η, _s(=〇)2〇H, girl 19 -c(=o)n( r, 2, R, 2Di, R (10), Ri5Di, Ri6Di - each independently a hydrogen atom or a carbon atom which may be substituted

(R 156591.doc -37- 201202390 數1〜50之烴基 R14D^r 190i 數 -30 之烷基，RnDi、R12Di 分別獨立為可經取代之碳原子(R 156591.doc -37- 201202390 Number 1 to 50 hydrocarbon group R14D^r 190i number -30 alkyl group, RnDi, R12Di are independently substituted carbon atoms

R l3DiR l3Di

R 14Di R15Di R咖、R”Di、R咖、R⑽及R”Di可分別相同亦可不同 Q2Di為_As(R23Di)_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Di)_、-Ρ(=〇)(]125、_、·Μ=〇)(κ26〜_、p(=s)(R27Di)、或·Α㈣) 〇l28Di)- e R22Di、R23Di 25DiR 14Di R15Di R, R"Di, R, R(10) and R"Di may be the same or different Q2Di is _As(R23Di)_, and 2 of the heterocyclic compounds containing a nitrogen atom which may be substituted are removed. a group of hydrogen atoms, _N(R24Di)_, -Ρ(=〇)(]125, _,·Μ=〇)(κ26~_, p(=s)(R27Di), or ·Α(4)) 〇l28Di )-e R22Di, R23Di 25Di

R 26Di R27Di u D28Di 及R2SDl分別獨 立為氫原子或可經取代之碳原子數卜⑼之烴基，R；MDi為可 經取代之碳原子數1~30之烷基，r22〇 R25Di、、R27Di 菸卩2801«^八 w J K 及R 可分別相同亦可不同 R2Dl為碳原子數50以下之2價基，然而，於所鍵結之QlDi 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 r4Di為碳原子數70以下之4價基。R 26Di R27Di u D28Di and R2SDl are each independently a hydrogen atom or a substituted carbon atom (9), R; MDi is a substituted alkyl group having 1 to 30 carbon atoms, r22〇R25Di, R27Di卩2801«^八w JK and R may be the same or different, and R2Dl is a divalent group having 50 or less carbon atoms. However, the bonded QlDi is one hydrogen removed from the heterocyclic compound containing a nitrogen atom. In the case of a base formed by an atom or a bond formed by removing two hydrogen atoms from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. r4Di is a tetravalent group having 70 or less carbon atoms.

R 23DiR 23Di

R 24Di 選自 R"Di、Ri2Di、Rl3Di、Rl4Di、Rl5Di、Rl6Di、尺”⑴、R 24Di is selected from the group consisting of R"Di, Ri2Di, Rl3Di, Rl4Di, Rl5Di, Rl6Di, ruler" (1),

Ri8D,、R丨9Di、R21Di、尺22〇丨、尺加丨、尺2仙、尺25〇丨、仙、 j^27Di、R28Di p2Di β ώ —r tt. \ R 、R及自可經取代之含氮原子之雜環 式化合物中去掉1個〜2個氫原子而成的基中的2個以上之基 亦可任意鍵結而形成環。 式（Dj)t，Q丨〜為冲⑺丨叫）2、·^^丨叫）2、自可經取代之 含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R J)(RMDj)、-0-、-S·、-s(=0)20·、_C(=0)〇-、-P(=〇) (R15%、-As(=〇)(R_)2、·ρ(=δ)(ρΠ0』）2、_As(=s)(Rl8Dj)2、 156591.doc s -38 - 201202390 -CN、-OH、-SH、-C(=0)0H ' _s(=〇)2〇h、-SR19Dj、戍 -C(=0)N(R21Dj)2。R11Dj、H12Dj、RUDj、Rl5Dj、Rl6Dj、 R17D』、R丨8以及“叫分別獨立為氫原子或可經取代之碳原子 數1〜50之烴基，R14D』及R19Dj分別獨立為可經取代之碳原子 數 1 〜30 之烷基 ’ R"Dj、R丨叫、R"Dj、Rl4Dj、Rl5Dj、 R^j、RnDj、尺丨叫、尺丨叫及尺2丨〇』可分別相同亦可不同。 Q2Dj為-P(R22Dj)-、-As(R23Dj)·、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、-N(R24Dj)_、 -P(=0)(R25D】)_、_As(=〇)(R2，-、_P(==s)(R27Dj)·、或 _As(=s) (R2，· e R22Dj、R酬、R25Dj、R26Dj、R27Dj*R28Dj 分別獨 立為氫原子或可經取代之碳原子數^50之烴基，R24Dj為可 經取代之碳原子數1〜30之烷基，R22Dj、R23Dj、R24Dj、 R25Dj、R26Dj、R27Dj及R28Dj可分別相同亦可不同。 R」為碳原子數50以下之2價基’然而，於所鍵結之QiDj 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之Q2〇j為自含氮原子之雜環式化合物中 去掉2個氫原子而成的基之情形時，亦可為直接鍵結。 R3Dj為碳原子數50以下之3價基。 選自 R11Dj、R12Dj、Rl3Dj、Rl4Dj、Rl5Dj、Rl6Dj、尺叫、 R 丨8Dj、R丨 9Dj、R2 丨 Dj、R22Dj、R23Dj、R24Dj、R25Dj、R26Dj、 R27~、R28Dj、R2Dj、R3Dj及自可經取代之含氮原子之雜環 弋化s物中去掉1個〜2個氫原子而成的基中的2個以上之基 亦可任意鍵結而形成環。 式（Dk)中 H_p(RnDk)2、_As(Rl2Dk)2、自可經取代 156591.doc •39· 201202390 之含氮原子之雜環式化合物中去掉i個氫原子而成的基、 、〇·、_s-、·δ(=〇)2〇·、_c(=〇)〇·、_p(=〇) (R’2、_As(=〇)(Rl6Dk)2、外離^ 姊 s)(严)2、 CN、-0H、-SH、_c(=0)〇H、_s(=〇)2〇h、_sr隱或 -C(-〇)N(R21Dk)2。R 丨丨Dk、R12Dk、Rl3Dk、Ri5Dk、R16Dk、 、R職及R脈分別獨立為氫原？或可經取代之碳原 子數1〜50之烴基，R〗4Dk&Rl9Dk分別獨立為可經取代之碳 原子數 1 〜30 之燒基 ’ R11Dk、Rl2Dk、Ri3Dk、r14D1c、Rl5Dk、Ri8D, R丨9Di, R21Di, ruler 22〇丨, ruler plus 尺, ruler 2 sen, ruler 25〇丨, 仙, j^27Di, R28Di p2Di β ώ —r tt. \ R , R and self-replaceable The two or more groups in which the one or two hydrogen atoms are removed from the heterocyclic compound containing a nitrogen atom may be arbitrarily bonded to form a ring. Formula (Dj)t, Q丨~ is a rush (7) squeaking) 2,·^^ squeaking) 2. A base obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, N(RJ)(RMDj), -0-, -S·, -s(=0)20·, _C(=0)〇-, -P(=〇) (R15%, -As(=〇)( R_)2,·ρ(=δ)(ρΠ0』)2, _As(=s)(Rl8Dj)2, 156591.doc s -38 - 201202390 -CN, -OH, -SH, -C(=0)0H ' _s(=〇)2〇h, -SR19Dj, 戍-C(=0)N(R21Dj)2. R11Dj, H12Dj, RUDj, Rl5Dj, Rl6Dj, R17D』, R丨8 and “called independently hydrogen atoms Or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R14D" and R19Dj are each independently a substituted alkyl group having 1 to 30 carbon atoms. R"Dj, R 丨, R"Dj, Rl4Dj, Rl5Dj , R^j, RnDj, ruler, ruler and ruler 2丨〇 can be the same or different. Q2Dj is -P(R22Dj)-, -As(R23Dj)·, self-substitutable nitrogen A group in which two hydrogen atoms are removed from a heterocyclic compound of an atom, -N(R24Dj)_, -P(=0)(R25D))_, _As(=〇)(R2,-,_P(== s)(R27Dj)·, or _As(=s) (R2,· e R22Dj, R reward, R25Dj, R26Dj, R27Dj*R28D j is independently a hydrogen atom or a substituted hydrocarbon group having a carbon number of 50, R24Dj is a substituted alkyl group having 1 to 30 carbon atoms, and R22Dj, R23Dj, R24Dj, R25Dj, R26Dj, R27Dj and R28Dj are respectively R" is a divalent group having 50 or less carbon atoms' However, in the case where the bonded QiDj is a group obtained by removing one hydrogen atom from a heterocyclic compound containing a nitrogen atom, or When the bonded Q2〇j is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R3Dj is a trivalent group having 50 or less carbon atoms. From R11Dj, R12Dj, Rl3Dj, Rl4Dj, Rl5Dj, Rl6Dj, ruler, R 丨8Dj, R丨9Dj, R2 丨Dj, R22Dj, R23Dj, R24Dj, R25Dj, R26Dj, R27~, R28Dj, R2Dj, R3Dj and Two or more groups in which a heterocyclic deuterated s-containing nitrogen atom is substituted with one to two hydrogen atoms may be arbitrarily bonded to form a ring. In the formula (Dk), H_p (RnDk) 2, _As (Rl2Dk) 2, removed from the heterocyclic compound containing a nitrogen atom of 156591.doc •39·201202390 Subgroups, 〇·, _s-, δ(=〇)2〇·, _c(=〇)〇·, _p(=〇) (R'2, _As(=〇)(Rl6Dk)2 , outside ^ ) s) (strict) 2, CN, -0H, -SH, _c (=0) 〇 H, _s (= 〇) 2 〇 h, _sr hidden or -C (- 〇) N (R21Dk) 2. R 丨丨 Dk, R12Dk, Rl3Dk, Ri5Dk, R16Dk, R, and R are independently hydrogenogens? Or a hydrocarbon group having a carbon number of 1 to 50 which may be substituted, and R 4Dk& Rl9Dk are independently a calcined group having a carbon number of 1 to 30, R11Dk, Rl2Dk, Ri3Dk, r14D1c, Rl5Dk,

Rl6Dk、Ri7Dk、pl8Dk、U19D1CH K R R 及尺咖可分別相同亦可不同。 Q3Dk&P、As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、n、p(=〇)、As(=〇)、p<=s)、 或 As(=S)。 R 為碳原子數50以下之2價基，然而，於所鍵結之QiDk 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之Q3Dk為自含氮原子之雜環式化合物中 去掉3個氫原子而成的基之情形時，亦可為直接鍵結。 選自 RllDk、Rl2Dk、Rl3Dk、Rl4Dk、Rl5Dk、Rl6Dk ' R17Dk、Rl6Dk, Ri7Dk, pl8Dk, U19D1CH K R R and ruler can be the same or different. Q3Dk&P, As, a group obtained by removing three hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, n, p(=〇), As(=〇), p<=s), Or As(=S). R is a divalent group having 50 or less carbon atoms, however, the bonded QiDk is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q3Dk is When a group in which three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom is used, it may be a direct bond. Selected from RllDk, Rl2Dk, Rl3Dk, Rl4Dk, Rl5Dk, Rl6Dk ' R17Dk,

Rl8Dk、Rl9Dk、R21Dk、R2D1自含氮原子之雜環式化合物 中去掉1個或3個氫原子而成的基中的2個以上之基亦可任 意鍵結而形成環。 式（D1)中，qid丨為_p(r"di)2、_As(Ri2Di)2、自可經取代之 含氮原子之雜環式化合物中去掉1個氫原子而成的基、 n(r13D1)(r14DI)、-0、-S·、-s(=0)20_、-c(=o)o·、-p(=〇) (R15DI)2、-As(=〇)(R16D1)2、-P(=S)(R17DI)2、-As(=S)(R18D1)2、 156591 .doc • 40- 201202390Rl8Dk, Rl9Dk, R21Dk, and R2D1 may be bonded to each other by forming a ring in which a group of one or three hydrogen atoms is removed from a heterocyclic compound containing a nitrogen atom. In the formula (D1), qid丨 is _p(r"di)2, _As(Ri2Di)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, n ( r13D1)(r14DI), -0, -S·, -s(=0)20_, -c(=o)o·, -p(=〇) (R15DI)2, -As(=〇)(R16D1) 2. -P(=S)(R17DI)2, -As(=S)(R18D1)2, 156591 .doc • 40- 201202390

-CN 〇H、-SH、-C(=〇)〇H、-s(=〇)2〇h、-SR19D1 或 -C(=0)N(R21D1)2。RUD1、Rl2D1 R、R &R21D1分別獨立為氫原子或可經取代之碳原子 數1 50之基’R di及Rl9D1*別獨立為可經取代之碳原子 數 1 〜30 之烧基，RllDl、R12D1、r13d丨、R14Di r> 16DI ^ τ, I7DI ^ 1 〇τμ ____-CN 〇H, -SH, -C(=〇)〇H, -s(=〇)2〇h, -SR19D1 or -C(=0)N(R21D1)2. RUD1, Rl2D1 R, R & R21D1 are each independently a hydrogen atom or a substitutable carbon atom number of 50 ''R di and Rl9D1* are independently a substitutable carbon atom number of 1 to 30, RllDl , R12D1, r13d丨, R14Di r> 16DI ^ τ, I7DI ^ 1 〇τμ ____

RR

R R18D丨、Or⑽可分別相同亦可不同 Q2D1 為-P(R22D1)_、_AwR23D1、 , _ )A (R )_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、-N(R，·、 -P(=〇)(R25,、·Α々〇)(κ_)_、_p(=s)(R2 、 $28D1>。y2D丨 - 、~R R18D丨, Or(10) may be the same or different, Q2D1 is -P(R22D1)_, _AwR23D1, _ )A (R )_, and 2 hydrogen atoms are removed from the heterocyclic compound containing a nitrogen atom which may be substituted The base, -N(R,·, -P(=〇)(R25,,·Α々〇)(κ_)_, _p(=s)(R2, $28D1>.y2D丨-,~

R 23D1 25D1 R26D丨、R27D丨及尺加丨分別獨 立為氫原子或可經取代之碳原子數卜5〇之烴基，r24〇i為可 經取代之碳原子數U0之烷基，R22D丨、r23D丨、r24d丨、 R:R_、R2、R細可分別相同亦可不同。 、 Q3DI為P、As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As(=〇)、p⑼、 或 As(=S)。 R2、碳原子數50以下之2價基’然而，於所鍵結之Q1D丨 為自含氮原子之雜環式化合物去掉i個氫原子而成的基之 情形，所鍵結之Q-為自含氮原子之雜環式化合物中去掉 2個氫原子而成的基之情形，或所鍵結之q3D1為自含氣原 子之雜環式化合物中去掉3個氫原子而成的基之情形時， 亦可為直接鍵結。 R3D1為碳原子數50以下之3價基。R 23D1 25D1 R26D丨, R27D丨 and 尺加丨 are each independently a hydrogen atom or a substituted carbon atom, and the number of carbon atoms is U0, R22D丨, r23D丨, r24d丨, R: R_, R2, and R may be the same or different. And Q3DI is a group in which P, As, a three-hydrogen atom is removed from a heterocyclic compound having a nitrogen atom which may be substituted, N, p (= 〇), As (= 〇), p (9), or As ( =S). R2, a divalent group having 50 or less carbon atoms' However, in the case where the bonded Q1D丨 is a group obtained by removing i hydrogen atoms from a heterocyclic compound containing a nitrogen atom, the bonded Q- is a case where a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded q3D1 is a group in which three hydrogen atoms are removed from a heterocyclic compound containing a gas atom. It can also be a direct bond. R3D1 is a trivalent group having 50 or less carbon atoms.

RR

選自R 11D1From R 11D1

RR

12DI12DI

R I3D1 ' R14DI、R15〇l、R16DI、r17D1 156591.doc •41 - 201202390R I3D1 ' R14DI, R15〇l, R16DI, r17D1 156591.doc •41 - 201202390

Rl8D丨、R酬、r21D丨、r22D丨、r23D丨、R24D1、r25d丨、r26di、 R27D1、R28D丨、r2D丨、R3D丨及自可經取代之含氮原子之雜環 式化合物中去掉1個〜3個氫原子而成的基中的2個以上之美 亦可任意鍵結而形成環。 式（Dm)中，Q1Dm 為 _P(R"Dm)2、_As(Rl2Dm)2、自可經取 代之含氮原子之雜環式化合物中去掉〖個氫原子而成的 基、-N(R13Dm)(RH)、〇·、_S-、·δ(=〇)2〇.、_c(=〇)〇-、 -P(=0)(R15Dm)2、-As(=〇)(R16Dm)2、-P(=S)(R17D，2、·Α8(=8) (R18Dm)2、_CN、_〇H、-SH、-C(=0)〇H、·8(=〇)2〇η、 -SR19Dm、或-C(=〇)N(R21Dm)2。RUDm、Ri2Dm、Rl3Dm、Rl8D丨, R, r21D丨, r22D丨, r23D丨, R24D1, r25d丨, r26di, R27D1, R28D丨, r2D丨, R3D丨 and one of the heterocyclic compounds containing a nitrogen atom which may be substituted Two or more of the groups of the three hydrogen atoms may be arbitrarily bonded to form a ring. In the formula (Dm), Q1Dm is _P(R"Dm)2, _As(Rl2Dm)2, and a radical formed by removing a hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N ( R13Dm)(RH), 〇·, _S-, ·δ(=〇)2〇., _c(=〇)〇-, -P(=0)(R15Dm)2, -As(=〇)(R16Dm) 2, -P (= S) (R17D, 2, · Α 8 (= 8) (R18Dm) 2, _CN, _ 〇 H, -SH, -C (=0) 〇 H, · 8 (= 〇) 2 〇 η, -SR19Dm, or -C(=〇)N(R21Dm)2. RUDm, Ri2Dm, Rl3Dm,

Rl5Dm、Rl6Dm、Rl7Dm、Rl8Dn^R21Dm分別獨立為氫原子或 可經取代之碳原子數1〜50之烴基，R丨4如及尺丨9〇01分別獨立 為可經取代之碳原子數1〜30之烷基，R"Dm、Rl2Dm、 RUDm、Rl4Din、Rl5Dm、Rl6Dm、R丨 7Dm、RUDm、广爪及 尺21£)111可分別相同亦可不同。 (^2心為-P(R22Dm)-、_As(R23Dm)_、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、_N(R24Dm)_ 、-P( = 〇)(R25Dm)-、-As( = 〇)(R26Dm)_、_p( = s)(R27Dm)、或 -As(=S)(R28Dm)_。R22Dm、R23Dm、R25Dm、R26Din、R27Dm 及 R28Dm分別獨立為氫原子或可經取代之碳原子數丨〜“之煙 基’ R24Dm為可經取代之碳原子數1〜3〇之烷基，R22Dm、 R23Dm、R24Dm、R25Dm、R26Dm、以胸及尺28如可分別相同亦 可不同。 Q4Dmg含有可配位於Ag+之P、含氮原子之雜環式化合物 156591.doc •42· 201202390 中之N、0、或S-中之任一個的碳原子數7〇以下之 。 R2Dm為碳原子數5〇以下之2價其，炒. 1Dm 彳貝基，然而，於所鍵結之 Q為自含氮原子之雜環式化合物中去掉】個氣原子而成 的基之情形’或所鍵結之C為自含氣原子之雜環式化a 物中去掉2個氫原子而成的基之情形時，亦可為直接鍵 結。 R12Dm、Rl3Dm、Rl4Dm、Ri5Dm R19Dm、R21Dm、R22Drn、R23Dm V ' R28Dm、R2Dm '广及自可經取代之 含氮原子之雜環式化合物中去掉〗個〜2個氫原子而成的基 中的2個以上之基亦可任意鍵結而形成環。 式㈣中’Q-n為-p(R丨、、姊丨、、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 •戰"、，)、_〇-、_s-、·δ(=〇)2〇·、c(=〇)〇.、_p(=〇) (R15%、-As(=〇)(R_)2、·Ρ(=δ)(κ17%、_As(=s)(Rl8Dn)2、 -CN、-OH、-SH、-C(=0)〇H、-S(=〇)2〇h、-SR丨9Dn、或 -C(=0)N(R21Dn)2。R11DnRl5Dm, Rl6Dm, Rl7Dm, Rl8Dn^R21Dm are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R丨4 and 丨9〇01 are respectively independently a carbon atom which can be substituted 1~ The alkyl group of 30, R"Dm, Rl2Dm, RUDm, Rl4Din, Rl5Dm, Rl6Dm, R丨7Dm, RUDm, wide claw and ruler 21) 111 may be the same or different. (^2 is -P(R22Dm)-, _As(R23Dm)_, a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, _N(R24Dm)_, -P ( = 〇)(R25Dm)-, -As( = 〇)(R26Dm)_, _p( = s)(R27Dm), or -As(=S)(R28Dm)_.R22Dm, R23Dm, R25Dm, R26Din, R27Dm And R28Dm are each independently a hydrogen atom or a carbon atom which may be substituted 丨~"the nicotyl group" R24Dm is a substitutable alkyl group having 1 to 3 carbon atoms, R22Dm, R23Dm, R24Dm, R25Dm, R26Dm, The chest and the ruler 28 may be the same or different, respectively. Q4Dmg contains any one of N, 0, or S- which may be assigned to a heterocyclic compound of 156591.doc •42· 201202390 of P+ containing Ag+. The number of carbon atoms is 7 〇 or less. R2Dm is a valence of 5 〇 or less, and is fried. 1Dm 彳 betyl, however, the bonded Q is removed from the heterocyclic compound containing a nitrogen atom. The case where the gas atom is formed or the bonded C is a group in which two hydrogen atoms are removed from the heterocyclic compound a of the gas-containing atom, and may be a direct bond. R12Dm, Rl3Dm, Rl4Dm, Ri5Dm R19Dm, R 21Dm, R22Drn, R23Dm V 'R28Dm, R2Dm' and two or more groups in which a heterocyclic compound containing a nitrogen atom which may be substituted may have two or more hydrogen atoms may be arbitrarily bonded. Forming a ring to form a ring. In the formula (4), 'Qn is -p (R丨, 姊丨, a group derived from a heterocyclic compound containing a nitrogen atom which may be substituted, and one hydrogen atom is removed, • war " ,,), _〇-, _s-, ·δ(=〇)2〇·, c(=〇)〇., _p(=〇) (R15%, -As(=〇)(R_)2, Ρ(=δ)(κ17%, _As(=s)(Rl8Dn)2, -CN, -OH, -SH, -C(=0)〇H, -S(=〇)2〇h, -SR丨9Dn, or -C(=0)N(R21Dn)2. R11Dn

R 選 17Dm & 11 D m 1 8DmR select 17Dm & 11 D m 1 8Dm

R25Dm N j^26Dm X p27Dm ^ d28D j^I 6Dm j^24DmR25Dm N j^26Dm X p27Dm ^ d28D j^I 6Dm j^24Dm

R 12DiR 12Di

R 13DiR 13Di

R 15DnR 15Dn

R 16DnR 16Dn

R 、R及R Dn分別獨立為氫原子或可經取代之碳原 子數卜50之烴基，分別獨立為可經取代之碳 原子數1~30之烷基，R11Dn、R 12DnR, R and R Dn are each independently a hydrogen atom or a hydrocarbon group of a carbon atom which may be substituted, and are independently a substituted alkyl group having 1 to 30 carbon atoms, R11Dn, R 12Dn

R 13DnR 13Dn

R 14DnR 14Dn

R 15Di p 1 6 D η ρ 1 7 D η p 1 8 D η 〇 1 9 D η Ώ η 2 1 D η R R R R及尺可分別相同亦可不同。 卩31)11為P ' As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、P(=c〇、As卜⑺、ppy、 或 As(=S)。 156591.doc 43- 201202390 R為碳原子數5 0以下之2價基，然而，於所鍵結之Q丨Dn 為自含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形，或所鍵結之Q3Dn為自含氮原子之雜環式化合物中 去掉3個氫原子而成的基之情形時，亦可為直接鍵結。 R3Dn為碳原子數5〇以下之3價基。 選自 RllDn、Rl2Dn、Rl3Dn、Ri4Dn、Ri5Dn、R16Dn、R17Dn、 1 8Dn R19Dn、R21Dn、R2Dn D3Dn„ 上 R R 及自可經取代之含氮原子 之雜環式化合物中去掉丨個或3個氫原子而成的基中的2個 以上之基亦可任意鍵結而形成環。 式（Do)中，Q 為-P(R11D〇)2、-As(R丨2Do)2、自可經取代 之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -N(R )(R14D〇) . .〇- , _s- , _S(=〇)2〇- , .〇(=〇)〇- . -P(=0) (R15%、·Α—〇)(ΪΙ⑽。)2 …p(=s)(Rl7Do)2、_As(=s)(r]8D〇)2、-CN、-〇H、_SH、_C(=0)0H、_s(=〇)2〇H、_SR]9D。、或 -C(=0)N(R21D，2。r"d。、r12d。、r13Dq、r,5D。、r16D〇、 R R及R21D°分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，尺丨4〇。及！^丨扣。分別獨立為可經取代之碳 原子數1〜30之统基，rIid。、r12d。、r13d(R 15Di p 1 6 D η ρ 1 7 D η p 1 8 D η 〇 1 9 D η Ώ η 2 1 D η R R R R and the ruler may be the same or different.卩31)11 is a group formed by removing P'As from a heterocyclic compound containing a nitrogen atom which may be substituted by three hydrogen atoms, N, P (=c〇, AsBu(7), ppy, or As ( =S) 156591.doc 43- 201202390 R is a divalent group having a carbon number of 50 or less. However, the bonded Q丨Dn is one in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom. In the case of a group, or when the bonded Q3Dn is a group in which three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R3Dn is a carbon number of 5 〇. The following trivalent group is selected from the group consisting of RllDn, Rl2Dn, Rl3Dn, Ri4Dn, Ri5Dn, R16Dn, R17Dn, 1 8Dn R19Dn, R21Dn, R2Dn D3Dn„ on RR and from a heterocyclic compound having a nitrogen atom which may be substituted. Two or more of the groups of three or three hydrogen atoms may be bonded to each other to form a ring. In the formula (Do), Q is -P(R11D〇)2, -As(R丨2Do)2 a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R)(R14D〇) . .〇, , _s- , _S(=〇)2〇- , .〇(=〇)〇- . -P(=0) (R15%,· Α—〇)(ΪΙ(10).)2 ...p(=s)(Rl7Do)2, _As(=s)(r]8D〇)2, -CN, -〇H, _SH, _C(=0)0H, _s (=〇)2〇H,_SR]9D., or -C(=0)N(R21D,2.r"d.,r12d.,r13Dq,r,5D.,r16D〇, RR and R21D° are independent It is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may be substituted, and has a ring length of 4 to 30, and rIid, r12d, which are independently substituted carbon atoms. , r13d(

RR

R 14DoR 14Do

R 16DoR 16Do

R 15Do χR 15Do χ

R 17Di d18Do tj21Do —- x R 及R 可分別相同亦可不同 Q為P As、自可經取代之含氮原子之雜環式化合物 中去掉3個氫原子而成的基、N、p(=〇)、As(=〇)、p⑼、 或 As(=S)。 r2D。為碳原子數50以下之2價基，然而，於所鍵結之QiD〇 為自含氮原子之雜環式化合物中去掉1個氫原子而成的基 156591.doc 201202390 之情形，或所鍵結之q3〇。為自含氮原子之雜環式化合物中 去掉3個氫原子而成的基之情形時，亦可為直接鍵結。 R4D°為碳原子數70以下之4價基。 7Do、 選自 R11Do、Ri2D〇、r13D〇、Rl4Do、Rl5D〇、r16D〇、 r18D〇、r19Do 21Do、r2Do D 4Do „ > . ^ R R R 及自含氮原子之雜環式化 合物中去掉1個或3個氫原子而成的基中的2個以上之基亦 可任意鍵結而形成環。 式（Dp)中 ’ QW為 _P(R"Dp)2、_As(r12Dp)2、自可經取代 之含氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Dp)(R丨4D”、_〇·、_S-、_S(=〇)2〇·、_c(=〇)〇·、_ρ(=〇) (r15Dp)2、-α8(=〇)(ι^ρ)2、_p(=s)(r17Dp)2、_As(=s)(Rl8Dp)2、 -CN、-〇H、-SH、-C(=0)0H、-S(=〇)2〇H、-SR19Dp、或 -C(=〇)N(R2丨Dp)2。RnDP、R12Dp、Rhdp、Rl5Dp、Rl6Dp、 R17Dp、R18Dp&R21Dp分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R〗4Dp及R〇dp分別獨立為可經取代之碳 原子數 1 〜30之烷基，R11Dp、R12DP、R丨3Dp、R14Dp、R〗5Dp、 R⑽p、RnDp、Rl8Dp、尺㈣及尺2丨4可分別相同亦可不同。 Q2Dp為-P(R22Dp)-、-As(R23Dp)-、自可經取代之含氮原子 之雜壞式化合物中去掉2個氫原子而成的基、_n(r24〇p)_、 -P(=0)(R25DP)-、-As(=〇)(R26Dp)-、·Ρ(=3)(κ27〇ρ)_、或 _As(=s) (R28Dp)-。R22Dp、R23DP、R25DP、R26Dp ' r27Dp&r28Dp 分別 獨立為氫原子或可經取代之碳原子數1〜50之烴基，R24Dp為 可經取代之碳原子數1〜30之烷基，R22DP、r23DP、R24Dp、 R25Dp、r26Dp、r27DP及r28Dp可分別相同亦可不同。 156591.doc -45- 201202390 R3Dp為碳原子數5〇以下之3價基。 R4Dp為碳原子數70以下之4價基。 選自 R11Dp、R12DP、RUDP、R14Dp、R15DP、R16DP、R17Dp、 R18Dp、ri9Dp、R21Dp、r22Dp、r23Dp、r24Dp、r25Dp、 R26Dp、R27Dp、R28Dp、R3Dp、R4Dp及自可經取代之含氮原子 之雜環式化合物中去掉1個〜2個氫原子而成的基中的2個以 上之基亦可任意鍵結而形成環。 式（Dq)中，（^ι_ρ(κ"ι^)2、_As(Rl2Dq)2、自可經取代 之含氛原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Dq)(R14Dq)、_〇·、_s·、_s(=〇)2〇·、_c(=〇)〇·、_p(=〇) (Rl5Dq)2、-As(=〇)(R16Dq)2、-P(=s)(R17Dq)2、_As(=s)(R18Dq)2、 -CN、-OH、-SH、-C(=0)0H、-S(=〇)2〇H、-SR19Dq、或 -C(=0)N(R21Dq)2。、Ri2Dq、Ri3Dq、Rl5Dq、Rl6Dq、 R R q及r Dq分別獨立為氫原子或可經取代之碳原 子數1〜50之烴基，R14〇q&Ri9Dq分別獨立為可經取代之碳 原子數 1〜30 之烧基，R11Dq、Rl2Dq、Ri3Dq、RMDq、R丨 5Dt)、R 17Di d18Do tj21Do --- x R and R may be the same or different Q is P As, a radical formed by removing three hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, N, p (= 〇), As (=〇), p(9), or As(=S). r2D. It is a divalent group having a carbon number of 50 or less. However, in the case where the bonded QiD〇 is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, 156591.doc 201202390, or a bond The knot is q3〇. In the case of a group in which three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. R4D° is a tetravalent group having 70 or less carbon atoms. 7Do, selected from R11Do, Ri2D〇, r13D〇, Rl4Do, Rl5D〇, r16D〇, r18D〇, r19Do 21Do, r2Do D 4Do „ > . ^ RRR and 1 from the heterocyclic compound containing nitrogen atom or Two or more groups of the three hydrogen atoms may be bonded to each other to form a ring. In the formula (Dp), 'QW is _P(R"Dp)2, _As(r12Dp)2, and a group in which one hydrogen atom is removed from a heterocyclic compound having a nitrogen atom, -N(R13Dp)(R丨4D", _〇·, _S-, _S(=〇)2〇·, _c( =〇)〇·, _ρ(=〇) (r15Dp)2, -α8(=〇)(ι^ρ)2, _p(=s)(r17Dp)2, _As(=s)(Rl8Dp)2, - CN, -〇H, -SH, -C(=0)0H, -S(=〇)2〇H, -SR19Dp, or -C(=〇)N(R2丨Dp)2. RnDP, R12Dp, Rhdp , Rl5Dp, Rl6Dp, R17Dp, R18Dp& R21Dp are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and R 4Dp and R〇dp are independently substituted carbon atoms of 1 to 30, respectively. The alkyl group, R11Dp, R12DP, R丨3Dp, R14Dp, R〗 5Dp, R(10)p, RnDp, Rl8Dp, ruler (4) and ruler 2丨4 may be the same or different. Q2Dp is -P(R22Dp)-, -As(R23Dp) )- a group obtained by removing two hydrogen atoms from a heterocyclic compound containing a nitrogen atom, _n(r24〇p)_, -P(=0)(R25DP)-, -As(=〇)( R26Dp)-, ·Ρ(=3)(κ27〇ρ)_, or _As(=s)(R28Dp)-. R22Dp, R23DP, R25DP, R26Dp ' r27Dp&r28Dp are each independently a hydrogen atom or can be substituted a hydrocarbon group having 1 to 50 carbon atoms, R24Dp being a substitutable alkyl group having 1 to 30 carbon atoms, and R22DP, r23DP, R24Dp, R25Dp, r26Dp, r27DP and r28Dp may be the same or different. 156591.doc -45 - 201202390 R3Dp is a trivalent group having 5 or less carbon atoms. R4Dp is a tetravalent group having 70 or less carbon atoms. It is selected from the group consisting of R11Dp, R12DP, RUDP, R14Dp, R15DP, R16DP, R17Dp, R18Dp, ri9Dp, R21Dp, and r22Dp. And r23Dp, r24Dp, r25Dp, R26Dp, R27Dp, R28Dp, R3Dp, R4Dp and two or more of the groups obtained by removing one to two hydrogen atoms from the heterocyclic compound having a nitrogen atom which may be substituted It can also be bonded to form a ring. In the formula (Dq), (^ι_ρ(κ"ι^)2, _As(Rl2Dq)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a substituted atomic group, -N( R13Dq)(R14Dq), _〇·, _s·, _s(=〇)2〇·, _c(=〇)〇·, _p(=〇) (Rl5Dq)2, -As(=〇)(R16Dq)2 , -P(=s)(R17Dq)2, _As(=s)(R18Dq)2, -CN, -OH, -SH, -C(=0)0H, -S(=〇)2〇H,- SR19Dq, or -C(=0)N(R21Dq)2, Ri2Dq, Ri3Dq, Rl5Dq, Rl6Dq, RR q and r Dq are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, R14〇 q&Ri9Dq are independently a calcined group having 1 to 30 carbon atoms which may be substituted, R11Dq, Rl2Dq, Ri3Dq, RMDq, R丨5Dt),

Rl6Dq 、 Rl7Dq 、 18Dq 、 9D K 及11 可分別相同亦可不同。 Q4D4含有可配位於Ag+之p '含氮原子之雜環式化合物 中之Ν、Ο、或S·中之任一個的碳原子數7〇以下之々價基。 R叫為碳原子數50以下之2價基’然而，於所鍵結之QlDq 為自含氮原子之雜環式化合物中去掉】個氫原子而成的基 之情形時’亦可為直接鍵結。 R3Dq為碳原子數50以下之3價基。 選自 R"Dq、ddRMDq、R,5Dq、Rl6Dq、Ri7Dq、 156591.docRl6Dq, Rl7Dq, 18Dq, 9D K and 11 may be the same or different. Q4D4 contains a fluorenyl group having a carbon number of 7 Å or less which may be assigned to any of ruthenium, osmium or S. in the heterocyclic compound of the p' nitrogen atom of Ag+. R is a divalent group having a carbon number of 50 or less. However, when the bonded QlDq is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, it may be a direct bond. Knot. R3Dq is a trivalent group having 50 or less carbon atoms. From R"Dq, ddRMDq, R, 5Dq, Rl6Dq, Ri7Dq, 156591.doc

S 201202390 Q4Dq及自可經取 虱原子而成的基S 201202390 Q4Dq and the base from which the atom can be taken

Rl8Dq、R19Dq、R21Dq、R2Dq、R2Dq、R3Dq、 代之含氮原子之雜環式化合物中去掉1個 中的2個以上之基亦可任意鍵結而形成環。 式（Dr)巾，Q1Dr 為 _p(RiiDr)2、_As(Rl2Dr) 自可經取代 之含氮原子之雜環式化合物中去掉i個氫原子而成的基、 -N(R13Dr)(R14Dr)、-〇-、_s- s S(-〇)2〇、-C(=〇)〇-、_P(=0) (R15Dr)2 ' -As(=〇)(R16Dr) > .p/-cvR17Dr\ 八 )2、_As(=s)(Rl8Dr)2、 C(=0)〇H、-S(=〇)2〇h、_SR19Dr、或Rl8Dq, R19Dq, R21Dq, R2Dq, R2Dq, R3Dq, and a heterocyclic compound having a nitrogen atom instead may be bonded to form a ring by arbitrarily bonding two or more groups. Formula (Dr) towel, Q1Dr is _p(RiiDr)2, _As(Rl2Dr) A group obtained by removing i hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R13Dr)(R14Dr ), -〇-, _s- s S(-〇)2〇, -C(=〇)〇-, _P(=0) (R15Dr)2 ' -As(=〇)(R16Dr) > .p/ -cvR17Dr\ 八)2, _As(=s)(Rl8Dr)2, C(=0)〇H, -S(=〇)2〇h, _SR19Dr, or

CN、·〇Η、-SH -C( = 〇)N(R21Dr>2。RllDr、Rl2Dr、Rl3Dr、Ri5Dr、R⑽r、 及R刀別獨立為氫原子或可經取代之碳原CN, ·〇Η, -SH -C( = 〇)N(R21Dr>2. RllDr, Rl2Dr, Rl3Dr, Ri5Dr, R(10)r, and R are independently hydrogen atoms or substituted carbon atoms

R 17Dr 子數1~50之烴基，尺丨仙及尺 子數1〜30之烷基，RllDr、 以⑴、R17D、Rl8〇r、r19D>r2 Q5Df為含有可配位於Ag+2P中之N、〇·、或s-_之任一個 基0 分別獨立為可經取代之碳原 R12Dr、Rl3Dr、Rl4Dr、Rl5Dr、 1D)·可分別相同亦可不同。 、含氮原子之雜環式化合物 的碳原子數1 〇〇以下之5價 R為奴原子數5〇以下之2價基，然而，於所鍵結之QlDr 為自3氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形時，亦可為直接鍵結。 選自 R1丨Dr、R12Dr、Rl3Dr、R〗4Dr、r丨仙、R]6Dr、汉丨…、R 17Dr is a hydrocarbon group of 1 to 50, an anthracene and an alkyl group having a number of 1 to 30, and RllDr, (1), R17D, Rl8〇r, r19D>r2 Q5Df are N which can be coordinated to Ag+2P. Any one of the 〇·, or s-_ groups 0 is independently a carbon atom which can be substituted, R12Dr, Rl3Dr, Rl4Dr, Rl5Dr, 1D)· can be the same or different. The 5-valent R having a carbon atom number of 1 〇〇 or less of a heterocyclic compound containing a nitrogen atom is a divalent group having a number of slave atoms of 5 Å or less, however, the bonded QlDr is a heterocyclic ring derived from 3 nitrogen atoms. In the case where a compound in which a hydrogen atom is removed from a compound is used, it may be a direct bond. Selected from R1丨Dr, R12Dr, Rl3Dr, R〗4Dr, r丨仙, R]6Dr, 汉丨...,

Rl8\d1DF、CH自可經取代之含氮原子 之雜％式化合物中去掉“固氫原子而成的基中的2個以上之 基亦可任意鍵結而形成環。 式（Ds)中，QiDs為-p(R丨丨丨2Ds)2、自可經取代 156591.doc •47- 201202390Rl8\d1DF and CH may be arbitrarily bonded to form a ring by removing two or more groups of a "hydrogen atom" from a heterocyclic compound having a nitrogen atom which may be substituted. In the formula (Ds), QiDs is -p(R丨丨丨2Ds)2, self-replaceable 156591.doc •47- 201202390

之含氮原子之雜環式化合物中去掉丨個氫原子而成的基、_N(R 丨 3D，丨，、_〇·、s.、a，。、。㈣。、*〇) (R15Ds)2 ^ -As(=〇)(R>6% . .P(=S)(r.7Ds)2 ^ _As(=s)(r18Ds)2 ^ -CN、-OH、-SH、-C(=0)〇H、-S(=〇)2〇H、_SRi9Ds、或 -C(=0)N(R21Ds)2 〇 R11Ds、R】2Ds、R 13D<a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, _N(R 丨3D, 丨, _〇·, s., a, ., . (4), *〇) (R15Ds) 2 ^ -As(=〇)(R>6% . .P(=S)(r.7Ds)2 ^ _As(=s)(r18Ds)2 ^ -CN, -OH, -SH, -C(= 0) 〇H, -S(=〇)2〇H, _SRi9Ds, or -C(=0)N(R21Ds)2 〇R11Ds, R]2Ds, R 13D<

R 15DsR 15Ds

R 16Ds 分別獨立為氫原？或可經取代之碳原 子數1〜50之烴基，1^4仏及尺丨仙分別獨立為可經取代之碳 原子數1〜30之烧基，R11Ds、Rl2DsR 16Ds are independently hydrogenogens? Or a hydrocarbon group having a carbon number of 1 to 50 which may be substituted, and 1^4仏 and 丨仙, respectively, are independently substituted carbon atoms having a carbon number of 1 to 30, R11Ds, Rl2Ds

R 13DsR 13Ds

R 14DsR 14Ds

R 16DsR 16Ds

R 1 5DsR 1 5Ds

R 17DsR 17Ds

R 18Ds R 及R21DS可分別相同亦可不同 Q〜(R，_、婦，、自可經取代之含氮原子 之雜環式化合物中去掉2個氫原子而成的基、娜24Ds)_、 P(=〇)(R2，·、_As(=0)(r2，_、·ρ(=8χιι27Γ)5)、或 A㈣ 叱严、R_、R⑽、R職、r27Dsar28Ds分別獨 立為氫原子或可經取代之碳原子數丨〜％之烴基，r24Ds為可 ―呈取代之故原子數1〜30之烧基，R22Ds、r23Ds r25::r26ds、r〜28ds可分別相同亦可不同。 R2Ds為碳原子數50以下之2價基，然而，於所鍵結之QiDs 為自含氮原子之雜環式化合物中去⑴個氣原子而成的基 之情形’或所鍵結之Q、自含氮原子之雜環式化合物中 去掉j個氫原子而成的基之情料，亦可為直接鍵結。 R 為碳原子數100以下之5價基。選自 R1,Ds、r】2Ds、RnDs、Rl4Ds、R丨5DS、R]6Ds、严、R18Ds、R_、r2,Ds、r22Ds、r23Ds、R24Ds、R25Ds、R臟、 R2-、R-、〜、自可經取代之含氮原子之雜環R 18Ds R and R21DS may be the same or different Q~(R, _, ,, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , P(=〇)(R2,·,_As(=0)(r2,_,·ρ(=8χιι27Γ)5), or A(iv) 叱, R_, R(10), R, r27Dsar28Ds are independently hydrogen atoms or can be Substituting a hydrocarbon group having a carbon number of 丨~%, r24Ds is a group which can be substituted with an atomic number of 1 to 30, and R22Ds, r23Ds r25::r26ds, r~28ds may be the same or different. R2Ds is a carbon atom. a divalent group having a number of 50 or less, however, the bonded QiDs is a group in which a (1) gas atom is derived from a heterocyclic compound containing a nitrogen atom' or a bonded Q, a self-containing nitrogen atom In the heterocyclic compound, a group in which j hydrogen atoms are removed may be a direct bond. R is a 5-valent group having 100 or less carbon atoms selected from R1, Ds, r] 2Ds, RnDs, Rl4Ds, R丨5DS, R]6Ds, Yan, R18Ds, R_, r2, Ds, r22Ds, r23Ds, R24Ds, R25Ds, R dirty, R2-, R-, ~, self-substitutable nitrogen-containing heterocyclic ring

R 24D- 156591.docR 24D- 156591.doc

S •48- 201202390 式化合物中去掉丨個〜2個氫原子而成的基十的2個以上之基 亦可任意鍵結而形成環。 式（Dt)中，dp(RllDt)2、_As(Rl2Dt)2、自可經取代之 含氮原子之雜環式化合物中去掉i個氫原子而成的基、 -N(R )(Rl4Dt)、·〇·、_s-、_s 卜⑺2〇-、c( = 〇)〇- p卜⑺ (R15%、-As(=〇Xr_)2、_p(=s)(Rl7Dt)2、_As、 -CN、-OH、-SH、_c(=〇)〇H、·δ(=〇)2〇Η、sRl9m、或 -C(=0)N(R_)2。RnDt、Rl2Dt、Rl3Dt、Ri5Dt、Ri6Dt、 R_、Rl8D> R21Dt分別獨立為氫原子或可經取代之碳原子 數1〜50之烴基，尺丨仙及尺丨9m分別獨立為可經取代之碳原子 數卜30 之烷基 ’ R丨丨m、Rl2Dt、Rl3Dt、RUDt、Ri5Dt、 R1S 48-201202390 Two or more groups of the decyl group obtained by removing one to two hydrogen atoms in the compound of the formula may be arbitrarily bonded to form a ring. In the formula (Dt), dp(RllDt)2, _As(Rl2Dt)2, a group obtained by removing i hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, -N(R)(Rl4Dt) ,·〇·, _s-, _s 卜(7)2〇-, c( = 〇)〇- p(7) (R15%, -As(=〇Xr_)2, _p(=s)(Rl7Dt)2, _As, - CN, -OH, -SH, _c(=〇)〇H,·δ(=〇)2〇Η, sRl9m, or -C(=0)N(R_)2. RnDt, Rl2Dt, Rl3Dt, Ri5Dt, Ri6Dt , R_, Rl8D> R21Dt are each independently a hydrogen atom or a substituted hydrocarbon group having 1 to 50 carbon atoms, and the 9m of the ruthenium and the ruthenium are independently the alkyl group of the carbon atom which can be substituted.丨m, Rl2Dt, Rl3Dt, RUDt, Ri5Dt, R1

R R1R R1

R R6Dt為碳原子數1 5〇以下之6價基 及R21Dt可分別相同亦可不同 選自R11Dt R】2Dt、RnDt、Rl4Dt、Rl5Dt、尺16叫 R17Dt、 R18Dt x R19Dt λ R21Dt 式化合物中去掉1個 而形成環。 R6Dt及自可經取代之含氮原子之雜環 氫原子而成的基中的基亦可任意鍵結 上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(以) 所表示之分子較佳為含有2個以上之可配位於Ag+之磷原 子。該鱗原子較佳為未鍵結sp3碳原子，其原因在於膜對 於氧之耐久性提高。 ' 以下’對上述式（Aa)、（Ab)、（Ba)〜_、（Ca)〜(ci)、及 (Da)〜(Dt)所表示之分子分別加以說明。 上述式（Aa)及（Ab)所表示之分子的結構較佳為 156591.doc -49- 201202390 具有3個磷原子之結構、 具有2個磷原子及1個氮原子之結構、 具有2個磷原子及1個氧陰離子之結構、 具有2個磷原子及1個硫陰離子之結構、或 具有2個磷原子及1個砷原子之結構， 更佳為 具有2個磷原子及1個氮原子之結構、或 具有2個磷原子及1個氧陰離子之結構。 上述式（Ba)〜(Bd)所表示之分子的結構較佳為 具有4個磷原子之結構、 具有3個磷原子及1個氮原子之結構、 具有3個磷原子及1個氧陰離子之結構、 具有3個磷原子及1個硫陰離子之結構、 具有3個磷原子及1個砷原子之結構、 具有2個磷原子及2個氮原子之結構、或 具有2個磷原子及2個砷原子之結構， 更佳為 具有4個磷原子之結構、 具有3個磷原子及1個氮原子之結構、 具有3個磷原子及1個氧陰離子之結構、 具有3個磷原子及1個硫陰離子之結構、或 具有2個磷原子及2個氮原子之結構， 進而較佳為 具有4個磷原子之結構、 156591.doc -50- 201202390 具有3個磷原子及1個氧陰離子之結構、或 具有2個磷原子及2個氮原子之結構， 尤佳為 具有3個磷原子及1個氧陰離子之結構、或 具有2個磷原子及2個氮原子之結構。 上述式（Ca)~(Ci)所表示之分子的結構較佳為 具有5個磷原子之結構、 具有4個磷原子及1個氮原子之結構、 具有4個磷原子及1個氧陰離子之結構、 具有4個磷原子及1個硫陰離子之結構、 具有4個磷原子及1個砷原子之結構、 具有3個磷原子及2個氮原子之結構、 具有3個磷原子及2個氧原子之結構、 具有3個磷原子及2個硫陰離子之結構、 具有3個磷原子及2個砷原子之結構、 具有2個磷原子及3個氮原子之結構、或 具有2個磷原子及3個砷原子之結構， 更佳為 具有5個磷原子之結構、 具有4個磷原子及1個氮原子之結構、 具有4個磷原子及1個氧陰離子之結構、 具有4個磷原子及1個硫陰離子之結構、 具有3個磷原子及2個氮陰離子之結構、或 具有2個磷原子及3個氮原子之結構， 156591.doc -51 - 201202390 進而較佳為 具有5個磷原子之結構、 具有4個磷原子及1個氧陰離子之結構、 具有4個磷原子及1個硫陰離子之結構、 具有3個磷原子及2個氮原子之結構、或 具有2個磷原子及3個氮原子之結構， 尤佳為 具有5個磷原子之結構、 具有4個磷原子及1個氧陰離子之結構、 具有3個磷原子及2個氮原子之結構、或 具有2個磷原子及3個氮原子之結構， 特佳為 具有5個磷原子之結構、或 具有4個磷原子及1個氧陰離子之結構。 上述式（Da)〜(Dt)所表示之分子的結構較佳為 具有6個磷原子之結構、 具有5個磷原子及1個氮原子之結構、 具有5個磷原子及1個氧陰離子之結構、 具有5個磷原子及1個硫陰離子之結構、 具有5個磷原子及1個砷原子之結構、 具有4個磷原子及2個氮原子之結構、 具有4個磷原子及2個氧陰離子之結構、 具有4個磷原子及2個硫陰離子之結構、 具有4個磷原子及2個砷原子之結構、 -52- 156591.docR R6Dt is a hexavalent group having a carbon number of 15 〇 or less and R21Dt may be the same or different from R11Dt R] 2Dt, RnDt, Rl4Dt, Rl5Dt, Rule 16 is called R17Dt, R18Dt x R19Dt λ R21Dt is removed from the compound. And form a ring. The group in the group of R6Dt and a heterocyclic hydrogen atom which may be substituted with a nitrogen atom may be arbitrarily bonded to the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to ( The molecule represented by Ci) and (Da) to (I) preferably contains two or more phosphorus atoms which can be coordinated to Ag+. The squamous atom is preferably an unbonded sp3 carbon atom because the durability of the film against oxygen is improved. The following formulas (Aa), (Ab), (Ba) to _, (Ca) to (ci), and (Da) to (Dt) are respectively described. The structure of the molecule represented by the above formulas (Aa) and (Ab) is preferably 156591.doc -49-201202390 having a structure of three phosphorus atoms, a structure having two phosphorus atoms and one nitrogen atom, and having two phosphorus a structure of an atom and one oxyanion, a structure having two phosphorus atoms and one sulfur anion, or a structure having two phosphorus atoms and one arsenic atom, more preferably having two phosphorus atoms and one nitrogen atom Structure, or a structure having two phosphorus atoms and one oxygen anion. The structure of the molecule represented by the above formulas (Ba) to (Bd) is preferably a structure having four phosphorus atoms, a structure having three phosphorus atoms and one nitrogen atom, having three phosphorus atoms and one oxygen anion. Structure, structure having three phosphorus atoms and one sulfur anion, a structure having three phosphorus atoms and one arsenic atom, a structure having two phosphorus atoms and two nitrogen atoms, or having two phosphorus atoms and two The structure of the arsenic atom is more preferably a structure having four phosphorus atoms, a structure having three phosphorus atoms and one nitrogen atom, a structure having three phosphorus atoms and one oxygen anion, three phosphorus atoms and one a structure of a sulfur anion or a structure having two phosphorus atoms and two nitrogen atoms, and further preferably a structure having four phosphorus atoms, 156591.doc -50-201202390 having three phosphorus atoms and one oxygen anion structure Or a structure having two phosphorus atoms and two nitrogen atoms, and particularly preferably a structure having three phosphorus atoms and one oxyanion, or a structure having two phosphorus atoms and two nitrogen atoms. The structure of the molecule represented by the above formula (Ca) to (Ci) is preferably a structure having five phosphorus atoms, a structure having four phosphorus atoms and one nitrogen atom, having four phosphorus atoms and one oxygen anion. Structure, structure having 4 phosphorus atoms and 1 sulfur anion, structure having 4 phosphorus atoms and 1 arsenic atom, structure having 3 phosphorus atoms and 2 nitrogen atoms, having 3 phosphorus atoms and 2 oxygen a structure of an atom, a structure having three phosphorus atoms and two sulfur anions, a structure having three phosphorus atoms and two arsenic atoms, a structure having two phosphorus atoms and three nitrogen atoms, or having two phosphorus atoms and The structure of three arsenic atoms is more preferably a structure having five phosphorus atoms, a structure having four phosphorus atoms and one nitrogen atom, a structure having four phosphorus atoms and one oxyanion, having four phosphorus atoms and a structure of one sulfur anion, a structure having three phosphorus atoms and two nitrogen anions, or a structure having two phosphorus atoms and three nitrogen atoms, 156591.doc -51 - 201202390 and further preferably having five phosphorus atoms Structure, having four phosphorus atoms and one oxygen anion structure, a structure having four phosphorus atoms and one sulfur anion, a structure having three phosphorus atoms and two nitrogen atoms, or a structure having two phosphorus atoms and three nitrogen atoms, and particularly preferably a structure having five phosphorus atoms a structure having four phosphorus atoms and one oxyanion, a structure having three phosphorus atoms and two nitrogen atoms, or a structure having two phosphorus atoms and three nitrogen atoms, and particularly preferably having five phosphorus atoms. Structure, or a structure having four phosphorus atoms and one oxygen anion. The structure of the molecule represented by the above formulas (Da) to (Dt) is preferably a structure having six phosphorus atoms, a structure having five phosphorus atoms and one nitrogen atom, having five phosphorus atoms and one oxygen anion. Structure, structure having 5 phosphorus atoms and 1 sulfur anion, structure having 5 phosphorus atoms and 1 arsenic atom, structure having 4 phosphorus atoms and 2 nitrogen atoms, having 4 phosphorus atoms and 2 oxygen Anionic structure, structure having 4 phosphorus atoms and 2 sulfur anions, structure having 4 phosphorus atoms and 2 arsenic atoms, -52-156591.doc

S 201202390 具有3個磷原子及3個氮原子之結構、 具有3個磷原子及3個砷原子之結構、 具有2個磷原子及4個氮原子之結構、或 具有2個磷原子及4個砷原子之結構， 更佳為 具有6個磷原子之結構、 具有5個磷原子及1個氮原子之結構、 具有5個磷原子及1個氧陰離子之結構、 具有5個磷原子及1個硫陰離子之結構、 具有4個磷原子及2個氮原子之結構、 具有4個磷原子及2個氧陰離子之結構、 具有4個磷原子及2個硫陰離子之結構、 具有3個磷原子及3個氮原子之結構、或 具有2個磷原子及4個氮原子之結構， 進而較佳為 具有6個磷原子之結構、 具有5個磷原子及1個氧陰離子之結構、 具有5個磷原子及1個硫陰離子之結構、 具有4個磷原子及2個氮原子之結構、或 具有3個磷原子及3個氮原子之結構 尤佳為 具有6個磷原子之結構、 具有5個磷原子及1個氧陰離子之結構、或 具有4個磷原子及2個氮原子之結構。 156591.doc -53- 201202390 於上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜 (Dt)所表示之分子中，較佳為含有i個可配位於Ag+之氧陰 離子或硫陰離子。 作為上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及 (Da)〜(Dt)所表示之分子中的含氮原子之雜環式化合物之 例，可列舉.η比咬、塔u井、π密咬、吨，井、三啡、喧琳、異 喹啉、咪唑、吡唑、呤唑、噻唑、噚二唑、噻二唑、氮雜 一唑及吖啶β由於容易形成成膜性良好之錯合物故較佳 為吡啶、咪唑、喹啉及異喹啉，更佳為吡啶、咪唑及喹 琳’進而較佳為咪唑及喹琳。 作為該含有氮原子之雜環式化合物可具有的取代基之 例，可列舉齒素原子、經齒素原子取代之碳原子數丨〜”之 烴基、碳原子數1〜50之烴基、碳原子數卜24之烴氧基及碳 原子數1〜24之二芳基胺基。其中，較佳為氟原子、氣原 子、溴原子、碘原子、三氟甲基、三氣曱基、曱基、乙 基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、己 基、庚基、辛基、壬基、癸基、十二烷基、十八烷基、二 十二烷基、環戊基、環己基、環辛基、環十二烷基、降宿 基、金剛烷基、乙烯基、丙烯基、3·丁烯基、2_丁烯基、 2-戊烯基、苯基、ι_萘基、2_萘基、2_甲基苯基、％曱基 苯基、4-甲基苯基、2-甲氧基苯基、3_甲氧基苯基、4_曱 氧基苯基、4-乙基苯基、4_丙基苯基、4第三丁基苯基、 4-己基苯基、4_環己基苯基、4_金剛烷基苯基、2_苯基苯 基、9-苐基、苯基曱基、卜苯基乙基、2苯基乙基曱氧 156591.doc -54- 201202390 基、乙氧基、丙氧基、丁氧基、己氧基、苯氧基、二苯基 胺基、雙（2-甲基苯基）胺基、雙（3_甲基苯基）胺基、雙（4_ 甲基苯基）胺基、雙（4-第三丁基苯基）胺基、二萘基胺基， 更佳為氟原子、氯原子、溴原子、三氟甲基、甲基、乙 基、丙基、異丙基、丁基、第三丁基、己基、辛基、十二 烷基、十八烷基、環己基、金剛烷基、乙烯基、苯基、2_ 曱基苯基、2-甲氧基苯基、4-曱氧基笨基、4_第三丁基苯 基、2-苯基苯基、9-苐基、苯基甲基、丨_苯基乙基、甲氧 基、乙氧基、丙氧基、丁氧基、己氧基、苯氧基、二苯基 胺基、雙（2-甲基苯基）胺基、雙（3_甲基苯基）胺基、雙（4_ 甲基苯基）胺基及雙（4-第三丁基苯基）胺基，進而較佳為氟 原子、氯原子、溴原子、甲基、乙基、丙基、異丙基、丁 基、第三丁基、己基、乙烯基、笨基甲基、曱氧基、乙氧 基、丁氧基、己氧基及苯氧基，尤佳為氟原子、氯原子、 曱基、丁基、曱氧基、丁氧基、及苯氧基。 含氮原子之雜環式化合物可具有之取代基之數較佳為〇 個〜4個，更佳為〇個〜3個，進而較佳為〇個〜2個尤佳為1 個〜2個。 可經取代之含氮原子之雜環式化合物可具有之該取代基 彼此亦可縮合而形成環結構。例如，亦可於咪唑之4,5-位 上鍵結乙烯基，該乙烯基彼此縮合而成為苯環，形成苯并 咪唑骨架。 以下示出上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(c〇、及 (Da)〜(Dt)所表示之分子中的可經取代之烴基的烴基之例·· 156591.doc •55· 201202390 甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁 基、戊基、己基、庚基 '辛基、壬基、癸基、Ί —炫> 基、 十二烷基、十五烷基、十八烷基、二十二烷基等碳原子數 1〜50之烷基； 環丙基、環丁基、環戊基、環己基、環壬基、環十二貌 基、降葙基、金剛烧基等碳原子數3〜50之環狀飽和烴基； 乙烯基、丙烯基、3-丁烯基、2-丁烯基、2-戊烯基、2- 己稀基、2 -壬稀基、2 -十一碳浠基等碳原子數2〜50之稀 基； 苯基、1-萘基、2-萘基、2-甲基苯基、3-甲基苯基、4- 甲基苯基、2,4,6-三甲基苯基、2-異丙基苯基、4-乙基苯 基、4-丙基苯基、4-異丙基苯基、4-丁基苯基、4-第三丁 基苯基、4-己基苯基、4-(2-乙基己基）苯基、4_環己基苯 基、4-金剛烷基苯基、4_苯基苯基、9_第基等碳原子數 6〜50之芳基； 苯基甲基、1-苯基乙基、2-苯基乙基、丨_苯基_丨丙基、 1-苯基-2-丙基、2-苯基-2-丙基、3-苯基丙基、4_苯基· 1-丁基、5-苯基-1-戊基、6_苯基_丨_己基等碳原子數7〜5〇之 芳烧基。 於對各事例並無特別記載之情形時，上述烴基較佳為甲 基、第三丁基、己基、十二烧基、環己基、苯基、卜蔡 基、2-萘基、2_甲基苯基、3·甲基苯基、扣甲基苯基、 2,4’6-三甲基苯基、2·異丙基苯基、4乙基苯基、4丙基苯 基、4-異丙基苯基、4·丁基苯基、4第三丁基苯基、4·己 15659J.docS 201202390 has a structure of three phosphorus atoms and three nitrogen atoms, a structure having three phosphorus atoms and three arsenic atoms, a structure having two phosphorus atoms and four nitrogen atoms, or two phosphorus atoms and four The structure of the arsenic atom is more preferably a structure having six phosphorus atoms, a structure having five phosphorus atoms and one nitrogen atom, a structure having five phosphorus atoms and one oxygen anion, having five phosphorus atoms and one a structure of a sulfur anion, a structure having four phosphorus atoms and two nitrogen atoms, a structure having four phosphorus atoms and two oxygen anions, a structure having four phosphorus atoms and two sulfur anions, having three phosphorus atoms and a structure of three nitrogen atoms or a structure having two phosphorus atoms and four nitrogen atoms, and further preferably a structure having six phosphorus atoms, a structure having five phosphorus atoms and one oxygen anion, and having five phosphorus The structure of an atom and a sulfur anion, a structure having four phosphorus atoms and two nitrogen atoms, or a structure having three phosphorus atoms and three nitrogen atoms, preferably having a structure of six phosphorus atoms and having five phosphorus The structure of an atom and an oxygen anion, or has 4 The structure of a phosphorus atom and two nitrogen atoms. 156591.doc -53- 201202390 Among the molecules represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt), it is preferred. It is composed of i oxyanions or sulfur anions which can be coordinated to Ag+. a heterocyclic compound containing a nitrogen atom in a molecule represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt) For example, η ratio bite, tower u well, π dense bite, ton, well, trimorphine, quinone, isoquinoline, imidazole, pyrazole, oxazole, thiazole, oxadiazole, thiadiazole, nitrogen The heteroazole and the acridine β are preferably pyridine, imidazole, quinoline and isoquinoline, and more preferably pyridine, imidazole and quinoline, and more preferably imidazole and quinoline, because they are easy to form a complex with good film forming properties. . Examples of the substituent which the heterocyclic compound containing a nitrogen atom may have include a dentate atom, a hydrocarbon group having a carbon atom number of 丨~” substituted by a dentate atom, a hydrocarbon group having 1 to 50 carbon atoms, and a carbon atom. a hydrocarbyloxy group and a diarylamino group having 1 to 24 carbon atoms. Among them, a fluorine atom, a gas atom, a bromine atom, an iodine atom, a trifluoromethyl group, a triazepine group or a mercapto group are preferred. , ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, dodecyl, octadecyl, Dodecyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, pentylene, adamantyl, vinyl, propenyl, 3·butenyl, 2-butenyl, 2 -pentenyl, phenyl, iotaphthyl, 2-naphthyl, 2-methylphenyl, % nonylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxy Phenylphenyl, 4-methoxyphenyl, 4-ethylphenyl, 4-propylphenyl, 4th butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4_gold Alkylphenyl, 2-phenylphenyl, 9-fluorenyl, phenylfluorenyl, benzene Ethyl ethyl, 2 phenylethyl fluorene 156591.doc -54- 201202390, ethoxy, propoxy, butoxy, hexyloxy, phenoxy, diphenylamino, bis (2- Methylphenyl)amino, bis(3-methylphenyl)amino, bis(4-methylphenyl)amino, bis(4-t-butylphenyl)amino, dinaphthylamino More preferably, it is a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, an octyl group, a dodecyl group, and a tenth Octaalkyl, cyclohexyl, adamantyl, vinyl, phenyl, 2-nonylphenyl, 2-methoxyphenyl, 4-decyloxy, 4-tert-butylphenyl, 2- Phenylphenyl, 9-fluorenyl, phenylmethyl, fluorenyl-phenylethyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, phenoxy, diphenylamine Base, bis(2-methylphenyl)amino, bis(3-methylphenyl)amine, bis(4-methylphenyl)amine and bis(4-t-butylphenyl)amine Further preferably a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a third group , hexyl, vinyl, benzyl, decyloxy, ethoxy, butoxy, hexyloxy and phenoxy, especially preferably a fluorine atom, a chlorine atom, a decyl group, a butyl group, a decyloxy group, The butoxy group and the phenoxy group. The heterocyclic compound having a nitrogen atom may have a substituent number of preferably ～4, more preferably 〜3, and further preferably 〜2. More preferably, it is one to two. The heterocyclic compound having a nitrogen atom which may be substituted may have a substituent which may be condensed with each other to form a ring structure. For example, it may be at the 4,5-position of imidazole. The vinyl group is bonded to each other to form a benzene ring to form a benzimidazole skeleton. The following formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (c, And an example of a hydrocarbon group of a hydrocarbon group which may be substituted in the molecule represented by (Da) to (Dt). 156591.doc • 55· 201202390 Methyl, ethyl, propyl, isopropyl, butyl, isobutyl Base, tert-butyl, pentyl, hexyl, heptyl 'octyl, decyl, fluorenyl, fluorene-> base, dodecyl, pentadecyl, octadecyl, docosane Carbon atom a number of 1 to 50 alkyl groups; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, a cyclododecyl group, a decyl group, an adamantyl group, and the like having a ring number of 3 to 50 a saturated hydrocarbon group; a carbon number such as a vinyl group, a propenyl group, a 3-butenyl group, a 2-butenyl group, a 2-pentenyl group, a 2-hexyl group, a 2-indenyl group, a 2-undecyl group or the like a dilute base of 2 to 50; phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4,6-trimethyl Phenyl, 2-isopropylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4 -hexylphenyl, 4-(2-ethylhexyl)phenyl, 4-cyclohexylphenyl, 4-adamantylphenyl, 4-phenylphenyl, 9-diyl, etc. 6 to 50 carbon atoms Aryl; phenylmethyl, 1-phenylethyl, 2-phenylethyl, 丨-phenyl- hydrazinopropyl, 1-phenyl-2-propyl, 2-phenyl-2-propenyl An aryl group having 7 to 5 carbon atoms such as a group, a 3-phenylpropyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group or a 6-phenyl-fluorenyl-hexyl group. In the case where there is no particular description for each case, the above hydrocarbon group is preferably a methyl group, a tert-butyl group, a hexyl group, a dodecaidyl group, a cyclohexyl group, a phenyl group, a phenyl group, a 2-naphthyl group, or a 2-methyl group. Phenylphenyl, 3·methylphenyl, methyl phenyl, 2,4′6-trimethylphenyl, 2·isopropylphenyl, 4 ethylphenyl, 4 propylphenyl, 4 -isopropylphenyl, 4-butylphenyl, 4th butylphenyl, 4·15659J.doc

S •56· 201202390 基苯基、4-(2-乙基己基）苯基、4-環己基苯基、4-金剛烷基 苯基、4-苯基苯基、9_苐基、苯基甲基，更佳為第三丁 基、環己基、苯基、2-甲基苯基、4-甲基苯基、2,4,6-三甲 基苯基、2-異丙基苯基、4-第三丁基苯基、4-己基苯基、 4-環己基苯基’進而較佳為苯基、2_甲基苯基、2,4,6•三甲 基苯基、4-第三丁基苯基'4-己基苯基，尤佳為苯基、2_ 甲基苯基。 該扭基可具有之取代基之例與上述含氮原子之雜環式化 合物可具有之取代基相同，為鹵素原子、碳原子數丨〜卯之 烴基、碳原子數1〜24之烴氧基及碳原子數卜24之二芳基胺 基。較佳為氟原子、氣原子、溴原子、碘原子、三氟甲 基、甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁 基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、 十八烧基、一十一烧基、環戊基、環己基、環辛基、環十 二烷基、降葙基、金剛烷基、乙烯基、丙烯基、3_丁烯 基、2-丁烯基、2-戊烯基、苯基、丨_萘基、2·萘基、2_甲 基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3_甲 氧基笨基、曱氧基笨基、4-乙基苯基、4-丙基苯基、4_ 第三丁基苯基、4-己基苯基、4_環己基苯基、4_金剛烷基 苯基、2-苯基苯基、9-苐基、苯基甲基、卜苯基乙基、2_ 苯基乙基、甲氧基、乙氧基、丙氧基、丁氧基、己氧基、 苯氧基、二苯基胺基、雙（2-甲基苯基）胺基、雙（3甲基苯 基）胺基、雙（4-甲基苯基）胺基、雙（4_第三丁基笨基）胺基 及一萘基胺基，更佳為氟原子、氣原子、溴原子、三氟甲 156591.doc •57· 201202390 基、甲基、乙基、丙基、丁基、第三丁基、己基、辛基、 十一烧基、環己基、金剛烧基、苯基、1-萘基、2-萘基、 2-甲基苯基、3-甲基苯基、4-甲基苯基、4-第三丁基苯 基、9-第基、苯基曱基、甲氧基、乙氧基、丙氧基、丁氧 基、己氧基、苯氧基、二苯基胺基、雙（2-甲基苯基）胺 基、雙（3-甲基苯基）胺基、雙（4-曱基苯基）胺基、雙（4_第 三丁基笨基）胺基及二萘基胺基，進而較佳為氟原子、三 氟甲基、甲基、第三丁基、己基、辛基、苯基、2_甲基苯 基、4-第三丁基苯基、苯基甲基、甲氧基、乙氧基、丁氧 基、己氧基、及苯氧基’尤佳為氟原子 '甲基、第三丁 基、及甲氧基。 作為上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及 (Da)〜(Dt)所表示之分子中的可經取代之烷基之例，可列舉 甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬 基、癸基、十一烷基、十二烷基、十五烷基、十八烷基、 一十二烧基等碳原子數1〜3〇之直鏈狀烴基，可為異丙基、 異丁基、第二丁基及2-乙基己基般具有分支結構之烧基， 亦可為環丙基、環丁基、環戊基、環己基、環壬基、環十 二烷基、降蒱基及金剛烷基般具有環狀結構之烷基。較佳 為甲基、乙基、丁基、第三丁基、己基、辛基、十二烷 基、十八烧基及環己基，更佳為甲基、丁基、己基、辛 基，進而較佳為甲基。 作為自上述可經取代之含氮原子之雜環式化合物中去掉 2個氫原子而成的基之例，可列舉與自上述可經取代之含 I56591.doc •58- 201202390 2原子之雜環式化合物之例中具有2個以上之氫原子之化 結構中去掉2個氫原子而成的基相同者。作為自上 述可經取代之含氮原子之雜環式化合物中去掉3個氫原子 而成的基之例，可列舉與自上述可經取代之含氮原子之雜 環式化合物之例令具有3個以上之氨原子之化合物之結構 中去掉3個氫原子而成的基相同者。作為自上述可經取代 之含氮原子之雜環式化合物中去掉4個氫原子而成心價基 之例，可列舉與自上述可經取代之含氮原子之雜環式化合 物之例中具有4個以上之氫原子之化合物之結構中去掉*個 氫原子而成的基相同者。作為自上述可經取代之含氮原子 之雜環式化合物中去掉5個氫原子而成的5價基之例，可列 舉與自上述可經取代之含氮原子之雜環式化合物之例中具 有5個以上之氫原子之化合物之結構中去掉5個氫原子而成 的基相同者。作為自上述可經取代之含氮原子之雜環式化 口物中去掉6個氫原子而成的6價基之例，可列舉與自上述 可經取代之含氮原子之雜環式化合物之例中具有6個以上 之氫原子之化合物之結構中去掉6個氫原子而成的基相同 者。 作為上述R2Aa、R2Ba、R2Bb、r2Bc、R2Ca、R2Cb、ye。、S •56· 201202390 phenyl, 4-(2-ethylhexyl)phenyl, 4-cyclohexylphenyl, 4-adamantylphenyl, 4-phenylphenyl, 9-fluorenyl, phenyl Methyl, more preferably tert-butyl, cyclohexyl, phenyl, 2-methylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, 2-isopropylphenyl 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl' is further preferably phenyl, 2-methylphenyl, 2,4,6•trimethylphenyl, 4 -T-butylphenyl '4-hexylphenyl, more preferably phenyl, 2-methylphenyl. The substituent which the twist group may have is the same as the substituent which the above-mentioned nitrogen atom-containing heterocyclic compound may have, and is a halogen atom, a hydrocarbon group having a carbon number of 丨~卯, and a hydrocarbon group having 1 to 24 carbon atoms. And a carbon atom number of 24 diarylamine groups. Preferred are fluorine atom, gas atom, bromine atom, iodine atom, trifluoromethyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, decyl, decyl, dodecyl, octadecyl, eleven alkyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, decyl, diamond Alkyl, vinyl, propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, phenyl, fluorenyl-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methyl Phenylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, decyloxy, 4-ethylphenyl, 4-propylphenyl, 4_ third Butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-adamantylphenyl, 2-phenylphenyl, 9-fluorenyl, phenylmethyl, phenylethyl, 2_ Phenylethyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, phenoxy, diphenylamino, bis(2-methylphenyl)amine, bis (3) Methylphenyl)amino, bis(4-methylphenyl)amino, bis(4-tert-butylphenyl)amino and naphthylamine, more preferably fluoro Atom, gas atom, bromine atom, trifluoromethyl 156591.doc •57· 201202390 base, methyl, ethyl, propyl, butyl, tert-butyl, hexyl, octyl, eleven alkyl, cyclohexyl, Adamantyl, phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-tert-butylphenyl, 9- , phenyl fluorenyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, phenoxy, diphenylamino, bis(2-methylphenyl)amine, double a (3-methylphenyl)amino group, a bis(4-mercaptophenyl)amino group, a bis(4-tert-butylphenyl)amino group, and a dinaphthylamino group, and more preferably a fluorine atom, Trifluoromethyl, methyl, tert-butyl, hexyl, octyl, phenyl, 2-methylphenyl, 4-tert-butylphenyl, phenylmethyl, methoxy, ethoxy, The butoxy group, the hexyloxy group, and the phenoxy group are particularly preferably a fluorine atom 'methyl group, a third butyl group, and a methoxy group. Examples of the substitutable alkyl group in the molecule represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt), Mention may be made of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, pentadecyl, octadecyl a linear hydrocarbon group having 1 to 3 carbon atoms such as a decyl group, which may have a branched structure such as an isopropyl group, an isobutyl group, a second butyl group or a 2-ethylhexyl group, or It is an alkyl group having a cyclic structure like a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, a cyclododecyl group, a norbornyl group, and an adamantyl group. Preferred are methyl, ethyl, butyl, tert-butyl, hexyl, octyl, dodecyl, octadecyl and cyclohexyl, more preferably methyl, butyl, hexyl, octyl, and further It is preferably a methyl group. Examples of the group in which two hydrogen atoms are removed from the above-mentioned substituted nitrogen-containing heterocyclic compound include a heterocyclic ring containing the above-mentioned substituted I56591.doc •58-201202390 2 atom. In the example of the compound of the formula, in the chemical structure having two or more hydrogen atoms, the same ones are obtained by removing two hydrogen atoms. Examples of the group in which three hydrogen atoms are removed from the above-mentioned heterocyclic compound having a nitrogen atom to be substituted include a compound having a heterocyclic compound derived from the above-mentioned nitrogen-containing atom. The structure in which three or more hydrogen atoms are removed from the structure of a compound having more than one atom of ammonia is the same. An example in which four hydrogen atoms are removed from the above-mentioned substituted nitrogen-containing heterocyclic compound to form a valence group, and examples thereof include a heterocyclic compound derived from the above-mentioned nitrogen-containing atom which may be substituted. The structure in which the hydrogen atom is removed from the structure of the compound of four or more hydrogen atoms is the same. Examples of the pentavalent group obtained by removing five hydrogen atoms from the above-mentioned substituted nitrogen-containing heterocyclic compound include an example of a heterocyclic compound derived from the above-mentioned nitrogen-containing atom which may be substituted. The structure in which five hydrogen atoms are removed from the structure of a compound having five or more hydrogen atoms is the same. Examples of the hexavalent group obtained by removing six hydrogen atoms from the heterocyclic ring-form of the above-mentioned substituted nitrogen atom include a heterocyclic compound derived from the above-mentioned nitrogen-containing atom which may be substituted. In the example, a compound having six or more hydrogen atoms has the same structure in which six hydrogen atoms are removed. Examples of the above R2Aa, R2Ba, R2Bb, r2Bc, R2Ca, R2Cb, and ye. ,

R2Cd、R2Ce、R 2CfR2Cd, R2Ce, R 2Cf

RR

2Ch、R2Da、R2Db、R R2Df、R2Dg、R2Dh、R2Di ' R2Dj、R2Dk2Ch, R2Da, R2Db, R R2Df, R2Dg, R2Dh, R2Di ' R2Dj, R2Dk

R 2Dc、R2Dd、R2De、 2D1、R2Dm、R2Dn、 R 、R及r2Ds所表示之基（以下記為r2Xx所表示 之基）之例’可列舉以下者。 可經取代之碳原子數丨〜“之烷二基；碳原子數2〜3〇之烯Examples of the radicals represented by R 2Dc, R2Dd, R2De, 2D1, R2Dm, R2Dn, R, R and r2Ds (hereinafter referred to as "bases represented by r2Xx") include the following. The number of carbon atoms which may be substituted 丨~"alkanediyl; alkene having 2 to 3 carbon atoms

R 156591.doc t •59. 201202390 二基；可經取代之主鍵碳原子數2〜3G之块：基；可經取代 之碳原子數4〜30之環烷二基；可經取代之碳原子數㈠。之 芳二基等伸烴基，即2價之烴基。 將可經取代之伸烴基與_〇_及/或·s•組合而成之基。 可經取代之下述式Γ1〜Γ12中之任一個所表示之基（例如下 述式Γ1·〜Γ12·中之任一個所表示之基）。 [化3]R 156591.doc t •59. 201202390 Diyl; a substituted primary bond having 2 to 3 G carbon atoms: a group; a substituted cycloalkyl 2 group having 4 to 30 carbon atoms; a carbon atom which may be substituted Number (a). The aryldiyl group is a hydrocarbon group, that is, a divalent hydrocarbon group. A group in which a substituted hydrocarbon group is combined with _〇_ and/or s•. A group represented by any one of the following formulas Γ1 to Γ12 (for example, a group represented by any one of the following formulas ·1· to Γ12). [Chemical 3]

(式中，Y1 為-(CH2)n-、_〇_、_S·、_n(r5〇)_、_Si(R51)2、 〇(CH2)n-、或 _0(CH2)n〇-所表示之基。γ2為 _(ch^_、_〇 、、或-Sl(R51)2-所表示之基。η為1〜3之整數，R5。為可 經取代之碳原子數1〜50之芳基，rm為可經取代之碳原子 數1〜50之烴基）。 作為上述R5G所表示之可經取代之芳基的芳基之例，可 列舉苯基、1-萘基、2-萘基、2-曱基苯基、3·甲基苯基、 甲基苯基、2,4,6-三甲基苯基、2_異丙基苯基、4乙基苯 基、4-丙基苯基' 4_異丙基苯基、4_丁基苯基、4_第三丁 _.doc ,60. s 201202390 基、4-金剛烷基苯基、4-苯基苯基及9-苐基。較佳為笨 基、2-甲基苯基、4-甲基苯基、2,4,6-三甲基苯基、2_異丙 基苯基、4-第三丁基苯基及4-己基苯基，更佳為苯基、2_ 甲基本基、2，4,6 -二甲基苯基及4-己基笨基，進而較佳為 苯基。 上述R51所表示之可經取代之烴基的烴基之例與上述式 (Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(Dt)所表示之 分子中之可經取代之烴基的烴基之例相同。 較佳為， 曱基、乙基、丙基、異丙基、丁基、異丁基、第三丁 基、戊基'己基、庚基、辛基、壬基、癸基、十一烧基、 十二烷基、十五烷基、十八烷基、二十二烷基等碳原子數 1〜50之烷基； 環丙基、環丁基、環戊基、環己基、環壬基、環十二院 基、降福基、金剛烧基等碳原子數3〜50之環狀飽和烴基； 苯基、1-萘基、2-萘基、2·曱基苯基、3_曱基笨基、4_ 甲基苯基、2,4,6·三曱基苯基、2-異丙基苯基、4-乙基笨 基、4-丙基苯基、4-異丙基苯基、4-丁基苯基、4-第三丁 基苯基、4-己基苯基、4-(2-乙基己基）苯基、4-環己基笨 基、4-金剛烷基苯基、4-苯基苯基、9-苐基等碳原子數 6〜50之芳基。更佳為， 曱基、乙基、丙基、異丙基、丁基、異丁基、第三丁 基、戊基、己基、庚基、辛基、壬基、癸基--烧基、 十二烷基、十五烷基、十八烷基等碳原子數丨〜^之烷基； 苯基、2-甲基苯基、3-曱基苯基、4-甲基苯基、2,4,6-三 156591.doc •61 · 201202390 甲基苯基、2-異丙基苯基、4-乙基苯基、4-丙基苯基、4-異丙基苯基、4-丁基苯基、4-第三丁基苯基、4-己基苯 基、4-(2-乙基己基）苯基、4_環己基苯基等碳原子數6〜24 之芳基。進而較佳為碳原子數1〜8之烷基及苯基。 以下示出作為上述可經取代之式rl〜rl2所表示之基之例 的可經取代之Srr〜rl2,所表示之基。 [化4](where Y1 is -(CH2)n-, _〇_, _S·, _n(r5〇)_, _Si(R51)2, 〇(CH2)n-, or _0(CH2)n〇- Γ2 is a group represented by _(ch^_, _〇, or -Sl(R51)2-. η is an integer of 1 to 3, and R5 is a substitutable carbon number of 1 to 50. The aryl group, rm is a hydrocarbyl group having 1 to 50 carbon atoms which may be substituted.) Examples of the aryl group of the substitutable aryl group represented by the above R5G include a phenyl group, a 1-naphthyl group, and 2 Naphthyl, 2-mercaptophenyl, 3-methylphenyl, methylphenyl, 2,4,6-trimethylphenyl, 2-isopropylphenyl, 4-ethylphenyl, 4- Propyl phenyl ' 4 isopropyl phenyl, 4- butyl phenyl, 4 _ _ _ _ doc, 60. s 201202390 base, 4-adamantyl phenyl, 4-phenyl phenyl and 9-fluorenyl group, preferably stupid base, 2-methylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 4-third group The phenyl group and the 4-hexylphenyl group are more preferably a phenyl group, a 2-methyl group, a 2,4,6-dimethylphenyl group or a 4-hexyl group, and further preferably a phenyl group. Examples of the hydrocarbyl group which may be substituted with the above formula (Aa), (Ab), Examples of the hydrocarbyl group of the substitutable hydrocarbyl group in the molecule represented by Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt). Preferably, a mercapto group, an ethyl group, Propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl 'hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, pentadecyl , an octadecyl group, a behenyl group, etc., an alkyl group having 1 to 50 carbon atoms; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, a cyclodene group, a ruthenium group a cyclic saturated hydrocarbon group having 3 to 50 carbon atoms such as an adamantyl group; a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-nonylphenyl group, a 3-indolyl group, a 4-methylphenyl group, 2,4,6·tridecylphenyl, 2-isopropylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4 -T-butylphenyl, 4-hexylphenyl, 4-(2-ethylhexyl)phenyl, 4-cyclohexylphenyl, 4-adamantylphenyl, 4-phenylphenyl, 9- An aryl group having 6 to 50 carbon atoms, such as a mercapto group, more preferably an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group or a hexyl group. Alkyl group, octyl group, fluorenyl group, fluorenyl group, alkyl group, dodecyl group, pentadecyl group, octadecyl group and the like, an alkyl group having a carbon number of 丨~^; phenyl, 2-methylphenyl group, 3-decylphenyl, 4-methylphenyl, 2,4,6-tri 156591.doc •61 · 201202390 methylphenyl, 2-isopropylphenyl, 4-ethylphenyl, 4- Propyl phenyl, 4-isopropylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-(2-ethylhexyl)phenyl, 4-ring An aryl group having 6 to 24 carbon atoms such as hexylphenyl group. Further, an alkyl group having 1 to 8 carbon atoms and a phenyl group are preferred. The base represented by the substitutable Srr to rl2 which is an example of the group represented by the above-mentioned substituted formulas rl to rl2 is shown below. [Chemical 4]

丁之基R為可經取代之碳原子數卜“之芳基，R53為可 經取代之碳原子數1〜18之烴基）。 上述R 2所表示之可經取代之碳原子數1〜18之芳基之例 及較佳結構奧卜H R 5〇 &也_ 興上tLR所表不之可經取代之芳基之例及較 佳例中碳原子數為1〜18者相同。 上述R53所表示之可經取代之碳原子數1〜18之烴基之例 156591.docThe base of R is a aryl group of a carbon atom which may be substituted, and R53 is a hydrocarbyl group having 1 to 18 carbon atoms which may be substituted. The number of carbon atoms which may be substituted by the above R 2 is 1 to 18 Examples of the aryl group and the preferred structure are the same as those of the aryl group which can be substituted by tLR and the preferred examples of the carbon atoms of 1 to 18. An example of a hydrocarbyl group having 1 to 18 carbon atoms which may be substituted. 156591.doc

S •62· 201202390 不之烴基之例及較佳結構中碳 及較佳結構與上述R51所表示 原子數為1〜18者相同。 ’較佳為可經取代之上述式S • 62· 201202390 Examples of hydrocarbon groups and preferred structures of carbon and preferred structures are the same as those in the above-mentioned R51. </ RTI> preferably substituted by the above formula

式中之Y3為-Si(CH3)2-之基。 作為上述R2Xx所表示之基， rl〜rl2中之任一個所表示的基， 上述R2Xx所表示之基可具有之取代基的例與上述式 (Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(Dt)所表示之 分子中之可經取代之烴基可具有的取代基相同，為齒素原 子、碳原子數1〜50之烴基、碳原子數卜24之烴氧基及碳原 子數1〜24之二芳基胺基。較佳為氟原子、氣原子、溴原 子、二氟甲基、甲基、乙基、丙基、丁基、異丁基'第三 丁基、戊基、己基、庚基、辛基、壬基、十二烷基、十八 烷基、環己基、乙烯基、丙烯基、3-丁烯基、苯基、丨_萘 基、2-萘基、2-甲基笨基、3-曱基苯基、4-曱基苯基、2-甲氧基苯基、3-曱氧基苯基、4-曱氧基苯基、4_第三丁基 笨基、4-己基苯基、4-環己基苯基、2-苯基苯基、2-笨基 乙基、曱氧基、丁氧基、苯氧基、二苯基胺基，更佳為氟 156591.doc •63· 201202390 原子、氣原子、三氟甲基、子基、乙基、丙基、丁基、第 三丁基、己基、辛基、環己基、苯基、2_f基苯基、4_甲 基苯基、2-甲氧基苯基、4_甲氧基苯基、4_第三丁基苯 基、4-己基苯基、甲氧基、丁氧基、苯氧基、二苯基胺 基’進而較佳為氟原子、三氟甲基、甲基、丁基、第三丁 基、苯基、4-甲基苯基、4_甲氧基苯基、肛第三丁基苯 基、甲氧基，尤佳為氟原子、甲基、第三丁基。 上述R2XX所表示之基可具有之取代基之數較佳為0〜4 個’更佳為0〜3個’冑而較佳為〇〜2個。純山所表示之基 為上述1* 1 *〜r 12 ·所表示夕其沾，降w + 衣丁之基的匱形時，上述取代基之位置 較理想為以下所示之位置。 Π’ ：較佳為選自2,及3,中之—處以 4’及5’中之一處以上，更佳為2, r2':較佳為選自2，、3，、 及5’兩處、或3'及4'兩處； 、6'及8’中之一處以上， 及5’兩處、2'、4,及6'三 r3':較佳為選自2'、3，、4'、 更佳為僅4’一處、2,及6,兩處、 處、或3’、4,及5'三處； Γ5 .較佳為選自2，、31、4'、51， 更佳為2’及7,兩處、或3,及6,兩處 處； r4':較佳為選自2'、3,、4, 更佳為2,及7'兩處、3,及6,兩處 Γ6·:較佳為選自2,、3,、4,、 處以上，更佳為2·及11,兩處 5’、6’及7’中之一處以上 或4'及5,兩處； 6'及7·中之一處以上， ’進而較佳為2'及7·兩 、8’、9,、10,及 11，中之一 '及10’兩處、或4'及9,兩 156591.docY3 in the formula is a group of -Si(CH3)2-. Examples of the group represented by R2Xx, a group represented by any one of rl to rl2, an example in which the group represented by R2Xx may have a substituent, and the above formula (Aa), (Ab), (Ba) to (Bd) And the substituted hydrocarbon group in the molecule represented by (Ca) to (Ci) and (Da) to (Dt) may have the same substituent, and is a dentin atom, a hydrocarbon group having 1 to 50 carbon atoms, A hydrocarbon group having a carbon number of 24 and a diarylamino group having 1 to 24 carbon atoms. Preferred are fluorine atom, gas atom, bromine atom, difluoromethyl, methyl, ethyl, propyl, butyl, isobutyl 't-butyl, pentyl, hexyl, heptyl, octyl, fluorene , dodecyl, octadecyl, cyclohexyl, vinyl, propenyl, 3-butenyl, phenyl, anthracenyl, 2-naphthyl, 2-methylindolyl, 3-indole Phenylphenyl, 4-nonylphenyl, 2-methoxyphenyl, 3-decyloxyphenyl, 4-decyloxyphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2-phenylphenyl, 2-phenylethyl, decyloxy, butoxy, phenoxy, diphenylamino, more preferably 156591.doc •63· 201202390 Atom, gas atom, trifluoromethyl, subunit, ethyl, propyl, butyl, tert-butyl, hexyl, octyl, cyclohexyl, phenyl, 2-f-phenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 4-hexylphenyl, methoxy, butoxy, phenoxy, diphenylamino' Preferred are fluorine atom, trifluoromethyl, methyl, butyl, tert-butyl, phenyl, 4-methylphenyl, 4-methoxybenzene Anal tert-butyl phenyl group, a methoxy group, particularly preferably a fluorine atom, a methyl, tert-butyl. The number of substituents which the base represented by the above R2XX may have is preferably from 0 to 4's more preferably from 0 to 3's and more preferably from 〇2. The base represented by the pure mountain is the above-mentioned 1* 1 *~r 12 · When the smear is formed, the position of the above-mentioned substituent is preferably the position shown below. Π' : preferably selected from 2, and 3, at one or more of 4' and 5', more preferably 2, r2': preferably selected from 2, 3, and 5' Two places, or two places of 3' and 4'; more than one of 6' and 8', and 5' two, 2', 4, and 6' three r3': preferably selected from 2', 3, 4', more preferably only 4' one place, 2, and 6, two places, at, or 3', 4, and 5' three places; Γ5. preferably selected from 2, 31, 4 ', 51, more preferably 2' and 7, two, or 3, and 6, two places; r4': preferably selected from 2', 3, 4, more preferably 2, and 7' , 3, and 6, two places Γ6·: preferably selected from 2, 3, 4, and above, more preferably 2 and 11, two of 5', 6', and 7' Above or 4' and 5, two; 6' and 7· or more, 'and preferably 2' and 7·2, 8', 9, 10, and 11, one of 'and 10 'Two, or 4' and 9, two 156591.doc

S • 64- 201202390 處； r7’ ：較佳為選自2,、3,、4,、5,、6,及7·中之一處以上， 更佳為2'及7'兩處； Γ8':較佳為選自 2,、3,、5,、6,、7·、8,、9，及 1〇，中之 _ 處以上，更佳為2'及6,兩處、或3,及5,兩處； r9':較佳為選自2,及5,中之一處以上； rl〇’ ：較佳為選自2·、3,、4'、5,、6,及7,中之一處以上， 更佳為2及7'兩處、或3'及6'兩處，進而較佳為2'及7'兩 處， rll’ ：較佳為選自2’、3,、4·及5,中之一處以上，更佳為 2·及5'兩處； r12’令於γ3為-CH2-之情形時：為選自2'、3,、4·、5·及7, 中之一處以上，更佳為7,中之兩處及選自2,、3,、4，及5，中 之一處以上的共計三處以上，進而佳為7,中之兩處及選自 2’、3’、4'及5,中之兩處以上的共計四處以上，進而較佳為 7'中之兩處以及2,及5,兩處的共計四處； rl2'中於γ3為_CH2_a外之情形時：為選 、 中之一處以上，更佳為選自2，、3，、4,及5,中之兩處以上， 進而佳為2'及5'兩處。 於上述R2Xx所表示之基為複數個之情形時，較佳為複數 個所表示之基中丨個以上所表示之基並非直^鍵 結，其原因在於可構建穩定之錯合物^例如， 平又佳為上述 式（Ba)中之3個R2Ba*l個以上之R2Ba並非直接鍵結，此情 形時之上述式（Ba)所表示之分子為下述式（Ba,)所表示之^ 156591.doc -65· 201202390 子。 [化5] (Ba_) p2Ba， p2Ba' p2Ba* QlBa’、Q2Ba〆、&quot;Q2Ba^、QlBa (式（Ba·)中，Q1Ba&amp;Q2Ba2定義與上述式（Ba)中之QiBa及 Q2Ba相同。 R2Ba_之定義、例及較佳例除了 3個R2Ba'中至少1個並非直 接鍵結以外，與上述式（Ba)中之R2Ba相同） 作為上述 R3Ab、R3Bb、R3Cb、R3Cd、R3Cf、R3Cg、R3Db R3De、R3Dg、R3Dh、R3Dj、r3D1、R3Dn5亥專基統稱為R x x )所表示之基之例， 、r3Dp及R3Dq(以下將 可列舉可經取代之下 述式r31及r32中之任一個所表示之基。 [化6] Y5&quot; R31_Y4_Y5_R33_Y6_ γ5 、R32 一 γ6— R3r Ν—R33-Y7— kY7— r31 r32 (式 r31、r32 中，Y4 炎 r _. , , 為C、s!、或B_。Y5、Y6及Y7分別獨立S • 64- 201202390; r7': preferably selected from one of 2, 3, 4, 5, 6, and 7·, more preferably 2' and 7'; Γ8 ': preferably selected from 2, 3, 5, 6, 6, 7, 8, 9, and 1 〇, _ above, more preferably 2' and 6, 2, or 3 And 5, two; r9': preferably selected from one of 2, and 5, above; rl〇': preferably selected from 2, 3, 4', 5, 6, and 7 or more, more preferably 2 and 7', or 3' and 6', and preferably 2' and 7', rll': preferably selected from 2', 3, 4, and 5, more than one, more preferably 2 and 5'; r12' when γ3 is -CH2-: from 2', 3, 4, 5 or more, more than one, more preferably 7, two of them, and one or more of the two, 2, 3, 4, and 5, more than three, and then preferably 7, Two of the two and two or more of 2', 3', 4' and 5, more than four, and more preferably two of 7' and 2, and 5, a total of four places; In the case where γ3 is outside _CH2_a in rl2': one or more of the selected ones, more preferably selected from 2 , 3, 4, and 5, in the two or more, and further good 2 'and 5' two. In the case where the above-mentioned R2Xx represents a plurality of groups, it is preferable that a plurality of the indicated groups are not directly bonded, because a stable complex can be constructed, for example, flat. Further, it is preferable that three R 2 Ba* or more R 2 Ba in the above formula (Ba) are not directly bonded, and in this case, the molecule represented by the above formula (Ba) is represented by the following formula (Ba,) ^ 156591 .doc -65· 201202390 子. (Ba_) p2Ba, p2Ba' p2Ba* QlBa', Q2Ba〆, &quot;Q2Ba^, QlBa (in the formula (Ba·), Q1Ba&amp;Q2Ba2 is defined to be the same as QiBa and Q2Ba in the above formula (Ba). The definition, examples and preferred examples of R2Ba_ are the same as R3Ba in the above formula (Ba) except that at least one of the three R2Ba's is not directly bonded, as the above R3Ab, R3Bb, R3Cb, R3Cd, R3Cf, R3Cg, Examples of the base represented by R3Db R3De, R3Dg, R3Dh, R3Dj, r3D1, and R3Dn5 are referred to as R xx ), r3Dp and R3Dq (hereinafter, any of the following formulas r31 and r32 which may be substituted may be cited. The expressed base. [Chemical 6] Y5&quot; R31_Y4_Y5_R33_Y6_ γ5 , R32 - γ6 - R3r Ν - R33-Y7 - kY7 - r31 r32 (in the formula r31, r32, Y4 inflammation r _. , , is C, s!, or B_.Y5, Y6 and Y7 are independent

為直接鍵結或可經取A 戈之-(CH2)nm- ’該CH2只要並非相鄰 之彼此則可取代*权立〜 _ γ5、γ6、 為任忍數之〇，nm為卜8之整數。複數個 了刀別相同亦可不同。R3!為可經取代之碳 子數1〜50之烴基。及32 ’、 R為直接鍵結或可經取代之上诚 r 1〜r 12中之任一袖^ 個所表示之基。R33為可經取代之上述式 &quot; 之任—個所表示之基。複數個R32、R33可分別^ 同亦可不同，選自γ5 7 ^ 』刀另J相 自γ、Y、y7、r31、R32及R33中之2個以 156591.docFor direct bonding or by taking A-go-(CH2)nm-', the CH2 can be replaced as long as it is not adjacent to each other. * 立立~ _ γ5, γ6, 任 忍 〇, nm is 卜Integer. A plurality of knives may be the same or different. R3! is a hydrocarbyl group having 1 to 50 carbon atoms which may be substituted. And 32 ′, R is a direct bond or can be replaced by a base represented by any of the sleeves r 1 to r 12 . R33 is a group represented by any of the above-mentioned formulas &quot; which may be substituted. A plurality of R32 and R33 may be different or different, and are selected from γ5 7 ^ 』K further J phase from 2 of γ, Y, y7, r31, R32 and R33 to 156591.doc

S •66, 201202390 上的基亦可任意鍵結而形成環）》 上述R31中之可經取代之烴基的烴基之例及較佳例與上 述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(Dt)所表 示之分子中之可經取代之烴基之例及較佳例相同。該烴基 可具有之取代基的例及較佳例亦與上述式（Aa)、（Ab)、 (Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(Dt)所表示之分子中之可 經取代之烴基可具有之取代基的例及較佳例相同。 上述R及R分別獨立為直接鍵結或可經取代之上述式 r 1〜r 12中之任一個所表示之基。較佳為可經取代之上述式 rl、r2、r4、Γ5、Γ8及rl〇中之任一個所表示之基，更佳為 可經取代之上述式rl、r2、r5及Γ1〇中之任一個所表示之 基。於上述R32及R33為上述式rl〜rl2中之任一個所表示之 基的情形時，上述式rl〜rl2所表示之基可具有之取代基的 例及較佳例與上述所表示之基可具有之取代基的例及 較佳例相同。 作為上述R4Bd、R4Ce、R4DdThe group on S 66, 201202390 may be arbitrarily bonded to form a ring.) Examples and preferred examples of the hydrocarbon group of the hydrocarbon group which may be substituted in the above R 31 and the above formula (Aa), (Ab), (Ba) 〜 Examples (Bd), (Ca) to (Ci), and (Da) to (Dt) of the substituted hydrocarbon group in the molecule are the same as in the preferred embodiment. Examples and preferred examples of the substituent which the hydrocarbon group may have are also the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt). Examples and preferred examples of the substituent which the substituted hydrocarbon group in the molecule may have are the same. R and R are each independently a group represented by either a direct bond or a substituted one of the above formulas r 1 to r 12 . It is preferably a group represented by any one of the above formulas rl, r2, r4, Γ5, Γ8 and rl〇 which may be substituted, and more preferably any of the above-mentioned formulas rl, r2, r5 and Γ1〇 which may be substituted A base expressed. In the case where the above R32 and R33 are a group represented by any one of the above formulas rl to rl2, examples and preferred examples of the substituent which the group represented by the above formula rl to rl2 may have and the above-described group may be used. Examples and preferred examples of the substituents are the same. As the above R4Bd, R4Ce, R4Dd

R 4Di R4D〇及 r4Dp (以下將該 等基統稱為R4Xx)所表示之4價基之例，可列舉可經取代之 下述式r41所表示之基。 [化7]Examples of the tetravalent group represented by R 4Di R4D〇 and r4Dp (hereinafter referred to as R4Xx) include a group represented by the following formula r41 which may be substituted. [Chemistry 7]

156591.doc -67· 201202390 (式中，Y為C、S!、或B-，γ9為直接鍵結或_(CH2)旧、_〇_ 、-S-、-N(R6。）-、或_Si(R6丨卜所表示之基。仙為丨一之整 數。2個Y9可相同亦可不@。r60為可經取代之碳原子數 1〜18之芳基，R61為可經取代之碳原子數卜以之烴基）。 r41可具有之取代基的例及較佳例與上述R2Xx所表示之基 可具有之取代基的例及較佳例相同。 R60所表不之芳基的例及較佳例分別與上述R52所表示之 芳基的例及較佳例相同。 R61所表示之烴基的例及較佳例分別與上述R53所表示之 烴基的例及較佳例相同。 作為r41之Y8與Y9之組合，較佳可列舉：γ8為〇且2個γ9 均為-〇-之組合、γ8為si且2個γ9均為_〇·之組合、 2個γ9均為-S-之組合、Y8為Sia2個Y9均為_s_之組合、及 Y8為B·且2個Y9均為-0-之組合。更佳組合為Y8為以且2個 Y9均為-0-。 上述式（Aa)、（Ab)及（Ba)〜(Bd)中之各基之組合的較佳例 如下。 上述式（Aa)中之之較佳組合為： (1) 1 個 Q1A1-P(RnAa)2， 另1個Q1A1-As(R12Aa)2、自可經取代之含氮原子之雜環 式化合物中去掉1個氫原子而成的基、-〇·、_s-、 、或-C(=〇)〇-， Q 3為-P(R22Aa)·、-As(R23Aa)·、或自可經取代之含氮原 子之雜環式化合物中去掉2個氫原子而成的基， I56591.doc156591.doc -67· 201202390 (where Y is C, S!, or B-, γ9 is a direct bond or _(CH2) old, _〇_, -S-, -N(R6.)-, Or _Si (R6 丨 所 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Examples of the substituents and preferred examples of the substituents which the R41 may have are the same as those of the substituents which the substituent represented by the above R2Xx may have. Examples of the aryl group represented by R60 And preferred examples are the same as the examples and preferred examples of the aryl group represented by the above R52. The examples and preferred examples of the hydrocarbon group represented by R61 are the same as those of the hydrocarbon group represented by the above R53, respectively. Preferably, the combination of Y8 and Y9 is: γ8 is 〇 and two γ9 are - 〇- combinations, γ8 is si, and two γ9 are _〇· combinations, and two γ9 are -S- The combination of Y8 is a combination of Sia2 Y9 and _s_, and Y8 is B· and two Y9 are -0-. More preferably, Y8 is Y2 and both Y9 are -0-. Preferred combinations of the groups in the above formulae (Aa), (Ab) and (Ba) to (Bd) The preferred combination of the above formula (Aa) is: (1) 1 Q1A1-P(RnAa)2, another Q1A1-As(R12Aa)2, and a heterocyclic ring containing a nitrogen atom which may be substituted a group in which one hydrogen atom is removed, -〇·, _s-, or -C(=〇)〇-, Q 3 is -P(R22Aa)·, -As(R23Aa)·, or a group in which a hydrogen atom can be removed from a heterocyclic compound having a substituted nitrogen atom, I56591.doc

S 201202390 R11Aa、R12Aa、RUAajg β23Α3 八 ¢,，從 * 认 及R 刀别獨立為可經取代之苯其 的組合； (2) 1個Qih為_P(R»iAa)2、_As(Ri2Aa)2、自可經取代之含氮 原子之雜環式化合物中去掉1個氫原子而成的基、·〇·、 -S、-S(=0)2〇-、或-C(=〇)〇·， 另1個Q為-P(R a)2、-As(R12Aa)2、自可經取代之含氮 原子之雜環式化合物中去掉1個氫原子而成的基、_〇.、_s_ 、-s(=o)2o·、或-C(=0)〇·， Q2A1 -P(R22Aa)-，S 201202390 R11Aa, R12Aa, RUAajg β23Α3 gossip, from * recognized and R knife independently as a combination of benzene which can be substituted; (2) 1 Qih is _P(R»iAa)2, _As(Ri2Aa) 2. A group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, 〇·, -S, -S(=0)2〇-, or -C(=〇) 〇·, another Q is -P(R a)2, -As(R12Aa)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, _〇. , _s_ , -s(=o)2o·, or -C(=0)〇·, Q2A1 -P(R22Aa)-,

RllAa、RUAa及R22Aa分別獨立為可經取代之苯基的組 合； (3) 1個， 另1個Q1AU(R11Aa)2 ' ·Α3(Κ12,2、自可經取代之含氮 原子之雜環式化合物中去掉1個氫原子而成的基、-〇·、_s. 、-S(=0)20·、或-C(=0)0·， Q2Aa為-As(R23Aa)-、或自可經取代之含氮原子之雜環式 化合物中去掉2個氫原子而成的基，RllAa, RUAa and R22Aa are each independently a combination of a phenyl group which may be substituted; (3) 1 and another Q1AU(R11Aa)2' ·Α3(Κ12,2, a heterocyclic ring containing a nitrogen atom which may be substituted A group in which one hydrogen atom is removed, -〇·, _s., -S(=0)20·, or -C(=0)0·, Q2Aa is -As(R23Aa)-, or a group obtained by removing two hydrogen atoms from a substituted heterocyclic compound containing a nitrogen atom,

RllAa、Rl2Aa&amp;R23Aa分別獨立為可經取代之笨基的組 合； 更佳為： 1個Q1A1-P(R11Aa)2、_As(R12Aa)2、自可經取代之含氮原 子之雜環式化合物中去掉1個氫原子而成的基、·〇·、_s-、-S(=0)2cr、或-C(=0)0.， 另1個Q Aa為-As(R12Aa)2、自可經取代之含原子之雜環 156591.doc -69- 201202390 式化合物中去掉1個氫原子而成的基、_〇·、-jg-、_μ = 〇&gt;2〇* 、或-C(=〇)〇·， Q2A4 -P(R22Aa)-， RUAa ' R12Aa&amp; R22Aa分別獨立為可經取代之苯基的組 合； 進而較佳為： 1個（^心為-P(R&quot;Aa)2、自η比咬或味峻中去掉1個氫原子而 成的基、-〇·、-C(=0)0·、或-S-， 另1個（^^為自吡啶或咪唑中去掉1個氫原子而成的基， Q2A1 -P(R22Aa)-，RllAa, Rl2Aa &amp; R23Aa are each independently a combination of a pallatable group which may be substituted; more preferably: 1 Q1A1-P(R11Aa)2, _As(R12Aa)2, a heterocyclic compound derived from a nitrogen atom which may be substituted The base formed by removing one hydrogen atom, ·〇·, _s-, -S(=0)2cr, or -C(=0)0., the other Q Aa is -As(R12Aa)2, Substitutable atom-containing heterocyclic ring 156591.doc -69- 201202390 A group in which one hydrogen atom is removed from a compound of the formula, _〇·, -jg-, _μ = 〇&gt;2〇*, or -C( =〇)〇·, Q2A4 -P(R22Aa)-, RUAa ' R12Aa&amp; R22Aa are each independently a combination of a phenyl group which may be substituted; further preferably: 1 (^ is a -P(R&quot;Aa)2 A group obtained by removing one hydrogen atom from η than bite or taste, -〇·, -C(=0)0·, or -S-, and the other one (^^ is removed from pyridine or imidazole a group of hydrogen atoms, Q2A1 -P(R22Aa)-,

RnAa及尺22^分別獨立為可經取代之苯基的組合。 對於上述式（Aa)中之（^心與Q2Aa之各組合的較佳…心之 結構如對上述R2Xx所表示之基加以說明般。 上述式（Ab)中之Q1A1^R3Ab之較佳組合為： 2個 Q1A4 _p(R11Ab)2， 另1個Q1Ab為自可經取代之吡啶或咪唑中去掉1個氣原子 而成的基、-〇_、-c(=o)cr、或 _s_， R11Ab為可經取代之苯基， R3Ab為上述可經取代之式r3 1及r3 2中之任一個所表示之 基的組合。 上述式（Ba)中之Q〗Ba、Q2Ba&amp;R2Ba之較佳組合為： 1個Q1Ba*-P(R11Ba)2、或自可經取代之含氮原子之雜環 式化合物中去掉1個氫原子而成的基，另1個Q 1 Ba為〇 ，c(=o)cr、或-s-， 156591.doc • 70· 201202390 Q為-P(R22Ba)_或自可經取代之含氮原子之雜環式化合 物中去掉2個氫原子而成的基， R及R2、別獨立為可經取代之苯基， R2Ba為直接鍵結或可經取代之上述式rl〜H2中之任一個 所表示之基的組合。 上述式_中之Q' Q2Bb、R2，R3Bb之較佳组合為： 2個Q1Bb分別獨立為·p(RllBb)2、或自可經取代之含氣原 子之雜環式化合物中去掉i個氫原子而成的基 -〇.、-c(=〇)0、或_8-， Q 為 Q Λ_Ρ(ΙΙ b)·、或自可經取代之含氮原子之雜環式化 合物中去掉2個氫原子而成的基， ㈣分別獨立為可經取代之苯基， R2Bb為直接鍵結或可經取代之上述式rl〜rl2中之任一個 所表示之基， 1138|1為可經取代之上 基的組合。 述式r3 1及r32中之任一 個所表示之 上述式（Be)中之Q'dR2Bc之較佳組合為： 2個Q-分別獨立為，η、、_As(r、、或自可哩取 代之含氮原子之雜環式化合物中去掉Μ氫原子而成的 基，剌〜ns(=〇)2〇.„·， Q-為P或自可經取代之含氮原子之雜環式化合物中去 掉3個氫原子而成的基，RnAa and 尺 22^ are each independently a combination of a phenyl group which may be substituted. For the above formula (Aa), the preferred structure of each of the combinations of the core and the Q2Aa is as described for the above-mentioned R2Xx. The preferred combination of Q1A1^R3Ab in the above formula (Ab) is : 2 Q1A4 _p(R11Ab) 2, and another Q1Ab is a group obtained by removing one gas atom from a pyridine or imidazole which may be substituted, -〇_, -c(=o)cr, or _s_, R11Ab is a phenyl group which may be substituted, and R3Ab is a combination of the groups represented by any of the above-mentioned substituted formulas r3 1 and r3 2. Preferably, Q:Ba, Q2Ba&amp;R2Ba in the above formula (Ba) The combination is: 1 Q1Ba*-P(R11Ba)2, or a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, and the other Q 1 Ba is 〇, c ( =o)cr, or -s-, 156591.doc • 70· 201202390 Q is -P(R22Ba)_ or a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, R and R2 are independently a phenyl group which may be substituted, and R2Ba is a combination of a direct bond or a group of the above-mentioned formulas rl to H2 which may be substituted. Q' Q2Bb, R2 in the above formula The preferred combination of R3Bb is: 2 Q1Bb is independently -p(RllBb)2, or a group -〇., -c(=〇)0, or _8 obtained by removing i hydrogen atoms from a heterocyclic compound having a gas atom which may be substituted. -, Q is Q Λ Ρ Ρ (ΙΙ b) ·, or a group obtained by removing two hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted, and (4) independently being a substituted phenyl group, and R 2 Bb is a direct bond or a group represented by any one of the above formulas rl to rl2, wherein 1138|1 is a combination of a group which may be substituted. The above formula represented by any one of the formulas r3 1 and r32 The preferred combination of Q'dR2Bc in (Be) is: 2 Q- are independently η, _As(r, or 去 a hydrogen atom is removed from the heterocyclic compound containing a nitrogen atom which can be substituted by a hydrazine The base, 剌~ns(=〇)2〇.„·, Q- is P or a group obtained by removing three hydrogen atoms from a heterocyclic compound having a nitrogen atom which may be substituted,

RllBm可經取代之芳基的組合； 更佳為： 156591.doc 201202390 2個Q1Be分別獨立為-p(R&quot;Be)2、或自可經取代之含氮原 子之雜環式化合物中去掉1個氫原子而成的基，1個Q!Bc為 ·〇、-C(=0)0、或-S， Q3BeS P或自可經取代之含氮原子之雜環式化合物中去 掉3個氫原子而成的基， R11Be為可經取代之苯基， R2B°為直接鍵結或可經取代之上述式r丨〜r丨2中之任一個 所表示之基的組合； 進而較佳為： 2 個 Q1Bc 為-P(R&quot;bC)2，i 個 QlBc 為 _p(RllBc)2 〇·、 _c(=o)o·、或 _s·， Q3B、P， R11Be為可經取代之苯基， R2Be為直接鍵結或可經取代之上述式rl〜rl2中之任一個 所表示之基的組合； 尤佳為： Q1Bc之中 1個為、_〇.、或 _8-, Q1Be之其餘2個為-P(R&quot;Bc)2 , q3B4p， R 為可經取代之苯基， 之任一個所表示之基 R2BC為可經取代之上述式rl，〜rl2,中 的組合； 特佳為： Q之中1個為-〇或-s_， 156591.docRllBm can be a combination of substituted aryl groups; more preferably: 156591.doc 201202390 Two Q1Be are independently -p(R&quot;Be)2, or are removed from a heterocyclic compound containing a nitrogen atom which can be substituted. a group of hydrogen atoms, one Q!Bc is ·〇, -C(=0)0, or -S, Q3BeS P or three hydrogens are removed from the heterocyclic compound containing a nitrogen atom which may be substituted a group formed by an atom, R11Be is a phenyl group which may be substituted, and R2B° is a combination of a group of a direct bond or a substituted one of the above formulas r丨 to r丨2; further preferably: 2 Q1Bc are -P(R&quot;bC)2, i QlBc is _p(RllBc)2 〇·, _c(=o)o·, or _s·, Q3B, P, R11Be are substituted benzene a group, R2Be is a combination of a direct bond or a group of the above-mentioned formulas rl to rl2 which may be substituted; more preferably: one of Q1Bc is _〇., or _8-, Q1Be The other two are -P(R&quot;Bc)2, q3B4p, R is a phenyl group which may be substituted, and the group R2BC represented by any one of them is a combination of the above formulas rl, rl2, which may be substituted; For: One of Q is -〇 or -s_, 156591.doc

S •72- 201202390 Q1BC之其餘2個為-P(R丨1Bc)2， Q3B1P， RUBe為可經取代之2,4,6-三曱基苯基， R2Bc為可經取代之上述式rr、r5,、rl〇，及rl2，中之任一個 所表不之基的组合。 上述式（Bd)中之QlBd與R4Bd之較佳組合為： 3個Q〗Bd分別獨立為_P(R_)2、_As(Rl2Bd)2、或自可經取 代之含氮原子之雜環式化合物中去掉i個氫原子而成的 基，1個 Q1Bd為，C(=〇)〇-、_〇-、_s-、_s(=〇)2〇-、a_c(=〇)〇.， (R )及（R12Bd)為可經取代之苯基， R4Bd為可經取代之上述式r41的組合。 更佳為： 3個Q1Bd分別獨立為_p(RllBd)2、自可經取代之含氮原子 之雜環式化合物中去掉1個氫原子而成的基，1個Q】Bd為 -C(=〇)〇·、或 , (R11Bd)為可經取代之苯基， 為可、’呈取代之上述式r41所表示之基且該r41中之γ8 為S i的組合。 作為L1之例 Bbl 、 Bel〜23 可列舉下述式Aal〜94、Abl〜4、Bal~20、 Bdl〜3、Cal〜8、Cel〜3、Cfl、Dal〜4 及S • 72- 201202390 The remaining two of Q1BC are -P(R丨1Bc)2, Q3B1P, RUBe is a substituted 2,4,6-tridecylphenyl group, and R2Bc is a substitutable formula rr, A combination of the bases of any of r5, rl, and rl2. The preferred combination of QlBd and R4Bd in the above formula (Bd) is: 3 Q 〗 Bd are independently _P (R_) 2, _As (Rl2Bd) 2, or a heterocyclic ring containing a nitrogen atom which may be substituted A group in which a hydrogen atom is removed from a compound, and one Q1Bd is C(=〇)〇-, _〇-, _s-, _s(=〇)2〇-, a_c(=〇)〇., ( R) and (R12Bd) are a phenyl group which may be substituted, and R4Bd is a combination of the above formula r41 which may be substituted. More preferably: three Q1Bd are independently _p(RllBd) 2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom which may be substituted, and one Q] Bd is -C ( 〇·, or (R11Bd) is a phenyl group which may be substituted, and is a combination of the group represented by the above formula r41 which is substituted, and the γ8 of the r41 is S i . Examples of L1 include Bbl and Bel~23, which are exemplified by the following formulas Aal to 94, Abl to 4, Bal to 20, Bdl to 3, Cal to 8, Cel~3, Cfl, and Dal to 4, and

Dkl所表示之分子。 156591.doc -73- 201202390 [化8]The molecule represented by Dkl. 156591.doc -73- 201202390 [Chem. 8]

Aa1Aa1

\ 71 71 R Aa2 R Aa3\ 71 71 R Aa2 R Aa3

Aa9Aa9

156591.doc -74- 201202390 [化9]156591.doc -74- 201202390 [Chemistry 9]

Aa19Aa19

156591.doc -75- 201202390 [化 ίο]156591.doc -75- 201202390 [化 ίο]

R 72 Aa24R 72 Aa24

R 72 Aa25R 72 Aa25

Aa30 72Aa30 72

Aa31 156591.doc -76 201202390 [化 ii]Aa31 156591.doc -76 201202390 [Chemistry ii]

Aa40 156591.doc -77- 201202390 [化 12]Aa40 156591.doc -77- 201202390 [Chem. 12]

Aa49Aa49

Aa50Aa50

Aa51 156591.doc -78- s 201202390 [化 13]Aa51 156591.doc -78- s 201202390 [Chem. 13]

Aa56Aa56

Aa55Aa55

156591.doc -79- 201202390 [化 14]156591.doc -79- 201202390 [Chem. 14]

156591.doc • 80 · s 201202390 [化 15]156591.doc • 80 · s 201202390 [Chem. 15]

Aa75Aa75

RR

R 72 Aa79 Aa80 156591.doc -81 201202390 [化 16]R 72 Aa79 Aa80 156591.doc -81 201202390 [Chem. 16]

Aa92 156591.doc -82- s 201202390 [化 17]Aa92 156591.doc -82- s 201202390 [Chem. 17]

Ba1 156591.doc -83- 201202390Ba1 156591.doc -83- 201202390

Ba5 [化 19] αΛρBa5 [Chemical 19] αΛρ

156591.doc -84- s 201202390156591.doc -84- s 201202390

Ba9Ba9

Ba10 156591.doc -85 - 201202390Ba10 156591.doc -85 - 201202390

RR

Ba12Ba12

Ba13 [化 21]Ba13 [Chem. 21]

RR

Ba14Ba14

R 72 RR 72 R

R 74 m 156591.doc -86- s 201202390R 74 m 156591.doc -86- s 201202390

Ba19 Ba20Ba19 Ba20

Ba18 [化 22]Ba18 [化22]

Ar1 Ar1Ar1 Ar1

156591.doc •87· 201202390 [化 23]156591.doc •87· 201202390 [Chem. 23]

R RR R

7272

156591.doc -88- s 201202390 [化 24]156591.doc -88- s 201202390 [Chem. 24]

156591.doc -89- 201202390 [化 25]156591.doc -89- 201202390 [Chem. 25]

156591.doc •90- s 201202390 [化 26]156591.doc •90- s 201202390 [Chem. 26]

156591.doc •91 201202390 [化 27]156591.doc •91 201202390 [Chem. 27]

Ar^PAr^P

72 ,72 Ca3 156591.doc -92- s 201202390 [化 28]72,72 Ca3 156591.doc -92- s 201202390 [28]

Ca4Ca4

Ar12PAr12P

Cd5Cd5

156591.doc •93- 201202390 [化 29]156591.doc •93- 201202390 [Chem. 29]

156591.doc -94- s 201202390 [化 30]156591.doc -94- s 201202390 [化30]

式中R為氫原子、氟原子、氯原子、溴原子、三氟 曱基、甲基、乙基、丙基、異丙基、丁基、異丁基戊 基、己基、庚基、辛基、壬基、癸基、曱氧基、乙氧基、 丙氧基、丁氧基、第三丁氧基、或苯氧基。尺^為氫原子 或碳原子數1〜12之烴基^ R72為氫原子、氟原子、三氟甲 基、曱基、乙基、丙基、異丙基、丁基、異丁基、第三丁 基、戊基、己基、庚基、辛基、壬基、癸基、甲氧基、或 二苯基胺基。R73之例與R7G之例相同，但R73亦可成為直接 鍵結而與R74連結。R74為-CH2- ’ §亥CH2只要並非相鄰之彼 156591.doc •95- 201202390 此則可取代為任意數之〇 ^ m為卜12之整數。複數個 r7&lt;)〜R74可相同亦可不同。 AJ為可經取代之苯基，複數個Afl可相同亦可不同。A〆 為可經取代之伸苯基。 Y10為-CH2-、·〇_、或-s_所表示之基。γ丨丨為_C(CH3)2_ 、-(CH2)2-、·〇_、冬、·Si(CH3)2_、心、或 _Si(Ph)2-所表示之基。Ph為苯基《複數個γΐ〇與γ11可相同 亦可不同。 上述R較佳為氫原子、氟原子、氣原子、曱基、乙 基、丙基、異丙基、丁基、己基、辛基、甲氧基乙氧 基、丙氧基、丁氧基、第三丁氧基、或苯氧基，更佳為氫 原子、氟原子、氣原子、甲基、丁基、己基、辛基、甲氧 基丁氧基、第三丁氧基 '或苯氧基，進而較佳為氫原 子、氟原子、氣原子、甲氧基、丁氧基、第三丁氧基、或 苯氧基，尤佳為氟原子或氣原子。 上述R71較佳為氫原子、笨基、曱基、乙基、丙基、丁 戊基己基、庚基、辛基、壬基、癸基、或十二燒 基’更佳為氫原子、曱基、乙基、丙基、丁基、己基、辛 基或十一烷基，進而較佳為氫原子、甲基、乙基、丁 基、或己基，尤佳為曱基。 上述R較佳為氫原子、氟原子、三氟甲基、甲基、丁 基、第二丁基、己基、辛基、甲氧基、或二苯基胺基，更 佳為氫原子、氟原子、三敗甲基、第三丁基、辛基、或甲 氧基，進而較佳為氫原子或氟原子。 156591.docWherein R is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutylpentyl group, a hexyl group, a heptyl group, an octyl group. , anthracenyl, fluorenyl, decyloxy, ethoxy, propoxy, butoxy, tert-butoxy, or phenoxy. The ruler is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R72 is a hydrogen atom, a fluorine atom, a trifluoromethyl group, a decyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a third group. Butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, methoxy, or diphenylamino. The example of R73 is the same as the case of R7G, but R73 can also be a direct bond and connected to R74. R74 is -CH2-'. CH2 is not adjacent to each other. 156591.doc •95- 201202390 This can be replaced by an arbitrary number ^ m is an integer of 12 . A plurality of r7&lt;)~R74 may be the same or different. AJ is a phenyl group which may be substituted, and a plurality of Afl may be the same or different. A〆 is a phenyl group which can be substituted. Y10 is a group represented by -CH2-, ·〇_, or -s_.丨丨 丨丨 is a group represented by _C(CH3)2_, -(CH2)2-, ·〇_, winter, Si(CH3)2_, core, or _Si(Ph)2-. Ph is a phenyl group. The plural γ ΐ〇 and γ 11 may be the same or different. The above R is preferably a hydrogen atom, a fluorine atom, a gas atom, a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a methoxyethoxy group, a propoxy group, a butoxy group, or the like. a third butoxy group or a phenoxy group, more preferably a hydrogen atom, a fluorine atom, a gas atom, a methyl group, a butyl group, a hexyl group, an octyl group, a methoxyoxy group, a third butoxy group or a phenoxy group. The group is further preferably a hydrogen atom, a fluorine atom, a gas atom, a methoxy group, a butoxy group, a third butoxy group or a phenoxy group, and more preferably a fluorine atom or a gas atom. The above R71 is preferably a hydrogen atom, a strepto group, a mercapto group, an ethyl group, a propyl group, a butyylhexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group or a dodecapine group, more preferably a hydrogen atom or a hydrazine. The group is preferably an alkyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group or an undecyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a butyl group or a hexyl group. The above R is preferably a hydrogen atom, a fluorine atom, a trifluoromethyl group, a methyl group, a butyl group, a second butyl group, a hexyl group, an octyl group, a methoxy group or a diphenylamino group, more preferably a hydrogen atom or a fluorine atom. An atom, a tri-substituted methyl group, a tert-butyl group, an octyl group, or a methoxy group is further preferably a hydrogen atom or a fluorine atom. 156591.doc

S •96- 201202390 73 R之較佳例與上述r7〇之較佳例相同e R73亦可為直接鍵 結而與R74連結。 m較佳為1〜1〇之整數，更佳為3〜1〇之整數，進而較佳為 4〜9之整數，尤佳為5〜8之整數。A preferred embodiment of S 96-201202390 73 R is the same as the preferred embodiment of r7〇. e R73 may be directly bonded to R74. m is preferably an integer of 1 to 1 Å, more preferably an integer of 3 to 1 Å, still more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8.

Ar較佳為本基、2-甲基苯基、3 -曱基苯基、4_甲基苯 基、2-乙基苯基、2-丙基苯基、2-異丙基苯基、2_ 丁基苯 基、2-第三丁基苯基、4_第三丁基苯基、4己基苯基、2_ 氟苯基、4-氟笨基、3-二苯基胺基苯基、4-二苯基胺基苯 基、3-雙（2-甲基苯基）胺基苯基、3-雙（4-甲基苯基）胺基笨 基、2-甲氧基苯基、3_曱氧基苯基、4_曱氧基苯基、‘苯 氧基苯基、2,6-二曱基苯基、3,5-二甲基苯基、2,4,6-三甲 基苯基、2,6-二乙基苯基、2,6-二異丙基苯基、2,6-二氟苯 基、2,4,6-三氟笨基、2,3,4,5,6-五氟苯基、2,6•二甲氧基、 3,4,5-三甲氧基、3,5-二甲氧基、3,5-二-第三丁基或3,5-二- 第三丁基-4-曱氧基’更佳為苯基、2_甲基苯基、4·甲基笨 基、4-第三丁基苯基、4-己基苯基、2-氟苯基、4-氟笨 基、3-二苯基胺基苯基、4-二苯基胺基苯基、3-雙（2-甲基 苯基）胺基苯基、2-曱氧基苯基、4-甲氧基苯基、4-苯氧基 苯基、2，4,6-三甲基苯基、2,6-二甲基苯基、3,5-二乙基苯 基、2,6-二氟苯基、2,4,6-三氟苯基、2,3,4,5,6-五氟苯基、 2,6-二甲氧基、3,5-二曱氧基、3,5-二-第三丁基-4-曱氧 基’進而較佳為苯基、2-甲基苯基、2,6-二甲基苯基、3,5-二曱基苯基、4-第三丁基苯基、4-己基笨基、4-氟苯基、 4-二苯基胺基苯基、4-甲氧基苯基、4-苯氧基苯基、3,5- 156591.doc -97- 201202390 二-第三丁基-4-甲氧基，尤佳為苯基。Ar is preferably a benzyl group, 2-methylphenyl, 3-nonylphenyl, 4-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2-isopropylphenyl, 2_butylphenyl, 2-tert-butylphenyl, 4_t-butylphenyl, 4-hexylphenyl, 2-fluorophenyl, 4-fluorophenyl, 3-diphenylaminophenyl, 4-diphenylaminophenyl, 3-bis(2-methylphenyl)aminophenyl, 3-bis(4-methylphenyl)aminophenyl, 2-methoxyphenyl, 3_nonyloxyphenyl, 4-methoxyphenyl, 'phenoxyphenyl, 2,6-didecylphenyl, 3,5-dimethylphenyl, 2,4,6-tri Methylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2,3, 4,5,6-pentafluorophenyl, 2,6•dimethoxy, 3,4,5-trimethoxy, 3,5-dimethoxy, 3,5-di-t-butyl or 3,5-di-t-butyl-4-decyloxy' is more preferably phenyl, 2-methylphenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-hexylbenzene Base, 2-fluorophenyl, 4-fluorophenyl, 3-diphenylaminophenyl, 4-diphenylaminophenyl, 3-bis(2-methylphenyl)aminophenyl, 2-methoxyphenyl, 4-methoxy Phenylphenyl, 4-phenoxyphenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-diethylphenyl, 2,6-difluoro Phenyl, 2,4,6-trifluorophenyl, 2,3,4,5,6-pentafluorophenyl, 2,6-dimethoxy, 3,5-dimethoxy, 3,5 -di-t-butyl-4-decyloxy' is further preferably phenyl, 2-methylphenyl, 2,6-dimethylphenyl, 3,5-didecylphenyl, 4- Tert-butylphenyl, 4-hexylphenyl, 4-fluorophenyl, 4-diphenylaminophenyl, 4-methoxyphenyl, 4-phenoxyphenyl, 3,5-156591 .doc -97- 201202390 Di-tert-butyl-4-methoxy, especially preferably phenyl.

Ar2較佳為1，2-伸苯基、1，3-伸苯基、1，4·伸苯基、3-甲 基-1,2-伸苯基、4-曱基-1，2-伸苯基、5-甲基-12•伸苯基、 6-甲基-1，2-伸苯基、6-乙基-1,2-伸苯基、6-丙基-1，2-伸苯 基、6-甲氧基-1，2-伸苯基、6-甲基-1，3-伸苯基、6-甲基_ M-伸苯基、6-甲氧基-1,3-伸苯基或6-氟-1，3_伸苯基，更 佳為1,2-伸笨基、1，3-伸苯基、1,4-伸苯基、6-曱基_ι，2-伸 苯基、6-甲基-1，3-伸苯基、6-甲基-1,4-伸苯基、6-曱氧基_ 1.3- 伸苯基或6-氟-1,3-伸苯基，進而較佳為ι，2_伸苯基、 1.3- 伸苯基、1，4-伸苯基、6-甲基-1,3-伸苯基或6_氟-13_伸 苯基，尤佳為1，2-伸苯基、1，3-伸苯基或1,4-伸苯基。 Y10較佳為-ch2-或-〇-，更佳為-〇-。y11較佳為_C(CH3)2_ 、-(CH2)2-、_〇_、_Si(CH3)2-、-Si(n-C6H13)2_、或 _si(Ph)2- ’進而較佳為-C(CH3)2-、-Si(CH3)2-、或-Si(Ph)2-，尤佳 為-C(CH3)2-及-Si(CH3)2-。 Z1 為-〇_或-(：(=0)0·，較佳為-0·。 Z2為-S_或-s(=0)20·，較佳為-S·。 上述例之中，L1較佳為上述式Aal〜94、Abl〜4、 Bal〜20、Bbl、Bel〜23、Bdl〜3所表示之分子，更佳為式Ar2 is preferably 1,2-phenylene, 1,3-phenylene, 1,4·phenyl, 3-methyl-1,2-phenyl, 4-mercapto-1,2- Phenyl, 5-methyl-12•phenyl, 6-methyl-1,2-phenyl, 6-ethyl-1,2-phenyl, 6-propyl-1,2- Phenyl, 6-methoxy-1,2-phenylene, 6-methyl-1,3-phenylene, 6-methyl-M-phenylene, 6-methoxy-1, 3-phenylene or 6-fluoro-1,3_phenylene, more preferably 1,2-extended base, 1,3-phenylene, 1,4-phenylene, 6-fluorenyl ι, 2-phenylene, 6-methyl-1,3-phenylene, 6-methyl-1,4-phenylene, 6-fluorenyl-1-1.3-phenyl or 6-fluoro- 1,3-phenylene, further preferably ι, 2_phenyl, 1.3-phenyl, 1,4-phenyl, 6-methyl-1,3-phenyl or 6-fluoro -13_Extended phenyl group, particularly preferably 1,2-phenylene, 1,3-phenylene or 1,4-phenylene. Y10 is preferably -ch2- or -〇-, more preferably -〇-. Y11 is preferably _C(CH3)2_, -(CH2)2-, _〇_, _Si(CH3)2-, -Si(n-C6H13)2_, or _si(Ph)2-' and further preferably It is -C(CH3)2-, -Si(CH3)2-, or -Si(Ph)2-, and more preferably -C(CH3)2- and -Si(CH3)2-. Z1 is -〇_ or -(:(=0)0·, preferably -0·. Z2 is -S_ or -s(=0)20·, preferably -S·. L1 is preferably a molecule represented by the above formulas Aal to 94, Ab1 to 4, Bal to 20, Bbl, Bel to 23, and Bdl to 3, more preferably

Aal~40 、 Aa60~66 、 Aa77〜80 、 Aa91〜94 、 Abl~4 、Aal~40, Aa60~66, Aa77~80, Aa91~94, Abl~4,

Bal〜16、Bal8〜20、Bbl、Bel〜21、及Bdl〜3所表示之分 子，進而較佳為式 Aal、Aa3、Aa5、Aal3、Aal5、The molecules represented by Bal~16, Bal8~20, Bbl, Bel~21, and Bdl~3 are further preferably of the formulas Aal, Aa3, Aa5, Aal3, Aal5,

Aa23、Aa24、Aa33、Aa35、Bal、Ba2、Ba3、Ba6、 Ba7、Ba9、Ball、Bal2、Bal3、Bal4、Bal5、Bai6、 -98- 156591.doc s 201202390Aa23, Aa24, Aa33, Aa35, Bal, Ba2, Ba3, Ba6, Ba7, Ba9, Ball, Bal2, Bal3, Bal4, Bal5, Bai6, -98- 156591.doc s 201202390

Bel、Bc3、Bc4、Bc5、Bc6、Bc7、Bc8、Bc9、BclO、 Bcl4、Bcl5、Bcl8、Bcl9、Bc21、及Bdl所表示之分子， 尤佳為Ba3、Ba6、Ball、Bal2、Bal6、Bc4、Bc5、及 Bc9 所表示之分子》 作為L1之較佳例’可列舉下述式Aal,、Aal，-2、Aa3,、The molecules represented by Bel, Bc3, Bc4, Bc5, Bc6, Bc7, Bc8, Bc9, BclO, Bcl4, Bcl5, Bcl8, Bcl9, Bc21, and Bdl, and more preferably Ba3, Ba6, Ball, Bal2, Bal6, Bc4, The molecule represented by Bc5 and Bc9", as a preferable example of L1, can be exemplified by the following formulas Aal, Aal, -2, Aa3,

Aa5’、Aal5’、Aa23’、Aa35’、Aa60'、Bal·、Ba3'、Ba6'、 Ball’、Bal3,、Bal6’、Bal9,、Bel'、Bc4,、Bc9·、Bcl5'、Aa5', Aal5', Aa23', Aa35', Aa60', Bal·, Ba3', Ba6', Ball', Bal3, Bal6', Bal9, Bel', Bc4, Bc9, Bcl5',

Bc21’及Bdl1所表示之分子。 [化 31]Molecules represented by Bc21' and Bdl1. [化31]

Aa23* 156591.doc -99- 201202390Aa23* 156591.doc -99- 201202390

Ph2PPh2P

BarBar

Ba3’ [化 32]Ba3’ [化32]

[化 33][化33]

156591.doc -100- s 201202390156591.doc -100- s 201202390

Ba19' [化 34]Ba19' [34]

Bc1,Bc1,

Me MeMe Me

Bc4, C： 156591.doc 101 · 201202390Bc4, C: 156591.doc 101 · 201202390

[化 35][化35]

[化 36] R72[化36] R72

Μ6 Bc21. 156591.doc -102- s 201202390Μ6 Bc21. 156591.doc -102- s 201202390

Aa23'、Bal'、Ba3’、Ba6'、Ball，、Bal6’、Bal3,、Bc4·、Aa23', Bal', Ba3', Ba6', Ball, Bal6', Bal3, Bc4·,

Bcl5’、或Bc2r所表示之分子，更佳為式Ba3,、Ba6,、 Ball’、Bal6’、Bc4'、或以21·所表示之分子。 組成式（1)中之L2為具有選自磷原子、氮原子、氧原子、 硫原子、珅原子、氧陰離子及硫陰離子中之原子或離子作 為可配位於Ag+之原子或離子的分子，且L2具有之可配位 於Ag+之原子及離子的總數為2個。 於組成式（1)所表示之錯合物中，較佳為L2配位於Ag+， 可作為單牙配位基而配位於Ag+，亦可作為雙牙配位基而 配位於Ag κ圭為作為雙牙配位基而配位於八经+。 L之炭原子數通常為2〜250，較佳為3〜200，更佳為 進而較佳為6〜1〇〇，尤佳為1〇〜8〇。 156591.doc 201202390 L2較佳為下述式（E)所表示之分子。 Q，e-R2e-Q1e(E) (式(E)中 ’ qie 為 _p(r11e)2、_(]?=〇狀12、、_(p=sxRl3E)2、 _AS(R )2 ' -〇H、〇·、-C02H、-C〇2·、-SH、-S·、-SR16E、 S〇sH SC&gt;3、_N(Rl8E)2、或自可經取代之含氮原子之雜 裒式化σ物中去掉1個氩原子而成的基，2個qIE可相同亦 可不同，2個Q1E亦可鍵結而形成環。r11e〜r14E分別獨立為 氫原子或可經取代之碳原子數1〜50之烴基，R16E&amp;R18E分 別獨立為可經取代之碳原子數卜儿之烷基，2個r11e、2個 R12E、2個R丨3E、2個Rl4E、Rl6E、及之個尺呢可相同亦可不 同。汉^為2價基，然而，於2個QlE中之任一個為自可經取 代之含氮原子之雜環式化合物中去掉丨個氫原子而成的基 之情形時’亦可為直接鍵結。選自R11E、R12E、R13E、 R、R e、r18E、r2E及自可經取代之含氮原子之雜環中 去掉1個氫原子而成的基中的2個以上之基亦可任意鍵結而 形成環） R丨丨E〜R丨4E中之可經取代之烴基的烴基之例及較佳例分別 與上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及（Da)〜(Dt) 所表示之分子中之可經取代之烴基之例及較佳例相同。 R及R _之可經取代之烷基及該烷基可具有之取代 基之例及較佳例與上述式（Aa)、（Ab)、（Ba)〜(Bd)、 (Ca)〜(Ci)、及（Da)〜(Dt)所表示之分子中之可經取代之烷基 及該烷基可具有之取代基之例相同。 Q e中之可經取代之含氮原子之雜環式化合物之例及較 •104· I5659I.docThe molecule represented by Bcl5' or Bc2r is more preferably a compound of the formula Ba3, Ba6, Ball', Bal6', Bc4' or 21. L2 in the composition formula (1) is a molecule having an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, an oxyanion, and a sulfur anion as a molecule or ion which can be coordinated to Ag+, and L2 has a total of two atoms and ions that can be assigned to Ag+. Among the complexes represented by the formula (1), it is preferred that L2 is coordinated to Ag+, and may be assigned to Ag+ as a monodentate ligand or as a bidentate ligand. The double-dentate ligand is located in the eight-pass+. The number of carbon atoms of L is usually from 2 to 250, preferably from 3 to 200, more preferably still more preferably from 6 to 1 Torr, still more preferably from 1 Torr to 8 Torr. 156591.doc 201202390 L2 is preferably a molecule represented by the following formula (E). Q, e-R2e-Q1e(E) (in the formula (E), 'qie is _p(r11e)2, _(]?=〇12, _(p=sxRl3E)2, _AS(R)2' -〇H,〇·, -C02H, -C〇2·, -SH, -S·, -SR16E, S〇sH SC&gt;3, _N(Rl8E)2, or from a nitrogen atom which may be substituted A group of argon atoms is removed from the sigma sigma. The two qIEs may be the same or different, and the two Q1Es may also be bonded to form a ring. r11e~r14E are independently hydrogen atoms or substituted carbons. a hydrocarbon group having an atomic number of 1 to 50, and R16E&amp;R18E are independently a substituted alkyl group, 2 r11e, 2 R12E, 2 R丨3E, 2 Rl4E, Rl6E, and The ruler may be the same or different. Han^ is a divalent group, however, any one of the two QlEs is a group obtained by removing one hydrogen atom from the heterocyclic compound having a nitrogen atom which may be substituted. In the case of ', it may also be a direct bond. It is selected from the group consisting of R11E, R12E, R13E, R, R e, r18E, r2E and a hydrogen atom from a heterocyclic ring which may be substituted with a nitrogen atom. Two or more groups may also be bonded to form a ring. The substituted hydrocarbon in R丨丨E~R丨4E Examples and preferred examples of the hydrocarbon group are respectively in the numerators represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt). Examples of the hydrocarbyl group which may be substituted are the same as the preferred examples. The alkyl group which may be substituted with R and R and the substituent which may have the alkyl group and preferred examples thereof are the same as the above formula (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and the alkyl group which may be substituted in the molecule represented by (Da) to (Dt) and the substituent which the alkyl group may have. Examples of heterocyclic compounds containing nitrogen atoms which can be substituted in e and compared with 104. I5659I.doc

S 201202390 佳例與上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca卜(Ci)、及 (Da)〜(Dt)所表不之分子中之可經取代之含氮原子之雜環式 化合物及該含I原子之雜環式化合物可具有之取代基之例 及較佳例相同。S 201202390 Excellent case and substitutable in the above formula (Aa), (Ab), (Ba) ~ (Bd), (Ca (Ci), and (Da) ~ (Dt) The heterocyclic compound of the nitrogen atom and the heterocyclic compound containing the I atom may have the same substituents and preferred examples.

2E 中之2價基之例及較佳例與上述R2xx所表示之基之例 及較佳例相同。 2個Q1E之組合較佳為-P(R11E)22個、-As(R14E)22個、自含 氮原子之雜環式化合物中去掉丨個氫原子而成的基2個、 ·〇_ 與-p(r11e)2 各 1個、_c〇2U(R&quot;E)2 各 1個、或 _s-與 -P(RllE)2各1個，更佳為-P(R11E)22個、或自含氮原子之雜 環式化合物中去掉1個氫原子而成的基2個。 作為上述L2之例’可列舉可經取代之下述式a丨〜a3 7、 bl〜bll、cl〜C4l、dl〜d30所表示之分子。 [化 37]The examples and preferred examples of the two-valent group in 2E are the same as the examples and preferred examples of the base represented by the above R2xx. The combination of two Q1Es is preferably a group of -P(R11E)22, -As(R14E)22, and a radical of a heterocyclic compound containing a nitrogen atom, wherein two hydrogen atoms are removed, and 〇_ -p(r11e)2, one each, _c〇2U(R&quot;E)2, or one each of _s- and -P(RllE)2, more preferably -P(R11E)22, or Two bases obtained by removing one hydrogen atom from a heterocyclic compound containing a nitrogen atom. Examples of the above L2 include a molecule represented by the following formulas a丨 to a3, bl to bll, cl to C41, and dl to d30 which may be substituted. [化37]

156591.doc -】05· 201202390156591.doc -】05· 201202390

[化 38][化38]

MeMe

Ph2PX/PPh2 Ph2PsK=/PPh2 Ph2P^^PPh2 ph2p^^^PPh2 156591.doc a 20 a21 • 106. a22 a23Ph2PX/PPh2 Ph2PsK=/PPh2 Ph2P^^PPh2 ph2p^^^PPh2 156591.doc a 20 a21 • 106. a22 a23

S 201202390S 201202390

Ph2P\^\^\^PPh2 a24Ph2P\^\^\^PPh2 a24

Me Me MeMe Me Me

a26A26

MeO OMe OMeMeO OMe OMe

OMeOMe

a29A29

Me MeMe Me

[化 39][化39]

a 34a 34

156591.doc •107· 201202390[化 40]156591.doc •107· 201202390[化 40]

n-Bu n-Bun-Bu n-Bu

c10 c11 c12 c13 156591.doc 108·C10 c11 c12 c13 156591.doc 108·

S 201202390 [化 41] N N=S 201202390 [化41] N N=

c14C14

BrBr

Cl Br c18Cl Br c18

MeO Cl p c19MeO Cl p c19

c20 Γν~ίΛ -) &gt;=N N=&lt; \ F F F c21C20 Γν~ίΛ -) &gt;=N N=&lt; \ F F F c21

=N N= Cl Cl c23=N N= Cl Cl c23

=N N= Br Br c25=N N= Br Br c25

CF3 F3C N N、CF3 MecTN N=Ue MeC^ N: OMe c27 C28 c29CF3 F3C N N, CF3 MecTN N=Ue MeC^ N: OMe c27 C28 c29

..=N N=&lt; )=N N=&lt; &gt;=N N=&lt; &gt;=N N: PhO OPh PhO 〇Ph H5C20 OC2H5 H5C20 c30 &gt;=N N=&lt; t-BuO Ot-Bu c34 c31 c32 c33 &quot;W Λ V t-BuO =N N: =( Ot-Bu Vn n=q )=N N=&lt; c35 c36 c37..=NN=&lt;)=NN=&lt;&gt;=NN=&lt;&gt;=NN: PhO OPh PhO 〇Ph H5C20 OC2H5 H5C20 c30 &gt;=NN=&lt; t-BuO Ot-Bu c34 c31 c32 C33 &quot;W Λ V t-BuO =NN: =( Ot-Bu Vn n=q )=NN=&lt; c35 c36 c37

OC2HOC2H

:N N c38:N N c38

:N N=&lt; &gt; F MeO c40 c41:N N=&lt;&gt; F MeO c40 c41

156591.doc •109- 201202390[化 42]156591.doc •109- 201202390[化42]

OH SMe SMe COOHOH SMe SMe COOH

d13 d14D13 d14

d17D17

d18 d11 d12 OH COOH d15 d16 d19 d20D18 d11 d12 OH COOH d15 d16 d19 d20

156591.doc -110- s 201202390 [化 43]156591.doc -110- s 201202390 [Chem. 43]

d27 0° SMeD27 0° SMe

d28 SMe C〇2D28 SMe C〇2

d29D29

d30 上述式al〜a37、bl〜bll、cl〜c41、及dl〜d30所表示之分 子中’ L較佳為式a 1〜a 16、a25〜a37、c 1〜c6、c 12〜c41、 d22〜d24、或d26所表示之分子，更佳為式ai〜a2、a4〜a8、 alO〜al2、al5〜al6、a25〜a32、cl4〜c41、d22、d23、或 d26所表示之分子’進而較佳為式a2、a4~a7、alO、al5、 a25〜a26 、 a30〜a32 、 C15 、 cl7〜c25 、 c28〜c41 、 d22 、 d23 、 或d26所表示之分子，尤佳為式a6、a7、a25、a26、a31、 Cl5、c22、或c23所表示之分子。 於組成式（1)中，L3為具有1個選自磷原子、氮原子、氧 156591.doc -111 - 201202390 原子、硫原子、砷原子、氧陰離子及硫陰離子中之原子或 離子作為可配位於Ag+之原子或離子的分子^ 5 L3之碳原子數通常為2〜150，較佳為3〜丨〇〇，更佳為 4〜75 ’進而較佳為5〜60，尤佳為6〜50。 L3較佳為可經取代之含氮原子之雜環式化合物、 P(R丨％、(P=〇)(R丨2F)3、(P=S)(R、、As(R，3、R丨5:_ OH、R】6F-0-、R17F-C02H、R18F-C〇2-、Rm_SH、r20f_s.、 r21F-so3h、R22F-so3·、或N(Rw)3所表示之分子。 此處，R11F〜R22F分別獨立為氫原子或可經取代之烴基， «241?為可經取代之碳原子數1〜30之烷基，3個riif、3個 R12F、3個 R13F、3個 R】4F、rMf、Rl6F、Rl7F、r18f、r19f、 R2〇f、rW、r22f、及3個r24f可相同亦可不同。 3個RnF中任意2個以上亦可鍵結而形成環，3個1^21?中任 意2個以上亦可鍵結而形成環，3個Ri3f中任意2個以上亦可 鍵結而形成環，3個R14F中任意2個以上亦可鍵結而形成 環’ 3個R24F亦可鍵結而形成環。 作為L3之可經取代之含氮原子之雜環式化合物之例及較 佳例與上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及 (Da)〜(Dt)所表示之分子中的可經取代之含氮原子之雜環式 化合物之例及較佳例相同。D30 In the numerators represented by the above formulas a1 to a37, bl to bll, cl to c41, and dl to d30, 'L is preferably a type a1 to a16, a25 to a37, c1 to c6, c12 to c41, The molecule represented by d22 to d24 or d26 is more preferably a molecule represented by the formulas ai~a2, a4~a8, alO~al2, al5~al6, a25~a32, cl4~c41, d22, d23, or d26' Further preferred are molecules represented by the formulas a2, a4 to a7, alO, al5, a25 to a26, a30 to a32, C15, cl7 to c25, c28 to c41, d22, d23, or d26, and more preferably, the formula a6, A molecule represented by a7, a25, a26, a31, Cl5, c22, or c23. In the composition formula (1), L3 is an atom or ion having one atom selected from a phosphorus atom, a nitrogen atom, an oxygen 156591.doc -111 - 201202390 atom, a sulfur atom, an arsenic atom, an oxyanion, and a sulfur anion. The molecule of the atom or ion of Ag+^5 L3 usually has a carbon number of 2 to 150, preferably 3 to 丨〇〇, more preferably 4 to 75', more preferably 5 to 60, and particularly preferably 6 to 6. 50. L3 is preferably a heterocyclic compound having a nitrogen atom which may be substituted, P(R丨%, (P=〇)(R丨2F)3, (P=S)(R,, As(R, 3, R丨5: _OH, R] 6F-0-, R17F-C02H, R18F-C〇2-, Rm_SH, r20f_s., r21F-so3h, R22F-so3·, or N(Rw)3. Here, R11F to R22F are each independently a hydrogen atom or a substituted hydrocarbon group, «241? is a substitutable alkyl group having 1 to 30 carbon atoms, 3 riif, 3 R12F, 3 R13F, 3 R] 4F, rMf, Rl6F, Rl7F, r18f, r19f, R2〇f, rW, r22f, and three r24f may be the same or different. Any two or more of the three RnFs may be bonded to form a ring, three Any two or more of 1^21? may be bonded to form a ring, and any two or more of the three Ri3f may be bonded to form a ring, and any two or more of the three R14F may be bonded to form a ring '3' R24F may also be bonded to form a ring. Examples and preferred examples of the nitrogen-containing heterocyclic compound which may be substituted as L3 and the above formula (Aa), (Ab), (Ba) to (Bd), a heterocyclic compound of a nitrogen-containing atom which may be substituted in a molecule represented by (Ca) to (Ci) and (Da) to (Dt) And the same preferred embodiment.

RnF〜R22F中之可經取代之烴基及該氫烷基可具有之取代 基之例及較佳例分別與上述式（Aa)、（Ab)、（Ba)〜(Bd)、 (Ca)〜(Ci)、及（Da)〜(Dt)所表示之分子中的可經取代之烴基 及該氣院基可具有之取代基之例及較佳例相同。 156591.doc •112- 201202390 r24F中之可經取代之烧基及該烧基可具有之取代基之例 及較佳例與上述式（Aa)、（Ab)、（Ba)〜(Bd)、（Ca)〜(Ci)、及 (Da)〜(Dt)所表示之分子中的可經取代之烷基及該烷基可具 有之取代基之例及較佳例相同。 L3較佳為可經取代之含氮原子之雜環式化合物、 p(R11f)3、r16f-〇·、Rw_c〇2-、r2〇f_s·、或 r22F_s〇3-所表 不之分子，更佳為可經取代之含氮原子之雜環式化合物、 p(R】1F)3、R18F-rn · ·+、wof . 2、或R -S所表示之分子，進而較佳 為含氮原子之雜環式化合物、或p(RllF)4表示之分子。 一作為上述L3之例，可列舉可經取代之下述式η〜…所 示之分子。 [化 44]Examples of the substituted hydrocarbon group in RnF to R22F and the substituent which the hydrogen alkyl group may have, and preferred examples are the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca)~ (Ci), and the substituents in the molecule represented by (Da) to (Dt) and the substituents which the gas group may have are the same as the preferred examples. 156591.doc • 112- 201202390 The substitutable alkyl group in r24F and the substituents which may have the substituents and preferred examples thereof are the above formulas (Aa), (Ab), (Ba) to (Bd), Examples of the replaceable alkyl group in the molecule represented by (Ca) to (Ci) and (Da) to (Dt) and the substituent which the alkyl group may have are the same as the preferred examples. L3 is preferably a substituted heterocyclic compound containing a nitrogen atom, a molecule represented by p(R11f)3, r16f-〇·, Rw_c〇2-, r2〇f_s·, or r22F_s〇3-, more Preferably, the nitrogen-containing heterocyclic compound, p(R]1F)3, R18F-rn··+, wof. 2, or R-S, which may be substituted, further preferably a nitrogen-containing atom A heterocyclic compound or a molecule represented by p(RllF)4. As an example of the above L3, a molecule which can be substituted by the following formulas η to ... can be cited. [化44]

156591.doc -113· 201202390156591.doc -113· 201202390

e10E10

[化 45][化45]

156591.doc - 114- s 201202390156591.doc - 114- s 201202390

e22E22

?〇P SOaH?〇P SOaH

e24 e25 e26E24 e25 e26

CO OHCO OH

e27 ό ό e28 e29E27 ό ό e28 e29

e3〇 e31 e32 [化 46]E3〇 e31 e32 [Chem. 46]

上述式所表示之分子及離子中，L3較佳為式el〜el3、 el6 〜e20、e25、e26、e28、e32、e33、及 e34 中之任一個所 表示之分子，更佳為式el〜el3、el6〜e2〇、e28、及eD中 之任一個所表示之分子。 於：成式⑴所表示之銀錯合物中，X、 除了鹵化物離子（彻t / 丁 如 氟化物離子、氯化物離子、溴化物 156591.doc •115· 201202390 離子、碘化物離子）、四氟硼酸根離子、六氟磷酸根離 子、六氟銻酸根離子、六氟砷酸根離子、三氟曱磺酸根離 子、二氟乙酸根離子、四（五氟苯基）硼酸根離子之外，可 列舉硫酸根離子、硝酸根離子、碳酸根離子、乙酸根離 子、過氣酸根離子、曱磺酸根離子、苯磺酸根離子、對甲 笨石《心根離子、十二烧基苯續蜂根離子、四笨基棚酸根離 子、及含有具有該等離子結構之重複單元的高分子化合 物，由於對錯合物之配位力良好，故較佳為齒化物離子、 四氟硼酸根離子、六氟磷酸根離子、三氟甲磺酸根離子、 三氟乙酸根離子、四（五氟苯基）硼酸根離子、硫酸根離 子、硝酸根離子、碳酸根離子、乙酸根離子、過氣酸根離 子、對甲苯磺酸根離子、及四苯基硼酸根離子，更佳為鹵 化物離子，進而較佳為溴化物離子、碘化物離子，尤佳為 蛾化物離子。 於組成式（1)中，a為大於0.5之數，b' c&amp;d分別獨立為〇 以上之數。 此處，將把上述a、b、c及d代入至數式（zxa)+(2xb)+c+d 而求出之值定義為上述組成式（〇中之平均配位數。式中， 2為1^中之可配位於Ag+之原子及離子的總數。該平均配位 數較佳為2.0以上且7.〇以下。即，上述a、b、c&amp;d較佳為 滿足下述數式（2)。 7.0^ (zxa)+(2xb)+c+d&gt;2.0 (2) (數式（2)中，z為L1中之可配位於Ag+之原子及離子的總 數）。 〜 156591.docIn the molecule and ion represented by the above formula, L3 is preferably a molecule represented by any one of the formulas el to el3, el6 to e20, e25, e26, e28, e32, e33, and e34, more preferably an elf type A molecule represented by any of el3, el6~e2〇, e28, and eD. In the silver complex represented by the formula (1), X, in addition to halide ions (total t / butyl such as fluoride ions, chloride ions, bromide 156591.doc • 115 · 201202390 ions, iodide ions), a tetrafluoroborate ion, a hexafluorophosphate ion, a hexafluoroantimonate ion, a hexafluoroarsenate ion, a trifluorosulfonate ion, a difluoroacetate ion, or a tetrakis(pentafluorophenyl)borate ion, There may be mentioned sulfate ion, nitrate ion, carbonate ion, acetate ion, percarbonate ion, sulfonate ion, benzenesulfonate ion, p-type stone "heart root ion, twelve-burning benzene continuation bee root ion" a polymer compound having a repeating unit having the plasma structure and a polymer compound having a repeating unit having the plasma structure, preferably having a complexing property to a complex compound, is preferably a tooth ion, a tetrafluoroborate ion, or a hexafluorophosphoric acid. Root ion, trifluoromethanesulfonate ion, trifluoroacetate ion, tetrakis(pentafluorophenyl)borate ion, sulfate ion, nitrate ion, carbonate ion, acetate ion, peracid acid radical P-toluenesulfonic acid ion, and a tetraphenylborate ion, more preferably a halide ion, and further preferably bromide ion, iodide ion, and particularly preferably of moth ion. In the composition formula (1), a is a number greater than 0.5, and b' c & d are each independently a number above 〇. Here, the values obtained by substituting the above a, b, c, and d into the equation (zxa) + (2xb) + c + d are defined as the above-mentioned composition formula (the average coordination number in the equation). 2 is a total number of atoms and ions which can be coordinated to Ag+. The average coordination number is preferably 2.0 or more and 7. 〇 or less. That is, the above a, b, c &amp; d preferably satisfy the following numbers Equation (2) 7.0^ (zxa)+(2xb)+c+d&gt;2.0 (2) (In the formula (2), z is the total number of atoms and ions in the L1 that can be assigned to Ag+.) ~ 156591 .doc

S •116· 201202390 MM式⑴中之平均配位數更佳為3〇以上且6〇以 下，進而較佳為3.5以上且5.5以下，尤佳為4〇以上且5 〇以 下。 a較佳為大於0.5且為h5以下之數，更佳為〇 η 4之數， 進而較佳為0.7Μ.3之數，尤佳為〇8〜12之數。 b較佳為〇〜L5之數，更佳為〇〜1〇之數，進而較佳為 〇〜0.3或1.0之數，尤佳為〇。 c較佳為0七之數，更佳為…之數，$而較佳為 0〜0.3或1.〇之數，尤佳為〇。 d之較佳態樣有兩個。作為—個態樣，較佳為⑷之 ’更佳為0〜0.2之數，進而較佳為G〜G1之數尤佳為〇。 作為另—態樣，較佳為之數，更佳為“〜以 數’進而較佳為ο™之數，尤佳為G8〜i2之數。 兩個態樣之中，更佳為前一態樣。 本發明之膜中的發光性銀錯合物可為單核錯合物、城 ^合物、3核錯合物、4核錯合物、5核錯合物、6核錯合 及7核以上之錯合物之任_種，亦可為該等之混合 ’但較佳為單核錯合物、2核錯合物、或3核錯合物，更 佳為單核錯合物或2核錯合物，進而較佳為單核錯合物。 將本發明之膜中的銀錯合物之例示於表1·1及表卜2中。 =號^上述組成式⑴中之a、b、^，但對於各化合 物編唬可分別取上述所記載之適當的數。 156591.doc •117- 201202390 [表 i-i] &lt;表 ι-ι&gt; 化合物編號 L1 L2 L3 X1 化合物編號 L1 L2 L3 X1 1 Aal' - - F_ 42 Bal' - - F· 2 Aal， - - cr 43 Bal' - - cr 3 Aal' - - Br· 44 Bal' - - Br· 4 Aal' - - Γ 45 Bar _ - Γ 5 Aal' - - BF4- 46 Bal' - - bf4· 6 Aal' - - pf6· 47 Bal， - - pf6· 7 Aal， - N〇3· 48 Bal' • - no3· 8 Aal' - - cf3so3' 49 Bal' - - CF3S03' 9 Aal， - - BPLT 50 Bal， - - BPh/ 10 Aa3, - - F_ 51 Bal， c22 - pf6- 11 Aa3' - Cl— 52 Ba3' - - Br' 12 Aa3' - - Br 53 Ba3' - - Γ 13 Aa3, - - Γ 54 Ba3' - - BF4- 14 Aa5, - - F_ 55 Ba3' - - PF6- 15 Aa5' - - Cl— 56 Ba3' - - no3· 16 Aa5' - - Br· 57 Ba3' - - CF3S03· 17 Aa5' - - Γ 58 Ba3' c22 - PF6- 18 Aal 5, - - F_ 59 Ba6' - - - 19 Aal 5' - - cr 60 Ball， - - Br· 20 Aal5, - _ Bf 61 Ball' - - Γ 21 Aal 5, - - Γ 62 Ball' - bf4- 22 Aa23' - - F_ 63 Ball' - - pf6· 23 Aa23' - - cr 64 Ball' - N03. 24 Aa23' - - Br' 65 Ball' - - CF3SO3· 25 Aa23' - - Γ 66 Bal5' - - Br— 26 Aa35, - _ F· 67 Bal5' - - Γ 27 Aa35' - - cr 68 Bal5' - - bf4· 28 Aa35' - - Br 69 Bal5' - - PFfi' 29 Aa35, - - Γ 70 Bal5' - - NO3' 30 Aa60, - - Γ 71 Bal5' - - CF3SO3' 31 Aa60, - - cr 72 Bal9, c22 - bf4· 32 Aa60' - - Bf 73 Bal 9' c22 - pf6_ 33 Aa60' - - Γ 74 Bal 9, c22 - N03- 34 Aa60' - el cr 75 Bal9* c22 - CF3S03' 35 Aa60' - el3 cr 76 Bel' - - F_ 36 Aa60' - el6 cr 77 Bel' - - Cl— 37 Aa60' - el9 cr 78 Bel' - - Br. 38 Aa60, - el Br· 79 Bel' - - Γ 39 Aa60, - el3 Br&quot; 80 Bel' _ - bf4_ 40 Aa60' - el6 Br· 81 Bel’ _ pf6· 41 Aa60, - el9 Br. 82 Bel， - - CF3SO3' 156591.doc -118- 201202390 [表 1-2] 〈表 1-2&gt; 化合物編號 L1 L2 L3 X1 83 Bel' - el6 bf4- 84 Bel' - el9 BF4· 85 Bel' - e22 - 86 Bel' - e30 _ 87 Bc4' - - F· 88 Bc4' - - cr 89 Bc4' - - Br· 90 Bc4' - - I— 91 Bc4' - - BF4' 92 Bc4' - - pf6· 93 Bc4， - - CF3SO3· 94 Bc9' - - - 95 Bc9' - F_ 96 Bc9' - - cr 97 Bc9， - - Bf 98 Bc9' - - Γ 99 Bc9' - - bf4· 100 Bc9' - - pf6- 101 Bcl5' - - - 102 Bc21' - - F_ 103 Bc21' - - cr 104 Bc21' - - Br· 105 Bc21’ - - r 106 Bc21' - - bf4- 107 Bc21， - - pf6- 108 Bc21' - - CF3SO3' 109 Bdl' - - F_ 110 Bdl， - - cr 111 Bdl， - - Bf 112 Bdl' - - Γ 113 Bdl， - - BF4' 114 Bdl' _ - pf6— 115 Bdl' - - CF3S03' 116 Bdl' - c20 BF4' 117 Bdl' - c22 bf4· 118 Bdl· _ c29 BF4- 119 Bdl' - c37 bf4' 120 Bdl' - c20 pf6· 121 Bdl' - c22 pf6· 122 Bdl' - c29 pf6_ 123 Bdl· - c37 pf6· 化合物編號 L1 L2 L3 X1 124 Aa3' - - bf4· 125 Aa3' - - PF6- 126 Aa3* - - N03- 127 Aa3' - CF3S03· 128 Aa3' - - BPh/ 129 Aal'-2 - - F_ 130 Aal'-2 - - cr 131 Aal'-2 - - Br· 132 Aal'-2 - - Γ 133 Aal'-2 - - bf4- 134 Aal'-2 - - pf6- 135 Aal'-2 - - N〇3· 136 Aar-2 - - CF3S03- 137 Aal，-2 - BPh4' 138 Bal6, - - F_ 139 Bal6, - - Cl· 140 Bal6, - - Br 141 Bal6, - - Γ 142 Bal6, - - BF4' 143 Bal6, - - pf6· 144 Bal6, - - N〇3· 145 Bal6, - - CF3SO3' 146 Bal6, - - BPtu· 147 Aa3' - el bf4· 148 Aa3' - el3 pf6_ 149 Aa3' - el6 NO3· 150 Aa3' el9 BPI14· 151 Bal6' - el bf4_ 152 Bal6' - el3 pf6- 153 Bal6' - el6 N03· 154 Bal6' - el9 BPh4_ 156591.doc -119- 201202390 表1-1及表1-2中「-」表示不包含的意思。 於表1 -1及表1 -2中所示之組合中，較佳為化合物編號 1〜13、22〜25、及31〜108、及124-154所表示之組合，更佳 為化合物編號1〜9、3 1〜41、72~ 108、及124〜154所表示之 組合’進而較佳為化合物編號1〜9、31〜41、72〜75、 94〜1〇〇、及124〜154所表示之組合，尤佳為1〜9、31〜41、 94〜1〇〇、124〜137、及148-154所表示之組合。 以下示出本發明之膜中之銀錯合物的代表例。式1〇,、 32·、68’、94’、及95,所表系之銀錯合物分別為具有上述化 合物編號10、32、68、94、95所表示之組合的具代表性之 銀錯合物。 [化 47]S • 116· 201202390 The average coordination number in the MM formula (1) is more preferably 3 Å or more and 6 Å or less, further preferably 3.5 or more and 5.5 or less, and particularly preferably 4 Å or more and 5 Å or less. a is preferably more than 0.5 and is not more than h5, more preferably 〇 η 4 , more preferably 0.7 Μ .3, and particularly preferably 〇 8 to 12. b is preferably a number of 〇~L5, more preferably 〇~1〇, and further preferably 〇~0.3 or 1.0, and particularly preferably 〇. Preferably, c is a number of seven or seven, more preferably a number of, $ and preferably 0 to 0.3 or 1. a number of 〇, particularly preferably 〇. There are two preferred aspects of d. As a mode, it is preferable that the number of (4) is more preferably 0 to 0.2, and further preferably the number of G to G1 is preferably 〇. Preferably, the number is preferably "~ by number" and preferably οTM, and more preferably G8~i2. Among the two aspects, the former is better. The luminescent silver complex in the film of the present invention may be a mononuclear complex, a city complex, a 3-nuclear complex, a 4-nuclear complex, a 5-nuclear complex, a 6-nuclear complex. And any of the complexes of 7 or more cores may also be such a mixture 'but preferably a mononuclear complex, a 2 nucleus complex, or a 3 nucleus complex, more preferably a single nucleus. The compound or the two-core complex compound is further preferably a mononuclear complex. Examples of the silver complex in the film of the present invention are shown in Tables 1 and 1 and Table 2. The above composition formula (1) Among them, a, b, and ^, but for each compound, the appropriate number can be taken as described above. 156591.doc •117- 201202390 [Table ii] &lt;Table ι-ι&gt; Compound No. L1 L2 L3 X1 Compound No. L1 L2 L3 X1 1 Aal' - - F_ 42 Bal' - - F· 2 Aal, - - cr 43 Bal' - - cr 3 Aal' - - Br· 44 Bal' - - Br· 4 Aal' - - Γ 45 Bar _ - Γ 5 Aal' - - BF4- 46 Bal' - - bf4· 6 Aal' - - pf6· 4 7 Bal, - - pf6· 7 Aal, - N〇3· 48 Bal' • - no3· 8 Aal' - - cf3so3' 49 Bal' - - CF3S03' 9 Aal, - - BPLT 50 Bal, - - BPh/ 10 Aa3, - - F_ 51 Bal, c22 - pf6- 11 Aa3' - Cl— 52 Ba3' - - Br' 12 Aa3' - - Br 53 Ba3' - - Γ 13 Aa3, - - Γ 54 Ba3' - - BF4- 14 Aa5, - - F_ 55 Ba3' - - PF6- 15 Aa5' - - Cl- 56 Ba3' - - no3· 16 Aa5' - - Br· 57 Ba3' - - CF3S03· 17 Aa5' - - Γ 58 Ba3' C22 - PF6- 18 Aal 5, - - F_ 59 Ba6' - - - 19 Aal 5' - - cr 60 Ball, - - Br· 20 Aal5, - _ Bf 61 Ball' - - Γ 21 Aal 5, - - Γ 62 Ball' - bf4- 22 Aa23' - - F_ 63 Ball' - - pf6· 23 Aa23' - - cr 64 Ball' - N03. 24 Aa23' - - Br' 65 Ball' - - CF3SO3· 25 Aa23' - - Γ 66 Bal5' - - Br— 26 Aa35, - _ F· 67 Bal5' - - Γ 27 Aa35' - - cr 68 Bal5' - - bf4· 28 Aa35' - - Br 69 Bal5' - - PFfi' 29 Aa35, - - Γ 70 Bal5' - - NO3' 30 Aa60, - - Γ 71 Bal5' - - CF3SO3' 31 Aa60, - - cr 72 Bal9, c22 - bf4· 32 Aa60' - - Bf 73 Bal 9' c22 - pf6_ 33 Aa60' - - Γ 74 Bal 9, c22 - N03- 34 Aa60' - el cr 75 Bal9* c22 - CF3S03' 35 Aa60' - el3 cr 76 Bel' - - F_ 36 Aa60' - el6 cr 77 Bel' - - Cl— 37 Aa60' - El9 cr 78 Bel' - - Br. 38 Aa60, - el Br· 79 Bel' - - Γ 39 Aa60, - el3 Br&quot; 80 Bel' _ - bf4_ 40 Aa60' - el6 Br· 81 Bel' _ pf6· 41 Aa60 , - el9 Br. 82 Bel, - - CF3SO3' 156591.doc -118- 201202390 [Table 1-2] <Table 1-2> Compound No. L1 L2 L3 X1 83 Bel' - el6 bf4- 84 Bel' - el9 BF4 · 85 Bel' - e22 - 86 Bel' - e30 _ 87 Bc4' - - F· 88 Bc4' - - cr 89 Bc4' - - Br· 90 Bc4' - - I- 91 Bc4' - - BF4' 92 Bc4' - - pf6· 93 Bc4, - - CF3SO3· 94 Bc9' - - - 95 Bc9' - F_ 96 Bc9' - - cr 97 Bc9, - - Bf 98 Bc9' - - Γ 99 Bc9' - - bf4· 100 Bc9' - - pf6- 101 Bcl5' - - - 102 Bc21' - - F_ 103 Bc21' - - cr 104 Bc21' - - Br· 105 Bc21' - - r 106 Bc21' - - bf4- 107 Bc21, - - pf6- 108 Bc21' - - CF3SO3' 109 Bdl' - - F_ 110 Bdl, - - cr 111 Bdl, - - Bf 112 Bdl' - - Γ 113 Bdl, - - BF4' 114 Bdl' _ - pf6— 115 Bdl' - - CF3S03' 116 Bdl' - c20 BF4' 117 Bdl' - c22 bf4· 118 Bdl· _ c29 BF4- 119 Bdl' - c37 bf4' 120 Bdl' - c20 pf6· 121 Bdl' - c22 Pf6· 122 Bdl' - c29 pf6_ 123 Bdl· - c37 pf6· Compound No. L1 L2 L3 X1 124 Aa3' - - bf4· 125 Aa3' - - PF6- 126 Aa3* - - N03- 127 Aa3' - CF3S03· 128 Aa3 ' - - BPh/ 129 Aal'-2 - - F_ 130 Aal'-2 - - cr 131 Aal'-2 - - Br· 132 Aal'-2 - - Γ 133 Aal'-2 - - bf4- 134 Aal' -2 - - pf6- 135 Aal'-2 - - N〇3· 136 Aar-2 - - CF3S03- 137 Aal,-2 - BPh4' 138 Bal6, - - F_ 139 Bal6, - - Cl· 140 Bal6, - - Br 141 Bal6, - - Γ 142 Bal6, - - BF4' 143 Bal6, - - pf6· 144 Bal6, - - N〇3· 145 Bal6, - - CF3SO3' 146 Bal6, - - BPtu· 147 Aa3' - el Bf4· 148 Aa3' - el3 pf6_ 149 Aa3' - el6 NO3· 150 Aa3' el9 BPI14· 151 Bal6' - el bf4_ 152 Bal6' - el3 pf6- 153 Bal6' - el6 N03· 154 Bal6' - el9 BPh4_ 156591.doc -119- 201202390 "-" in Table 1-1 and Table 1-2 means not included. The combination shown in Table 1-1 and Table 1-2 is preferably a combination of compound numbers 1 to 13, 22 to 25, and 31 to 108, and 124 to 154, more preferably compound number 1. Combinations of ～9, 3 1 to 41, 72 to 108, and 124 to 154' are further preferably compound numbers 1 to 9, 31 to 41, 72 to 75, 94 to 1 〇〇, and 124 to 154. The combination of the representations is particularly preferably a combination of 1 to 9, 31 to 41, 94 to 1 , 124 to 137, and 148 to 154. Representative examples of the silver complex in the film of the present invention are shown below. Formulae 〇, 32, 68', 94', and 95, and the silver complexes of the formula are representative silver having the combination of the above compound numbers 10, 32, 68, 94, and 95, respectively. Complex compound. [化47]

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S 201202390S 201202390

發光壽命以較長為佳。因此，較佳為s 1能量與τ 1能量之差 為0.3 eV以下’更佳為〇·2 eV以下，由於三重態容易有助 於發光，故進而較佳為〇.1 eV以下。若81能量與T1能量之 差為0·3 eV以下’則可表現出2〇〇 ns以上之發光壽命。 此處’以下舉出一例對81能量與T1能量之差的求出方法 加以說明。首先’藉由密度泛函數法對銀錯合物之初期結 構進行結構最適化計算。結構最適化計算時，可使用 B3LYP作為泛函數’作為基底函數，對於銀原子（或Ag+)及 函素原子可使用LANL2DZ，對於其他原子可使用6_ 3 1 G(d) ° 计异程式可使用 Gaussian〇3(Gaussian Inc.製造）。 作為上述銀錯合物之初期結構，於上述組成式（丨）中之 1 2 3 L·、L及L均不具有可配位於Ag+之陰離子，且χι並非F-、Cl、Br及I中之任一個之情形時，較佳為將總電荷設為 + 1，於L1、L2及L3中之任一個以上具有可配位於Ag+之陰 離子，或X1為F·、Cl·、及1_中之任一個之情形時，較佳 為將總電荷設為〇，且使用以L1、L2及L3之各配位原子距 離銀原子（或Ag+)成為3·〇 A以下之方式而配置者。於χΐ為 156591.doc • 121 - 201202390 鹵化物離子之情形時，較佳為使用以^亦距離銀原子（或 Ag )成為3.0 A以下之方式而配置者。 此處所謂之S1能量，係指於單電子激發狀態下以基底狀 態作為基準時的最低激發單重態之能量，所謂T1能量，係 指於單電子激發狀態下以基底狀態為基準時的最低激發三 重態之旎量。s 1能量及T1能量可藉由以下方法而求出：對 藉由上述結構最適化计算所得之經最適化的結構應用時間 相關密度泛函數法，計算單電子激發狀態。時間相關密度 泛函數法中使用之計算方法中，可使用B3LYIM,為泛函 數，作為基底函數，對於Ag+及鹵素原子可使用 LANL2DZ，對於其他原子可使用6-31 G(d)。計算程式可使 用 Gaussian03(Gaussian Inc.製造）〇 本發明之膜中的銀錯合物中，於Li具有丨個以上的可經 取代之含氮原子之雜環式化合物中之氮原子作為可配位於 Ag之氮原子之情形時，關於Ll中之可配位於Ag+之所有氮 原子，L中之可配位於Ag+之氮原子與Ag+之距離較佳為 2.00 A以上且3.50 A以下。更佳為2.1〇 A以上且3.40人以 下’進而較佳為2.20 A以上且3.30 A以下，尤佳為2.30 A 以上且3.20入以下，特佳為23〇人以上且27〇人以下。 可配位於Ag+之氮原子與Ag+之距離例如可藉由利用上述 密度泛函數法進行銀結構最適化計算的方法而求出。 本發明之膜中的銀錯合物例如可藉由在溶劑中將銀鹽與 構成銀錯合物之分子混合的方法而製造。 關於本發明之膜中之銀錯合物的製造方法之例，若舉出 156591.docThe luminescence lifetime is preferably longer. Therefore, it is preferable that the difference between the energy of s 1 and the energy of τ 1 is 0.3 eV or less, more preferably 〇 2 eV or less, and since the triplet state is likely to contribute to light emission, it is preferably 〇.1 eV or less. If the difference between the 81 energy and the T1 energy is 0·3 eV or less, the luminescence lifetime of 2 〇〇 ns or more can be exhibited. Here, an example of the method for determining the difference between the energy of 81 and the energy of T1 will be described below. First, the structural optimization of the initial structure of the silver complex was performed by the density-spread function method. For structural optimization calculations, B3LYP can be used as a general function 'as a basis function, LANL2DZ can be used for silver atoms (or Ag+) and atomic atoms, and 6_3 1 G(d) ° can be used for other atoms. Gaussian 〇 3 (manufactured by Gaussian Inc.) was used. As the initial structure of the above silver complex, 1 2 3 L·, L and L in the above composition formula (不) do not have an anion which can be coordinated to Ag+, and χι is not in F-, Cl, Br and I. In any case, it is preferable to set the total electric charge to +1, and to have an anion which can be coordinated to Ag+ in any one of L1, L2 and L3, or X1 is F·, Cl·, and 1_ In any case, it is preferable to set the total electric charge to 〇, and to arrange the respective coordinate atoms of L1, L2, and L3 so that the silver atom (or Ag+) becomes 3 〇A or less. In the case of a halide ion, it is preferable to use a method in which the silver atom (or Ag) is 3.0 A or less. The S1 energy referred to herein refers to the energy of the lowest excited singlet state when the substrate state is used as a reference in the single electron excitation state, and the T1 energy refers to the lowest excitation when the substrate state is used as the reference in the single electron excitation state. The amount of triplet. The s 1 energy and the T1 energy can be obtained by calculating the single electron excitation state by applying the time-dependent density-universal function method to the optimized structure calculated by the above-described structure optimization. Time-Dependent Density In the calculation method used in the general function method, B3LYIM can be used as the functional function. As a basis function, LANL2DZ can be used for Ag+ and halogen atoms, and 6-31 G(d) can be used for other atoms. The calculation program can use Gaussian 03 (manufactured by Gaussian Inc.) in the silver complex in the film of the present invention, and the nitrogen atom in the heterocyclic compound having more than one of the substituted nitrogen-containing atoms in Li can be used as a match. In the case of the nitrogen atom of Ag, the distance between the nitrogen atom which can be assigned to Ag+ and the Ag+ in L is preferably 2.00 A or more and 3.50 A or less in relation to all nitrogen atoms which can be coordinated to Ag+ in L1. More preferably, it is 2.1 〇A or more and 3.40 Å or less, and further preferably 2.20 A or more and 3.30 A or less, particularly preferably 2.30 A or more and 3.20 or less, particularly preferably 23 〇 or more and 27 〇 or less. The distance between the nitrogen atom and the Ag+ which can be assigned to Ag+ can be determined, for example, by a method for calculating the silver structure by the above-described density functional method. The silver complex in the film of the present invention can be produced, for example, by a method of mixing a silver salt with a molecule constituting a silver complex in a solvent. An example of a method for producing a silver complex in the film of the present invention is 156591.doc.

S 122· 201202390 上述式32.所表示之錯合物為例加以說明，則可藉由將】 之漠化銀⑴' i _〇1之工仏6〇,所表示之分子及溶劑 (例如乙腈、二氯甲燒）50 mL混合，加熱30分鐘左右並使 其回流’將反應液進行m驗之溶劑緩緩蒸館去除 並再結晶，而製造上述式32,所表示之錯合物。 本發明所提供之膜的厚度通常為i nm〜5〇叫，較佳為2 ⑽〜Η)㈣，更佳為3 nm〜5卿，進而較佳為5⑽〜3叫， 尤佳為H)nm〜細⑽，其原因在於用於發光元件時容易流 通電荷。膜亦可含有針孔或凹凸，但較佳為不含針孔及凹 凸。 本發明之膜例如可藉由包括將銀錯合物與其他成分以任 意比例於基板上蒸^步㈣方*、或包括使銀錯合物與 其他成分以任意比㈣浮或溶解於溶财並進行塗佈之步 驟的方法而製造。較佳為藉由包括使银錯合物與其他成分 以任意比例懸浮或溶解於溶劑中並進行塗佈之步驟的方法 而製造。 /乍為用於上述塗佈步驟令之溶劑，例如可列舉苯、甲 本、二甲苯、氯仿、二氯乙烧、u，2,2四氯乙烧、二 氯f烧、四氫心南' 2_甲基四氣㈣^二号院、· 二甲基曱醯胺、二甲基亞砜、丙酮、甲基乙基酮、 乙酸乙醋、曱醇、乙醇、異丙醇、己烧、環己燒、及該等 之混合物》 t 減 作為使溶劑乾燥之方法的例，可列舉風乾 壓乾燥、加熱減壓乾燥、及噴附氮氣進行 、加熱乾燥、 之乾燥，較佳 156591.doc •123· 201202390 為几乾或加熱乾燥，更佳為加熱乾燥。 作為塗佈方法，例如可列舉旋塗法 凹版印刷法、棒塗法m &amp;鱗塑法、浸塗法、 版印刷法^ U法'網版印刷法、柔 p刷法、喷墨法及套版印刷法， 法、輕塗法、喷塗法、網版印刷法：為旋塗法、鎮塑 及套版印刷法。 、柔版印刷法、喷墨法 分二 =亦可含有其他成分。關於該成分，可使用低 =:=:有機材料、有機無機複合材料、無 八及合物’可根據用途任意選擇。作為該成 刀’：如可列舉：咔唑衍生物、三唑衍生物、啰唑衍生 物D坐衍生物&quot;米唾衍生物、多芳基院煙衍生物、口比 唾琳衍生物、吼唾相衍生物、苯二胺衍生物、芳基胺衍 ^物、胺基取代查爾酮衍生物、苯乙稀基蒽衍生物、第酮 何生物、月不何生物、二苯乙稀衍生物、石夕氮烧衍生物、苯 乙稀基胺衍生物、芳㈣二次甲純生物、㈣衍生物、 噻吩低聚物、聚噻吩等導電性高分子低聚物，蒽醌二甲烷 衍生物、蒽酮衍生物、聯苯醌衍生物、二氧化噻喃衍生 物、碳二亞胺衍生物、亞苐基罕烷衍生物、二苯乙烯基吡 **井衍生物、芳香環（萘、茈等）之四羧酸酐、酞菁衍生物、 金屬錯合物（例如8-羥基喹啉衍生物之金屬錯合物、以金屬 醜菁為配位基之金屬錯合物、以笨并噚唑為配位基之金屬 錯合物、以苯并噻唑為配位基之金屬錯合物）、鹼金屬、 驗土金屬、稀土金屬、鹼金屬之氧化物、鹼金屬之鹵化 物、驗土金屬之氧化物、鹼土金屬之齒化物、稀土金屬之S 122· 201202390 The complex represented by the above formula 32. is described as an example, and the molecule and solvent (for example, acetonitrile) can be represented by the process of dissolving silver (1)' i _ 〇 1 . 50 mL of methylene chloride was mixed and heated for about 30 minutes and refluxed. The solvent was slowly evaporated and recrystallized to prepare a complex represented by the above formula 32. The thickness of the film provided by the present invention is usually i nm~5 〇, preferably 2 (10) Η) (4), more preferably 3 nm 〜5 卿, and further preferably 5 (10) 〜3, especially preferably H) The reason why nm is fine (10) is that charge is easily distributed when used for a light-emitting element. The film may also contain pinholes or concavities and convexities, but is preferably free of pinholes and concavities. The film of the present invention can be floated or dissolved in an arbitrary ratio (IV) by, for example, including the silver complex and other components on the substrate at any ratio, or by dissolving the silver complex and other components at any ratio (four). It is produced by a method of performing the coating step. It is preferably produced by a method comprising the steps of suspending or dissolving a silver complex and other components in a solvent in an arbitrary ratio and applying the coating. /乍 is a solvent used for the above coating step, and examples thereof include benzene, methyl, xylene, chloroform, dichloroethene, u, 2, 2 tetrachloroethane, dichloro-f, tetrahydromangan ' 2_Methyl four gas (four) ^ No. 2, · Dimethyl decylamine, dimethyl sulfoxide, acetone, methyl ethyl ketone, ethyl acetate, sterol, ethanol, isopropanol, hexane And the mixture of the above, and the mixture of the above, as an example of the method for drying the solvent, for example, air drying and drying, heating under reduced pressure, and spraying with nitrogen, heating and drying, and drying, preferably 156591.doc •123· 201202390 is a few dry or heat drying, more preferably heat drying. Examples of the coating method include a spin coating gravure printing method, a bar coating method m &amp; a scale molding method, a dip coating method, a plate printing method, a U method, a screen printing method, a soft p brush method, and an ink jet method. The printing method, the method, the light coating method, the spraying method, the screen printing method: the spin coating method, the plastic molding method and the plate printing method. , flexographic printing, inkjet method 2 = can also contain other ingredients. Regarding this component, low =:=: organic material, organic-inorganic composite material, and octa-free compound can be used, and it can be arbitrarily selected according to the use. Examples of the forming tool include: a carbazole derivative, a triazole derivative, a carbazole derivative D-supplement derivative, a rice saliva derivative, a polyaryl-based tobacco derivative, a saliva derivative, and a saliva derivative.吼 saliva derivative, phenylenediamine derivative, arylamine derivative, amine-substituted chalcone derivative, styrene-based hydrazine derivative, ketone Ho, moon, biphenyl a conductive polymer oligomer such as a derivative, a sulphur derivative, a styrene derivative, an aryl (tetra) secondary pure organism, a (tetra) derivative, a thiophene oligomer, or a polythiophene, and a quinodimethane Derivatives, anthrone derivatives, biphenyl hydrazine derivatives, thiofuran derivatives, carbodiimide derivatives, fluorenylene derivatives, stilbene pyridine derivatives, aromatic rings a tetracarboxylic anhydride, a phthalocyanine derivative, a metal complex of naphthalene, anthracene, etc. (for example, a metal complex of an 8-hydroxyquinoline derivative, a metal complex having a metal ugly phthalocyanine as a ligand, and a stupid And carbazole is a metal complex of a ligand, a metal complex of benzothiazole as a ligand, alkali metal, soil test Genus, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of test earth metal, an alkaline earth metal compound of the teeth, of a rare earth metal

156591.doc . m. S 201202390 氧化物或稀土金屬之齒化物、驗金屬錯合物'驗土金屬錯 合物、稀土金屬錯合物、具有第骨架之化合物、具有㈣ 骨架之化合物、具有三，骨架之化合物、具有芳基矽烷骨 架之化：物、可含有支持電解質(三氟甲磺酸鋰、過氣酸 過氣s文四丁基銨、六氟鱗酸鉀、四氟硼酸四_正丁基 錄等）之溶劑（碳酸丙稀醋、乙猜、2_甲基四氣咬喊、J· 一氧雜呋喃、硝基苯、N，N_二甲基甲醯胺、二曱基亞砜、 甘油、丙醇、水等）及該等之混合物， 較佳為㈣料物、三。坐衍生物、十坐衍生物、吟二唾 方生物米坐衍生物、多芳基烧烴衍生物、。比。坐琳衍生 物、㈣相衍生物H衍生物、芳基胺衍生物、苯 乙烯基胺衍生4勿 '外琳衍生⑯、嗟吩低聚物、㈣苯酿衍生 物、芳香環（萘、托等）之四叛酸肝、狄菁衍生物、金屬錯 合物（例如8-羥基喹啉衍生物之金屬錯合物、以金屬酞菁為 配位基之金屬錯合物、以苯并呤唑為配位基之金屬錯合物 及以笨并噻嗤為配位基之金屬錯合物）、具有苐骨架之化 合物、具有吡啶骨架之化合物、具有三畊骨架之化合物及 具有芳基矽烷骨架之化合物， 更佳為咔唑衍生物、噚唑衍生物、噚二唑衍生物、咪唑 衍生物、苯二胺衍生物、芳基胺衍生物、卟啉衍生物、酞 菁付生物、具有第骨架之化合物、具有吼咬骨架之化合 物、具有三畊骨架之化合物及具有芳基矽烷骨架之化合 物， 進而較佳為咔唑衍生物、咩二唑衍生物、芳基胺衍生 15659l.doc •125· 201202390 物、有機矽烷衍生物、具有第骨架之化合物、具有三啩骨 架之化合物及具有芳基矽烷骨架之化合物。 其他成分可為一種，亦可為兩種以上之組合。 膜中之銀錯合物#含量相對於膜整體之重量通常為 〇·〇1〜100重量％ ’較佳為〇」〜99重量％，更佳為^，重量 %，進而較佳為5〜80重量％，尤佳為1〇〜5〇重量％。 本發明之膜較佳為使用高分子化合物作為用以形成膜的 成分。作為該高分子化合物，例如可列舉以下者。- 卡唾衍生物&quot;比嗤琳衍生物、Dtb唾琳_衍生物、芳基胺 街生物、二苯乙烯衍生物、三苯基二胺衍生物、苯二胺衍 生物、苯乙稀基葱衍生物、#乙烯基胺衍生物、芳香族二 次甲基衍生物、腙衍生物、聚芳香族三級胺化合物、胺基 取代查爾崎生物等含有電洞傳輸材料之殘基的聚合物； 多芳基烷烴衍生物、聚乙烯咔唑衍生物、聚矽烷衍生 物、於側鍵或主鍵上具有彡香族㉟結構之聚石夕氧院衍生 物、聚苯胺衍生物、聚（2,5_嗟吩乙炔）衍生物、苯胺系共 聚物、聚嗟吩等導電性高分子低聚物等高分子電洞傳輸材 料； 三唑衍生物、嘮二唑衍生物、咪唑衍生物、聯苯醌衍生 物、二氧化噻喃衍生物、碳二亞胺衍生物、亞苐基甲烷衍 生物、二苯乙烯基吡畊衍生物、芳香環羧酸酐衍生物 (萘、茈）、金屬錯合物（例如8_羥基喹啉衍生物之金屬錯合 物、以苯并啰唑為配位基之金屬錯合物、以苯并噻唑為配 位基之金屬錯合物）、萘醌衍生物、蒽醌衍生物、四氰基 15659丨.doc156591.doc . m. S 201202390 Oxide or rare earth metal toothing, metal complex complex 'soil metal complex, rare earth metal complex, compound with skeleton, compound with (iv) skeleton, with three a compound of a skeleton having an aryl decane skeleton: may contain a supporting electrolyte (lithium trifluoromethanesulfonate, peroxyacid s-tetrabutylammonium chloride, potassium hexafluorophosphate, tetrafluoroborate tetra _ Solvents of n-butyl group, etc. (propylene carbonate vinegar, B guess, 2_methyl four gas bite, J. oxafuran, nitrobenzene, N, N-dimethylformamide, diterpenes The sulfoxide, glycerol, propanol, water, etc.) and mixtures thereof are preferably (iv) materials, three. Sitting derivatives, ten-spot derivatives, sputum derivatives, polyaryl hydrocarbon derivatives. ratio. Selenium derivative, (four) phase derivative H derivative, arylamine derivative, styrylamine derivative 4 Beyondene derivative 16, porphin oligomer, (four) benzene brewing derivative, aromatic ring (naphthalene, torr Etc. 4, rebel liver, dicamba derivatives, metal complexes (such as metal complexes of 8-hydroxyquinoline derivatives, metal complexes with metal phthalocyanines as ligands, benzopyrene a metal complex having a azole as a ligand and a metal complex having a benzoindole as a ligand, a compound having an anthracene skeleton, a compound having a pyridine skeleton, a compound having a three-till skeleton, and having an aryl decane a compound of a skeleton, more preferably an oxazole derivative, a carbazole derivative, an oxadiazole derivative, an imidazole derivative, a phenylenediamine derivative, an arylamine derivative, a porphyrin derivative, a phthalocyanine derivative, or the like a compound of the first skeleton, a compound having a bite skeleton, a compound having a three-till skeleton, and a compound having an aryl decane skeleton, and further preferably a carbazole derivative, an oxadiazole derivative, and an arylamine derivative 15659l.doc • 125· 201202390, organic decane derived , The skeleton of the compound having three Gua skeleton of the compound and the compound having an aryl group having a skeleton of the Silane. The other components may be one type or a combination of two or more types. The content of the silver complex # in the film is usually 〇·〇1 to 100% by weight, preferably 〇% to 99% by weight, more preferably 2% by weight, still more preferably 5% by weight. 80% by weight, particularly preferably 1〇~5〇% by weight. The film of the present invention preferably uses a polymer compound as a component for forming a film. Examples of the polymer compound include the following. - Carpene Derivatives &quot;Bilin Derivatives, Dtb Salin_Derivatives, Arylamine Streets, Styrene Derivatives, Triphenyldiamine Derivatives, Phenylenediamine Derivatives, Phenylethyl Polymerization of residues containing hole transporting materials such as onion derivatives, #vinylamine derivatives, aromatic secondary methyl derivatives, anthracene derivatives, polyaromatic tertiary amine compounds, and amine-substituted Chalcazia organisms a polyarylene derivative, a polyvinyl carbazole derivative, a polydecane derivative, a polyoxan derivative having a ruthenium 35 structure on a side bond or a primary bond, a polyaniline derivative, a poly(2) Polymer hole transporting materials such as 5_ phenanthrene acetylene derivatives, aniline copolymers, and conductive polymer oligomers such as polybenzazole; triazole derivatives, oxadiazole derivatives, imidazole derivatives, and Benzoquinone derivative, thioanthene derivative, carbodiimide derivative, mercapto methane derivative, distyryl pyridinium derivative, aromatic cyclic carboxylic anhydride derivative (naphthalene, anthracene), metal mismatch a metal complex such as an 8-hydroxyquinoline derivative, benzoxazole a metal complex of a ligand, a metal complex of benzothiazole as a ligand, a naphthoquinone derivative, an anthracene derivative, a tetracyano group 15659丨.doc

S -126- 201202390 蒽醌二曱烷衍生物、苐酮衍生物、二伸苯基二氰乙烯衍生 物、聯苯醌衍生物、8-羥基喹啉衍生物、酞菁衍生物、金 屬。卜啉衍生物等含有電子傳輸材料之殘基的聚合物，聚三 畊衍生物、聚噚唑衍生物、聚萘衍生物、聚噻吩乙炔衍生 物、聚喹啉衍生物、聚喹噚啉衍生物 '於主鏈或側鏈上具 有方香族私結構的聚合物等電子傳輸材料； 聚氣乙烯、聚碳酸酯、聚笨乙烯、聚甲基丙烯酸甲酯 (PMMA，P〇lymethylmethaCrylate)、聚甲基丙烯酸 丁酯及 其衍生物、苐衍生物、聚酯及其衍生物、聚砜及其衍生 物聚本趟衍生物、聚丁 一烯衍生物、煙樹脂、酮樹脂、 苯氧樹脂、聚醯胺、乙基纖維素、乙酸乙烯酯、abs (Acrylonitrile-Butadiene-Styrene ,丙烯腈 _ 苯乙烯 _ 丁二烯） 樹脂、聚胺基甲酸冑、三聚氰胺樹月旨、不飽和《樹脂、 醇酸樹脂、環氧樹脂、矽樹脂、聚環氧乙烷及其衍生物、 聚丙烯腈及其衍生物'偏二I乙烯與六氟丙烯之共聚物等 高分子基質。 較佳為聚咔唑衍生物、聚芳基胺衍生物、聚苯二胺衍生 物、聚腙衍生物、含有聚芳香族三級胺化合物之殘基的聚 合物、多芳基⑥烴衍生物、聚乙料讀生物、聚石夕烧衍 生物、於側鏈或域上具有芳香族胺結構的聚⑦氧烧衍生 物、聚（2,5-。塞吩乙炔）衍生物、苯胺系共聚物聚三嗤衍 生物聚f __ 生物、聚_ 4衍生物、含有8 _經基唾琳 何生物之殘基的聚合物、聚欧菁衍生物、含有金屬外你衍 生物之殘基的聚合物、聚三畊衍生物、聚呵唑衍生物、聚 156591.doc -127- 201202390 萘衍生物、聚苯胺衍生物、聚售吩衍生物、聚〇g吩乙炔衍 生物、聚喹噚啉衍生物、於主鏈或側鏈上具有芳香族胺妹 構的聚合物、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚甲基丙 烯酸甲酯、苐衍生物、聚苯醚衍生物、烴樹脂、聚醯胺、 聚環氧乙烷及其衍生物， 更佳為聚味°坐衍生物、聚芳基胺衍生物、含有聚芳香族 三級胺化合物之殘基的聚合物、多芳基烷烴衍生物、聚乙 烯咔唑衍生物、聚矽烷衍生物、聚噻吩衍生物、聚呤二唑 衍生物、含有金屬卟啉衍生物之殘基的聚合物、聚三畊衍 生物、聚呤唑衍生物、聚萘衍生物、於主鏈或側鏈上具有 芳香族胺結構的聚合物、聚苯乙烯、聚甲基丙烯酸甲酯、 第衍生物、聚苯醚衍生物， 進而較佳為聚咔唑衍生物、含有聚芳香族三級胺化合物 之殘基的聚合物、多芳基烧烴衍生物、聚乙稀咔唑衍生 物、聚咩二唑衍生物、聚三畊衍生物、苐衍生物。 高分子化合物可為一種，亦可為兩種以上之組合。 上述高分子化合物之聚苯乙烯換算的數量平均分子量通 常為’較佳為1χ1〇3〜1χ1〇7，更佳為2⑽3〜 1X106,進而較佳為3χ103〜5χ1〇5，尤佳為5χι〇3〜ΐχι〇5。 於本發明之膜含有上述高分子化合物之情形時 銀錯合物的含量相對於膜整體之重量通常為〇_〇1 量％ ’較佳為(U〜99重量％，更佳為卜9〇重量％， 為5〜80重量％，尤佳為1〇〜5〇重量 ’膜中之 〜99.99重 進而較佳 本發明提供—種含有上述本發明之膜的發光元件。該發 15659l.docS-126-201202390 Dioxane derivative, anthrone derivative, diphenylene dicyanoethylene derivative, biphenyl hydrazine derivative, 8-hydroxyquinoline derivative, phthalocyanine derivative, metal. a polymer containing a residue of an electron transporting material such as a porphyrin derivative, a polytrimide derivative, a polycarbazole derivative, a polynaphthalene derivative, a polythiophene acetylene derivative, a polyquinoline derivative, or a polyquinoxaline derivative. An electron transporting material such as a polymer having a fragrant private structure on a main chain or a side chain; polyethylene, polycarbonate, polystyrene, polymethyl methacrylate (PMMA, P〇lymethylmetha Crylate), poly Butyl methacrylate and its derivatives, anthraquinone derivatives, polyesters and derivatives thereof, polysulfones and derivatives thereof, polybenzidine derivatives, polybutene derivatives, smoke resins, ketone resins, phenoxy resins, Polyamide, ethyl cellulose, vinyl acetate, abs (Acrylonitrile-Butadiene-Styrene, acrylonitrile styrene-butadiene) resin, urethane phthalate, melamine tree, unsaturated "resin, alcohol A polymer matrix such as an acid resin, an epoxy resin, an anthracene resin, a polyethylene oxide and a derivative thereof, a polyacrylonitrile and a derivative thereof, a copolymer of a vinylidene fluoride and a hexafluoropropylene. Preferred are polycarbazole derivatives, polyarylamine derivatives, polyphenylenediamine derivatives, polyfluorene derivatives, polymers containing residues of polyaromatic tertiary amine compounds, polyaryl 6 hydrocarbon derivatives , poly-batch reading organism, poly-stone derivative, poly 7-oxygen derivative with aromatic amine structure in side chain or domain, poly(2,5-exephene acetylene) derivative, aniline copolymerization Polymeric triterpene derivative polyf__bio, poly-4 derivative, polymer containing residues of 8 _ sulphate, poly phthalocyanine derivatives, and residues containing residues other than metals , polytrimide derivative, polyazole derivative, poly 156591.doc -127- 201202390 naphthalene derivative, polyaniline derivative, poly phenanthrene derivative, polyfluorene acetylene derivative, polyquinoxaline derivative a polymer having an aromatic amine structure in a main chain or a side chain, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, anthracene derivative, polyphenylene ether derivative, hydrocarbon resin Polyamide, polyethylene oxide and its derivatives, more preferably poly-scented derivatives, polyarylamine derivatives Organisms, polymers containing residues of polyaromatic tertiary amine compounds, polyarylalkane derivatives, polyvinylcarbazole derivatives, polydecane derivatives, polythiophene derivatives, polyoxadiazole derivatives, metal-containing a polymer of a residue of a porphyrin derivative, a polytrimide derivative, a polycarbazole derivative, a polynaphthalene derivative, a polymer having an aromatic amine structure in a main chain or a side chain, polystyrene, polymethyl a methyl acrylate, a derivative, a polyphenylene ether derivative, and more preferably a polycarbazole derivative, a polymer containing a residue of a polyaromatic tertiary amine compound, a polyaryl hydrocarbon derivative, and a polyethylene A carbazole derivative, a polyoxadiazole derivative, a polytrimide derivative, an anthracene derivative. The polymer compound may be one type or a combination of two or more types. The polystyrene-equivalent number average molecular weight of the above polymer compound is usually '1'1〇3~1χ1〇7, more preferably 2(10)3~1X106, further preferably 3χ103~5χ1〇5, and particularly preferably 5χι〇3 ~ΐχι〇5. In the case where the film of the present invention contains the above polymer compound, the content of the silver complex compound is usually 〇_〇1% by mass relative to the weight of the film as a whole (U~99% by weight, more preferably 〇9〇) The weight %, which is 5 to 80% by weight, particularly preferably 1 Torr to 5 Torr, is preferably ～99.99 重量 in the film. Further, the present invention provides a light-emitting element comprising the above-mentioned film of the present invention. The hair 15659l.doc

S -128- 201202390 光元件通常為夾持有包含陽極與陰極之—對電極、及 於該電極間之包含具有發光層之一層或複數層的層丄 層）者，且該層之一層以上為本發明之膜。 、 於本發明之發光元件中’含有本發明之臈的膜中之該銀 錯合物的含量相對於該層整體之重量通常為⑽〜⑽重量 %，較佳為0·卜99重量％，更佳為卜叩重量％，進而較 5〜80重量。/◦，尤佳為1〇〜5〇重量％。 作為本發明之發光元件，例如可列舉單層型發光元件 (陽極7發光層/陰極）及多層型發光元件。作為多層型發光 元件的層構成，例如可列舉以下之層構成。 (a) 陽極/電洞注入層/(電洞傳輸層）/發光層/陰極 (b) 陽極/發光層/電子注入層/(電子傳輸層陰極 (C)陽極/電洞注入層/(電洞傳輸層）/發光層/電子注入層/(電 子傳輸層）/陰極 (d) 陽極/發光層/(電子傳輸層）/電子注入層/陰極 (e) 陽極/電洞注入層/(電洞傳輸層V發光層/(電子傳輸層）/ 電子注入層/陰極 於本發明之發光元件中，只要構成該元件之任一層為本 發明之膜即可，該層並無限定，較佳為發光層。 於上述（a)〜(e)中，（電洞傳輸層）及（電子傳輸層）表示該 等層分別可存在亦可不存在於該位置上之任意的層。 陽極為向電洞注入層、電洞傳輸層、發光層等層供給電 洞者，較佳為具有4.5 eV以上之功函數。對於陽極之材 料，例如可使用金屬、合金、金屬氧化物、導電性化合物 156591.doc •129- 201202390 及該等之組合，較佳可列舉：氧化錫、氧化鋅、氧化銦、 氧化銦錫（ITO)等導電性金屬氧化物；金、銀、鉻、錦等 金屬；上述導電性金屬氧化物與上述金屬之混合物及積層 物；埃化銅、硫化銅等無機導電性物f苯胺類、聚嗟 吩類[聚乙二氧基售吩等]、聚料等有機導電性材料及該 等與ITO之組合。 &lt; 陰極為向電子注入層、電子傳輸層、發光層等供哈電子 者。對於陰極之材料’例如可使用金屬、合金、金屬齒化 物、金屬氧化物、導電性化合物及該等之組合，較佳可使 用：驗金屬（Li、Na、K、Cs#)及其敗化物及氧化物；驗 土金屬(Mg、Ca、Ba”及其敗化物及氧化物；金銀、 鉛、紹、合金及混合金屬類[納-鉀合金、鈉_鉀混合金屬、 链-銘合金、鋰-链混合金屬、鎂_銀合金、鎮_銀混合金屬 等];稀土金屬[镱等];銦；該等之組合。 電洞注入層及t洞傳輸層具有自陽極注入電洞之功能、 傳輸電洞之功能、或阻擋自陰極注入之電子之功能。作為 該等層中所使用之㈣的例，可麟：㈣衍生物、三唾 衍生物、W衍生物H衍生物n衍生物、多芳 基烧烴衍生物、衍生物、d仙衍生物、笨二胺 衍生物、芳基胺衍生物、胺基取代查爾嗣衍生物、苯乙稀 基蒽衍生物、_衍生物、腙衍生物、二苯乙騎生物、 矽氮烷衍生物、芳香族三級胺衍生物、苯乙烯基胺衍生 物、芳香族二次甲基衍生物、。卜琳衍生物、聚錢衍生 物、聚乙料唾）衍生物、有機錢衍生物、及含有該 156591.doc 201202390 等之殘基的聚合物；苯胺系共聚物…塞吩低聚物、聚嗟吩 等導電性高分子低聚物。電洞注人層及電洞傳輸層可為包 含該等之-種或兩種以上的單層構造，亦可為包含相同植 成或不同組成之複數層的多層構造。 電子注人層及電子傳輸層具有自陰極注人電子之功能、 傳輸電子之魏、或阻擋自陽極注人之電洞之功能。=為 該等之層中所使用之材料的_，可列舉：三唾衍生物&quot;号 。坐衍生物1二销生物、㈣衍生物、_衍生物、葱 醌二甲烷衍生物、蒽酮衍生物、聯苯醌衍生物、二氧化噻 喃衍生物、碳二醯亞胺衍生物、亞第基甲烷衍生物、二苯 乙烯基吡啩衍生物、芳香環(例如萘、幻之四羧酸酐、酞 菁何生物、金屬錯合物（例如8_羥基喹啉衍生物之金屬錯合 物、以金屬酞菁為配位基之金屬錯合物、以苯并呤唑為酉〇己 位基之金屬錯合物及以笨并噻唑為配位基之金屬錯合物） 及有機㈣衍生物。電子注人層及電子傳輸層可為包含該 等之-種或兩種以上的單層豸造’亦、可為包含相同組成或 不同組成之複數層的多層構造。 作為電子注入層及電子傳輸層之材料，亦可使用絕緣 體、半導體等無機化合物。若電子注入層及電子傳輸層包 含絕緣體或半導體，則可有效地防止電流洩漏，使電子注 入性提高。作為此種絕緣體之例，可列舉選自由鹼金屬硫 屬化合物、鹼土金屬硫屬化合物、鹼金屬之函化物及鹼土 金屬之函化物所組成之群中之一種以上之金屬化合物，較 佳為CaO、BaO、SrO、BeO、BaS及CaSe。作為半導體之 156591.doc -131- 201202390 例，可列舉選自由Ba、Ca、Sr、Yb、A1、Ga、inLi'S-128-201202390 The optical element is usually sandwiched between a counter electrode including an anode and a cathode, and a layer including a layer or a plurality of layers of a light-emitting layer between the electrodes, and one or more layers of the layer are The film of the invention. In the light-emitting element of the present invention, the content of the silver complex in the film containing the crucible of the present invention is usually (10) to (10)% by weight, preferably 0% to 99% by weight, based on the total weight of the layer. More preferably, it is a weight percent of the dip, and further a weight of 5 to 80. /◦, especially good for 1〇~5〇% by weight. Examples of the light-emitting element of the present invention include a single-layer type light-emitting element (anode 7 light-emitting layer/cathode) and a multilayer light-emitting element. The layer configuration of the multilayer light-emitting device is, for example, the following layer configuration. (a) Anode/hole injection layer/(hole transport layer)/light-emitting layer/cathode (b) anode/light-emitting layer/electron injection layer/(electron transport layer cathode (C) anode/hole injection layer/(electric Hole transport layer) / luminescent layer / electron injection layer / (electron transport layer) / cathode (d) anode / luminescent layer / (electron transport layer) / electron injection layer / cathode (e) anode / hole injection layer / (electric Hole transport layer V light-emitting layer / (electron transport layer) / electron injection layer / cathode In the light-emitting element of the present invention, any layer constituting the element may be a film of the present invention, and the layer is not limited, and is preferably In the above (a) to (e), the (hole transport layer) and the (electron transport layer) indicate that each of the layers may or may not exist at any position. The anode is a hole. The layer of the injection layer, the hole transport layer, and the light-emitting layer is preferably supplied with a work function of 4.5 eV or more. For the material of the anode, for example, a metal, an alloy, a metal oxide, or a conductive compound 156591.doc can be used. • 129-201202390 and combinations of these, preferably tin oxide, zinc oxide, indium oxide, a conductive metal oxide such as indium tin oxide (ITO); a metal such as gold, silver, chromium or bromine; a mixture of the above conductive metal oxide and the above metal; and a laminate; an inorganic conductive material such as copper or copper sulfide An organic conductive material such as an aniline, a polybenzazole, a polyethylene oxide, or the like, and a combination thereof with ITO. <The cathode is supplied to an electron injection layer, an electron transport layer, a light-emitting layer, or the like. For the material of the cathode, for example, a metal, an alloy, a metal tooth, a metal oxide, a conductive compound, and a combination thereof can be used, and it is preferable to use a metal (Li, Na, K, Cs#). And its ruins and oxides; soil test metals (Mg, Ca, Ba) and their ruins and oxides; gold and silver, lead, Shao, alloys and mixed metals [n-potassium alloy, sodium-potassium mixed metal, chain - Ming alloy, lithium-chain mixed metal, magnesium_silver alloy, town_silver mixed metal, etc.; rare earth metal [镱]; indium; combinations of these. The hole injection layer and the t-hole transport layer have self-anode injection The function of the hole, the function of the transmission hole, or the blocking of the cathode injection As a function of (4) used in the layers, Kelin: (iv) derivatives, trisal derivatives, W derivatives H derivatives n derivatives, polyaryl hydrocarbon derivatives, derivatives, d Xian derivatives, stupid diamine derivatives, arylamine derivatives, amine substituted chalcone derivatives, styrene derivatives, _ derivatives, anthracene derivatives, diphenyl acetylene, decazane Derivatives, aromatic tertiary amine derivatives, styrylamine derivatives, aromatic secondary methyl derivatives, peline derivatives, poly-mole derivatives, poly-salt derivatives, organic money derivatives And a polymer containing a residue such as 156591.doc 201202390; an aniline copolymer; a conductive polymer oligomer such as a phenanthrene oligomer or a polybenzazole. The hole injection layer and the hole transport layer may be a single layer structure containing the above-mentioned species or two or more layers, or a multilayer structure containing a plurality of layers of the same planting or different composition. The electronic injection layer and the electron transport layer have the function of injecting electrons from the cathode, transmitting electrons, or blocking the holes from the anode. = _ for the materials used in these layers, for example: the three-salt derivative &quot; number. Derivative derivative 1 second-selling organism, (four) derivative, _derivative, onion dimethane derivative, anthrone derivative, biphenyl hydrazine derivative, thiourethane derivative, carbodiimide derivative, sub a base methane derivative, a distyryl pyridinium derivative, an aromatic ring (for example, naphthalene, tetrazoic anhydride, phthalocyanine, a metal complex (for example, a metal complex of an 8-hydroxyquinoline derivative) a metal complex with a metal phthalocyanine as a ligand, a metal complex with a benzoxazole as a hexyl group, and a metal complex with a stupid thiazole as a ligand) and an organic (tetra) derivative The electron-injecting layer and the electron-transporting layer may be a single-layer structure comprising the one or more types of layers, or may be a multilayer structure comprising a plurality of layers of the same composition or different compositions. As the material of the electron transport layer, an inorganic compound such as an insulator or a semiconductor can be used. When the electron injecting layer and the electron transporting layer contain an insulator or a semiconductor, current leakage can be effectively prevented, and electron injectability can be improved. As an example of such an insulator, Can be enumerated by One or more metal compounds of the group consisting of an alkali metal chalcogen compound, an alkaline earth metal chalcogen compound, an alkali metal compound, and an alkaline earth metal compound are preferably CaO, BaO, SrO, BeO, BaS, and CaSe. Examples of 156591.doc-131-201202390 semiconductors are selected from the group consisting of Ba, Ca, Sr, Yb, A1, Ga, inLi'

Na、Cd、Mg、Si、Ta、SWZn所組成之群中之一種以上 之元素的氧化物、氮化物及氮氧化物。 於本發明之發光S件中，可於陰極與接觸陰極之膜的界 面區域添加還原性摻雜劑。作為上述還原性捧雜劑之例， 可列舉驗金屬、驗土金屬、稀土金屬、驗金屬之氧化物、 鹼金屬之齒化物、鹼土金屬之氧化物、鹼土金屬之齒化 物、稀土金屬之氧化物或稀土金屬之齒化物、驗金屬錯合 物、驗土金屬錯合物及稀土金屬錯合物。 發光層具有如下之任-功能：於施加電場時可自陽極、 電洞注入層或電洞傳輸層注入電洞，且可自陰極、電子注 入層或電子傳輸層注入電子的功能；利用電場力使注入之 電荷移動的功能；及提供電子與電洞之再結合場所，由此 進行發光的功能。於使發光層中含有本發明之膜之情形 夺亦可使本發明之膜中所含之銀錯合物作為客體材料而 包含於發光層中’進而使主體材料包含於發光層中。作為 主體材料，例如可列舉具有苐骨架之化合物、具有味嗤骨 架之化合物、具有二 —土胺月条之化合物、具有吡啶骨架 之化合物二具有”骨架之化合物、具_骨架之化合 物及/、有方基石夕燒骨架之化合物。主體材料之叫交佳為大 於客體材料1而較佳為其差大於02 ev。主體材料可為 低77子化α物’亦可為高分子化合物。主體材料亦可進而 含有電解質’作為該電解質，例如可列舉可含有支持電解 質（三氟甲磺酸鋰、#备Μ ^ 過氣馱鋰、過氣酸四丁基銨、六氟磷 156591.docAn oxide, a nitride, and an oxynitride of an element of one or more of the group consisting of Na, Cd, Mg, Si, Ta, and SWZn. In the light-emitting S member of the present invention, a reducing dopant may be added to the interface region between the cathode and the film contacting the cathode. Examples of the above-mentioned reducing dopant include metal examination, soil test metal, rare earth metal, metal oxide, alkali metal tooth, alkaline earth metal oxide, alkaline earth metal tooth, and rare earth metal oxidation. A tooth or a rare earth metal tooth, a metal complex, a soil metal complex, and a rare earth metal complex. The light-emitting layer has any function of: injecting a hole from an anode, a hole injection layer or a hole transport layer when an electric field is applied, and injecting electrons from a cathode, an electron injection layer or an electron transport layer; utilizing an electric field force The function of moving the injected charge; and providing a recombination place of the electron and the hole, thereby performing the function of emitting light. In the case where the film of the present invention is contained in the light-emitting layer, the silver complex contained in the film of the present invention may be contained in the light-emitting layer as a guest material, and the host material may be contained in the light-emitting layer. The host material may, for example, be a compound having an anthracene skeleton, a compound having a miso skeleton, a compound having a di-methane amine, a compound having a pyridine skeleton, a compound having a skeleton, a compound having a skeleton, and/or A compound having a square base stone sinter skeleton. The host material is preferably greater than the guest material 1 and preferably the difference is greater than 02 ev. The host material may be a low 77-mass alpha compound or a polymer compound. Further, the electrolyte may be contained as the electrolyte, and for example, a supporting electrolyte (lithium trifluoromethanesulfonate, lithium hydride, tetrabutylammonium pentoxide, hexafluorophosphorus 156591.doc) may be contained.

S •132- 201202390 酸鉀、四氟硼酸四-正丁基銨等)之溶劑(碳酸丙烯酯、乙 腈、2-甲基四氫呋喃、丨，3_二氧雜呋喃、硝基苯、^二 甲基甲醯胺、二f基亞砜、甘油、丙醇、水等)及經該溶 劑膨潤之凝膠狀高分子（聚環氧乙烧、聚丙稀腈、偏二說 乙烯與六氟丙烯之共聚物等）。藉由將主體材料與銀錯合 物混合並塗佈、或共蒸鍍，可形成於上述主體材料中摻雜 有發光材料的發光層。 於本發明之發光元件中，作為各層之形成方法之例，可 列舉真空蒸鍍法（電阻加熱蒸鍍法、電子束法等）、濺鍍 法、LB法（Langmuir_Blodgett，朗繆爾布洛傑特法）、分子 積層法及塗佈法（洗鑄法、旋塗法、棒塗法、刮塗法、輥 塗法及凹版印刷法、網版印刷法、喷墨法等），就可使製 把過程簡化方面而言較佳為塗佈法◊於上述塗佈法中可 藉由將作為各層之材料的上述銀錯合物、上述高分子化合 物°亥等之混合物等與溶劑混合而製備塗佈液，並將該塗 佈液於所需之層（或電極）上塗佈、乾燥而獲得。於塗佈液 中亦可含有樹脂作為主體材料及/或黏合劑。該樹脂可於 溶劑中成為溶解狀態，亦可成為分散狀態。 作為樹脂，例如可使用聚乙烯咔唑等非共軛系高分子、 聚烯焓系尚分子等共軛系高分子，較佳可列舉聚氯乙烯、 聚石厌酸醋、聚苯乙烯、聚曱基丙烯酸曱酯、聚曱基丙烯酸 丁知、聚酯、聚砜、聚苯醚、聚丁二烯、聚（N_乙烯咔 坐）、烴樹脂、酮樹脂、苯氧樹脂、聚醯胺、乙基纖維 素、乙酸乙烯酯、ABS樹脂、聚胺基曱酸酯、三聚氰胺樹 156591.doc -133- 201202390 脂、不飽和聚酯樹脂、醇酸樹脂、環氧樹脂及矽樹脂。樹 月曰之吟液亦可進而含有抗氧化劑、黏度調整劑等。作為上 述㈣中所使用之溶劑，較佳為均勾地溶解膜成分者或形 成穩定之分散液的溶劑，例如可列舉醇類（曱醇、乙醇、 異丙醇等）、酮類(丙酮、甲基乙基酮等）、氣化烴類(氯 仿、1,2-二氣乙烷等）、芳香族烴類（苯、甲苯、二甲苯 等)/脂肪族烴類（正己烧、環己院等）、胺類（二甲基甲酿 胺等）、亞砜類（二甲基亞砜等）及該等之混合物。 於喷墨法中’例如可使用高沸點之溶劑(苯甲醚、聯環 己基笨等）以抑制自喷嘴之蒸發。溶液之黏度較佳為於 25 C 下為 1〜1〇〇 mPa.s。 nm 〜1〇〇 本發明之發光元件之各層之厚度較佳為〇 5 μπι，更佳為1 nm〜1 μχη。 用於照明用光源、信'號用光 打印頭等。作為顯示裝置， 驅動電路等形成區段型、點 本發明之發光元件例如可 源、背光用光源、顯示裝置、 可列舉使用公知之驅動技術、 矩陣型等構成的裝置。 本發明提供-種下述組成式（3)所表示之銀錯合物。 (Ag+)(L4)e(L5)f(L6)g(X^)h (3) (組成式⑺中’ 1/為具有4個以上且6個以下之可配位於^ :磷：子的分子，或具有1個以上之磷原子以及選自氮原 子、氧原子、硫原子、衫+、氧陰離子及硫陰離子中之 Η固以上作為可配絲Ag+之原子、或原子及離子，並且广 所具有之可配位於Ag+之原子及離子的總數為3個以上心 I5659I.doc -134- 201202390 個以下的分子。l5為具有選㈣原子、氮原子、氧原子、 瓜原子中原子、氧陰離子及硫陰離子中之原子或離子作 為可配位於Ag之原子或離子的分子，且l5所具有之可配 位於Ag +之原子及離子的總數為2個。l6為具有&quot;固選自磷 原子氮原子、氧原子、硫原子、砰原子、氧陰離子及硫 陰離子中之原子或離子作為可配位於Ag+之原子或離子的 分子。Χ2為陰離子。e為大於0.5之數，f、g及h分別獨立為 0以上之數）。 L之較佳例及例與上述Li中之較佳例及例中 具有4個以上且6個以下之可配位於Ag+之磷原子者或 具有1個以上之磷原子以及選自氮原子、氧原子、硫原 子、砷原子、氧陰離子及硫陰離子中之丨個以上作為可配 位於Ag+之原子或原子及離子，並且L4所具有之可配位於 Ag之原子及離子的總數為3個以上且6個以下者 相同。 T 5 6 2 L、X、e、f、§&amp;h之定義分別與上述組成式（1)中 之L2、L3、X1、a、b、c、d相同。、l6、χ2、e、f、呂及 h之較佳例及例分別與上述組成式（1)中之L2、L3、χΐ、a、 b、c、d之較佳例及例相同。 本發明提供一種分子，其含有2個以上之二芳基膦基， 且含有1個或2個之選自從含氮原子之雜環式化合物中去掉 1個〜3個氫原子而成的基、·〇·、及-s-中之基，並且係以上 述式（Aa)、（Ab)、（Ba，）、（Bb)、（Bc)或（Bd)所表示。本發 明之分子例如可用於金屬錯合物之配位基或反應觸媒等， 156591.doc -135- 201202390 故較為有用。較佳為作為上述本發Solvents of propylene carbonate, acetonitrile, 2-methyltetrahydrofuran, hydrazine, 3-dioxafuran, nitrobenzene, dimethyl a gelatinous polymer which is swelled by the solvent (polyethylene oxide, polyacrylonitrile, ethylene and hexafluoropropylene) Copolymer, etc.). A light-emitting layer doped with a light-emitting material in the host material can be formed by mixing and coating a host material with a silver compound or co-evaporation. In the light-emitting element of the present invention, examples of the method for forming each layer include a vacuum deposition method (resistance heating vapor deposition method, electron beam method, etc.), a sputtering method, and an LB method (Langmuir_Blodgett, Langmuir Brojer). Special method), molecular layering method and coating method (washing method, spin coating method, bar coating method, knife coating method, roll coating method, gravure printing method, screen printing method, inkjet method, etc.) In terms of simplification of the process, it is preferred that the coating method is prepared by mixing the above-mentioned silver complex as a material of each layer, a mixture of the above polymer compound, etc. with a solvent. The coating liquid is obtained by coating and drying the coating liquid on a desired layer (or electrode). A resin may be contained as a host material and/or a binder in the coating liquid. The resin may be in a dissolved state in a solvent or may be in a dispersed state. As the resin, for example, a non-conjugated polymer such as polyvinyl carbazole or a conjugated polymer such as a polyene fluorene-based polymer can be used, and polyvinyl chloride, polyphenol vinegar, polystyrene, and poly are preferably used. Ethyl decyl acrylate, polydecyl acrylate, polyester, polysulfone, polyphenylene ether, polybutadiene, poly(N_ethylene squat), hydrocarbon resin, ketone resin, phenoxy resin, polyamine , ethyl cellulose, vinyl acetate, ABS resin, polyamino phthalate, melamine tree 156591.doc -133- 201202390 fat, unsaturated polyester resin, alkyd resin, epoxy resin and enamel resin. The sputum of the moon can also contain antioxidants, viscosity modifiers, and the like. The solvent used in the above (4) is preferably a solvent which dissolves the film component uniformly or forms a stable dispersion liquid, and examples thereof include alcohols (sterol, ethanol, isopropyl alcohol, etc.) and ketones (acetone, Methyl ethyl ketone, etc., gasified hydrocarbons (chloroform, 1,2-diethane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.) / aliphatic hydrocarbons (正己烧,环己Hospitals, etc.), amines (dimethyl ketone, etc.), sulfoxides (dimethyl sulfoxide, etc.) and mixtures thereof. In the ink jet method, for example, a solvent having a high boiling point (anisole, cyclohexyl, etc.) can be used to suppress evaporation from the nozzle. The viscosity of the solution is preferably 1 to 1 〇〇 mPa.s at 25 C. Nm ~ 1 厚度 The thickness of each layer of the light-emitting element of the present invention is preferably 〇 5 μπι, more preferably 1 nm to 1 μχη. It is used as a light source for illumination, a light head for letter ', and so on. The display device, the drive circuit, and the like are formed into a segment type, and the light-emitting device of the present invention is, for example, a light source for backlight or backlight, a display device, and a device using a known drive technique, a matrix type, or the like. The present invention provides a silver complex represented by the following composition formula (3). (Ag+)(L4)e(L5)f(L6)g(X^)h (3) (In the composition formula (7), '1/ is 4 or more and 6 or less can be assigned to ^: phosphorus: a molecule, or a phosphorus atom having one or more phosphorus atoms selected from a nitrogen atom, an oxygen atom, a sulfur atom, a shirt+, an oxyanion, and a sulfur anion, as an atom, or an atom, and an ion, The total number of atoms and ions that can be assigned to Ag+ is more than three molecules I5659I.doc -134- 201202390 or less. L5 is an atom having a selected (four) atom, a nitrogen atom, an oxygen atom, a melon atom, and an oxygen anion. And the atom or ion in the sulfur anion as a molecule which can be coordinated to the atom or ion of Ag, and the total number of atoms and ions which can be assigned to Ag + in the l5 is 2. The 16 is a &quot; An atom or ion in a nitrogen atom, an oxygen atom, a sulfur atom, a helium atom, an oxyanion, and a sulfur anion is a molecule that can be coordinated to an atom or ion of Ag+. Χ2 is an anion. e is a number greater than 0.5, f, g, and h Each is independently 0 or more). Preferred examples and examples of L and the preferred examples and examples of the above Li have four or more and six or less phosphorus atoms which may be coordinated to Ag+ or have one or more phosphorus atoms and are selected from nitrogen atoms and oxygen. One or more of an atom, a sulfur atom, an arsenic atom, an oxyanion, and a sulfur anion are atoms or atoms and ions that can be coordinated to Ag+, and the total number of atoms and ions that can be coordinated to Ag in L4 is three or more. The following six are the same. The definitions of T 5 6 2 L, X, e, f, § &amp;h are the same as L2, L3, X1, a, b, c, and d in the above composition formula (1), respectively. Preferred examples and examples of L6, χ2, e, f, and h are the same as preferred examples and examples of L2, L3, χΐ, a, b, c, and d in the above composition formula (1). The present invention provides a molecule comprising two or more diarylphosphino groups, and one or two groups selected from the group consisting of one to three hydrogen atoms removed from a heterocyclic compound containing a nitrogen atom, The group of 〇·, and -s-, and is represented by the above formula (Aa), (Ab), (Ba,), (Bb), (Bc) or (Bd). The molecule of the present invention can be used, for example, as a ligand for a metal complex or a reaction catalyst, and is useful as 156591.doc -135-201202390. Preferably as the above hair

Hn ^ -¾ ^ , 之膜中所含之銀錯合 物或銀錯合物中之配位基而有用。 該二芳基膦基及該含氮原子之 ”裒式化合物之例及較佳 例分別與上述式Aa中之_piRHAa〉 ,.. h、及該含氮原子之雜環 式化合物之例及較佳例相同。 Τ 本發明之分子含有2個以上之-笔甘 一方基膦基，且含有1個或 2個之選自楗含氮原子之雜環式化合 ^ 中去掉1個〜3個氫原 子而成的基、-〇.、-C(=0)0-、或_8•中之基。 較佳為含有 之雜環式化合物中去掉1 2個二芳基膦基及1個自含氮原子 個氫原子而成的基、 2個二芳基膦基及1個·〇·、 2個二芳基膦基及1個-C(=〇)〇-、 2個二芳基膦基及1個-s_、 2個二芳基膦基及2個自含氮原 個〜3個氫原子而成的基、 子之雜環式化合物中去掉1 3個二芳基膦基及1個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基、 早 2個二芳基膦基Μ個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基及1個_〇-、 去掉1 2個二芳基鱗基h個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基及1個、 2個二芳基膦基及丨個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基及1個_8-、 156591.doc -136- 201202390 3個二芳基膦基及1個-〇-、 3個二芳基膦基及1個-C(=0)〇-、或 3個二芳基膦基及1個_S·， 更佳為含有 去掉1 去掉1 2個二芳基膦基及!個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基、 2個二芳基膦基及2個自含氮原子之雜環式化合物中 個〜3個氫原子而成的基、 3個二芳基膦基及請自含氮原子之雜環式化合物 個〜3個氫原子而成的基、 3個二芳基膦基及1個·〇·、或 3個二芳基膦基及1個_c(=〇)〇-, 進而較佳為含有 2個-芳基膦基及2個自含氮原子之雜環式化合物中去掉 個〜3個氫原子而成的基、 3個二芳基膦基及㈣自含氮原子之雜環式化合物中去掉 個〜3個氫原子而成的基、 3個二芳基膦基及1個·〇·、或 3個二芳基膦基及1個_(：(=〇)〇_， 尤佳為含有 2個二芳基膦基及2個自含氮原子之雜環式化合物中去掉】 個〜3個氫原子而成的基、或 3個一芳基膦基及1個_〇·的化合物。 本發明之分子為上述式（Aa)、（Ab)、（Ba，）、_、_ 15659 丨.doc •137- 201202390 或（Bd)所表示之分子。作為本發明之分子之較佳例，可列 舉上述式 Aal〜Aa40、Aa77~Aa80、Aa91 〜Aa94、Ba4~ Bal6、Bbl、及 Bc6~Bc21。更佳為上述式 Aal~Aa40、 Ba4〜Ba 15、Ba21、及Bc6〜Be 18中之任一個，進而較佳為 上述式Ba4~Bal6、及Bc6~Bc 1 8中之任一個，尤佳為Ba4、 Ba6、Ba8、Ba9、Bal6、及Bc6~Bc 10 中之任一個。 本發明之分子較佳為上述式Aal，、Aal'-2、Aa3、 Aa5·、Aal5·、Aa23，、Aa35'、Ba6，、Ball，、Bal3'、 8316'、；^9'、或以15'所表示之分子。其中進而較佳為 Ba6’、Ball，、Bal3’、Bal6,、Bc9,、及 Bcl5,，尤佳為式 Ba6,、Bal6'、及 Bc9' » [實施例] 繼而，示出實施例對本發明加以說明，但本發明並不限 定於該等實施例。 以下，NMR(Nuclear Magnetic Resonance，核磁共振）測 定中使用Varian公司製造之300 MHz NMR光譜儀或Burker 公司製造之400 MHz NMR光譜儀，DART-MS(Direct Analysis in Real Time Mass Spectrometry，實時直接分析 質譜儀）測定中使用日本電子製造之The AccuTOF TLC (JMS-T100TD)。分離用 GPC(Gel Permeation Chromatograph， 凝膠滲透層析儀）中使用氣仿作為展開溶劑，且使用曰本 分析工業公司製造之LC908-C60、該公司製造之管柱 JAIGEL-1H-40及 JAIGEL-2H-40。 CHN之元素分析中使用自動分析法’ C1之元素分析中使Hn ^ -3⁄4 ^ is useful for the silver complex contained in the film or the ligand in the silver complex. Examples and preferred examples of the diarylphosphino group and the nitrogen atom-containing quinone compound are respectively exemplified by _piRHAa>, .. h in the above formula Aa, and a heterocyclic compound containing the nitrogen atom; The preferred embodiment is the same. Τ The molecule of the present invention contains two or more gens of phosphinyl groups, and one or two of the heterocyclic compounds selected from the group consisting of ruthenium containing nitrogen atoms are removed by one to three. a group derived from a hydrogen atom, a group of -〇., -C(=0)0-, or _8•. It is preferred to remove 12 diarylphosphino groups and one of the heterocyclic compounds contained therein. a group derived from a hydrogen atom containing a nitrogen atom, two diarylphosphino groups, and one 〇·, two diarylphosphino groups and one -C(=〇)〇-, two diaryl groups 1 3 diarylphosphino groups are removed from the phosphino group and 1 -s_, 2 diarylphosphino groups and 2 heterocyclic compounds derived from the original nitrogen atom of ~3 hydrogen atoms a group of one to three hydrogen atoms in a heterocyclic compound containing a nitrogen atom, two diarylphosphine groups, and one to three hydrogen atoms in a heterocyclic compound containing a nitrogen atom. The base and one _〇-, remove 12 diaryl squarings, h self-contained a group of ~3 hydrogen atoms in a heterocyclic compound of an atom and one or two diarylphosphino groups and one to three hydrogen atoms in a heterocyclic compound containing a nitrogen atom. And 1 _8-, 156591.doc -136- 201202390 3 diarylphosphino groups and 1 -〇-, 3 diarylphosphino groups and 1 -C(=0)〇-, or 3 a diarylphosphino group and one _S·, more preferably containing 1 to 2 diarylphosphino groups and 1 to 3 hydrogen atoms in a heterocyclic compound containing a nitrogen atom. a group of two diarylphosphino groups and two heterocyclic compounds of a nitrogen-containing atom, having three to three hydrogen atoms, three diarylphosphino groups, and a heterocyclic ring derived from a nitrogen atom a compound having three to three hydrogen atoms, three diarylphosphino groups, one hydrazine, or three diarylphosphino groups, and one _c(=〇)〇-, more preferably a heterocyclic ring containing 2 arylphosphino groups and 2 heterocyclic compounds derived from a nitrogen atom, a radical of 3 to 3 hydrogen atoms, 3 diarylphosphino groups and (4) a heterocyclic ring derived from a nitrogen atom A group of ~3 hydrogen atoms removed from the compound, 3 diarylphosphino groups and 1 ·, or 3 diarylphosphino groups and 1 _(:(=〇)〇_, especially preferably a heterocyclic compound containing 2 diarylphosphino groups and 2 self-containing nitrogen atoms] a group of three hydrogen atoms or three monoarylphosphino groups and one compound of _〇. The molecules of the present invention are the above formulas (Aa), (Ab), (Ba,), _, _ 15659 丨.doc • 137-201202390 or (Bd). The preferred examples of the molecule of the present invention include the above formulas Aal to Aa40, Aa77 to Aa80, Aa91 to Aa94, Ba4 to Bal6, Bbl, and Bc6~Bc21. More preferably, it is any one of the above formulas Aal to Aa40, Ba4 to Ba 15, Ba21, and Bc6 to Be 18, and more preferably any one of the above formulas Ba4 to Bal6 and Bc6 to Bc 18, and particularly preferably Any one of Ba4, Ba6, Ba8, Ba9, Bal6, and Bc6~Bc10. The molecule of the present invention is preferably the above formula Aal, Aal'-2, Aa3, Aa5·, Aal5·, Aa23, Aa35', Ba6, Ball, Bal3', 8316', ?9', or The molecule represented by 15'. Further preferably, Ba6', Ball, Bal3', Bal6, Bc9, and Bcl5, and more preferably BaBa, Bal6', and Bc9' are selected. [Examples] Next, the examples are shown to the present invention. It is to be noted that the invention is not limited to the embodiments. Hereinafter, a NMR (Nuclear Magnetic Resonance) measurement is performed using a 300 MHz NMR spectrometer manufactured by Varian or a 400 MHz NMR spectrometer manufactured by Burker, DART-MS (Direct Analysis in Real Time Mass Spectrometry). The AccuTOF TLC (JMS-T100TD) manufactured by JEOL was used for the measurement. GAPP (Gel Permeation Chromatograph) was used as a developing solvent in GPC (Gel Permeation Chromatograph), and LC908-C60 manufactured by Sugamoto Analytical Industries Co., Ltd., JAMAEL-1H-40 and JAIGEL-made by the company were used. 2H-40. In the elemental analysis of CHN, the automatic analysis method is used.

156591.doc - ^8- ^ S 201202390 用燒瓶燃燒-電位差滴定法，Br之元素分析中使用燒瓶燃 燒-離子層析法。 合成例1(表1-1中之化合物編號33) 利用J. Chem· Soc. 3930-3936 (1963)中記載之方法合成 雙-(鄰二苯基膦基苯基）苯基膦（Aa60')。 於氬氣環境下，於碘化銀（1)(80.7 mg，0.344 mmol)之乙 腈 5 mL溶液中添加 Aa60'(217 mg，0.344 mmol)並於 45°C 下 搅拌·3 0分鐘’追加二氣甲烧15 mL，一面檀拌一面回流1小 時。將反應液過渡並濃縮濾液，以氯仿-趟進行慢速擴散 之再結晶，使結晶乾燥而獲得淡黃色結晶之錯合物297 mg。 [化 48]156591.doc - ^8- ^ S 201202390 Using flask combustion-potentiometric titration, the elemental analysis of Br was carried out using flask combustion-ion chromatography. Synthesis Example 1 (Compound No. 33 in Table 1-1) Synthesis of bis-(o-diphenylphosphinophenyl)phenylphosphine (Aa60' by the method described in J. Chem. Soc. 3930-3936 (1963) ). Add Aa60' (217 mg, 0.344 mmol) to a solution of silver iodide (1) (80.7 mg, 0.344 mmol) in acetonitrile in argon, and stir at 45 °C for 30 minutes. 15 mL was burned and refluxed for 1 hour while the sandalwood was mixed. The reaction mixture was transferred, and the filtrate was concentrated, and recrystallized from chloroform-hydrazine, and the crystals were dried to give 297 mg of a pale yellow crystal. [化48]

AgAg

1.0 以下示出所得之錯合物的NMR資料。 !H NMR (300 MHz, CDC13) δ (ppm)=7.68-7.60 (m, 4H), 7.28-6.98 (m, 25H), 6.95-6.89 (m, 4H); 31P NMR (122 MHz, CDCU) δ (ppm)=_6.8--11.1 (m), -25.4--29,6 (m) 以下示出所得之錯合物之元素分析測定之結果。1.0 The NMR data of the resulting complex are shown below. !H NMR (300 MHz, CDC13) δ (ppm) = 7.68-7.60 (m, 4H), 7.28-6.98 (m, 25H), 6.95-6.89 (m, 4H); 31P NMR (122 MHz, CDCU) δ (ppm) = _6.8 - -11.1 (m), -25.4 - -29, 6 (m) The results of elemental analysis of the resulting complex are shown below.

Anal. Calcd for c42H33IP3Ag.H20 (%): C，57.10; H, 3.99; N，0·00. Found: C, 56.74; H，3.73; Ν&lt;0·3。 156591.doc -139- 201202390 以下示出錯合物之DART-MS測定之結果。 DART-MS (M/Z): found; 737.09. Calcd; 737.08 (M-I)+。 根據DART-MS確認為下述組成之錯合物。 [化 49]Anal. Calcd for c42H33IP3Ag.H20 (%): C, 57.10; H, 3.99; N, 0·00. Found: C, 56.74; H, 3.73; Ν &lt;0·3. 156591.doc -139- 201202390 The results of the DART-MS assay of the complex are shown below. DART-MS (M/Z): found; 737.09. Calcd; 737.08 (M-I)+. A complex of the following composition was confirmed according to DART-MS. [化49]

所得之錯合物之組成比係由產量、4 NMR、31P NMR、 產量、DART-MS測定、及元素分析值決定。 合成例2(表1-1中之化合物編號3 2) 於星氣環境下，於漠化銀（1)(53.0 mg，0.282 mmol)之乙 腈 5 mL溶液中添加 Aa60'(178 mg，0.282 mmol)並於 45°C 下 攪拌30分鐘，追加二氯甲烷15 mL，一面攪拌一面加熱回 流1小時。將反應液過濾並濃縮濾液，以氣仿-醚進行慢速 擴散之再結晶，使結晶乾燥而獲得淡黃色結晶之錯合物 223 mg 0 [化 50]The composition ratio of the resulting complex was determined by yield, 4 NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis values. Synthesis Example 2 (Compound No. 3 2 in Table 1-1) Aa60' (178 mg, 0.282 mmol) was added to a solution of desertified silver (1) (53.0 mg, 0.282 mmol) in acetonitrile in a star atmosphere. The mixture was stirred at 45 ° C for 30 minutes, and 15 mL of dichloromethane was added thereto, and the mixture was heated under reflux for 1 hour while stirring. The reaction solution was filtered, and the filtrate was concentrated, and recrystallized by a slow diffusion of a gas-ether, and the crystals were dried to obtain a pale yellow crystal compound 223 mg 0 [50]

AgBr +AgBr +

以下示出所得之錯合物之NMR資料。 -140- 156591.docThe NMR data of the resulting complex are shown below. -140- 156591.doc

S 201202390 4 NMR (300 MHz, CDC13) δ (ppm)=7.68-7.62 (m, 4H)， 7.29-7.00 (m, 25H), 6.93-6.86 (m, 4H); 31P NMR (122 MHz, CDCI3) δ (ppm)=-5.1--9.6 (m), -24.7--29.5 (m) 以下示出所得之錯合物之元素分析測定之結果。S 201202390 4 NMR (300 MHz, CDC13) δ (ppm) = 7.68-7.62 (m, 4H), 7.29-7.00 (m, 25H), 6.93-6.86 (m, 4H); 31P NMR (122 MHz, CDCI3) δ (ppm) = -5.1 - 9.6 (m), -24.7 - 29.5 (m) The results of elemental analysis of the resulting complex are shown below.

Anal. Calcd for C42H33BrP3Ag.H20 (%): C，60.31; H， 4.22; N, 0.00; Br, 9.55. Found: C, 60.53; H, 3.98; N&lt;0.3; Br，9.10。 以下示出所得之錯合物之DART-MS測定之結果。 DART-MS (M/Z): found; 816.04. calcd; 816.00 (M)+ 0 根據DART-MS確認為下述組成之錯合物。 [化 51]Anal. Calcd for C42H33BrP3Ag.H20 (%): C, 60.31; H, 4.22; N, 0.00; Br, 9.55. Found: C, 60.53; H, 3.98; N&lt;0.3; Br, 9.10. The results of the DART-MS measurement of the resulting complex are shown below. DART-MS (M/Z): found; 816.04. calcd; 816.00 (M)+ 0 A complex of the following composition was confirmed according to DART-MS. [化 51]

所得之錯合物之組成比係由4 NMR、31P NMR、產量、 DART-MS測定、及元素分析值決定。 合成例3(表1-1中之化合物編號31) 於氬氣環境下，於氣化銀（1)(56.8 mg，0.396 mmol)之乙 腈 6 mL 溶液中添加 Aa60’（250 mg，0.396 mmol)並於 45°C 下 攪拌30分鐘，追加二氯曱烷18 mL，一面攪拌一面加熱回 流1.5小時。將反應液過濾並濃縮濾液，以氣仿-醚進行慢 速擴散之再結晶，使結晶乾燥而獲得淡黃色錯合物284 156591.doc -141 - 201202390 mg。 [化 52]The composition ratio of the resulting complex was determined by 4 NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis values. Synthesis Example 3 (Compound No. 31 in Table 1-1) Aa60' (250 mg, 0.396 mmol) was added to a solution of silver sulfate (1) (56.8 mg, 0.396 mmol) in acetonitrile 6 mL under argon. The mixture was stirred at 45 ° C for 30 minutes, and 18 mL of dichloromethane was added thereto, and the mixture was heated under reflux for 1.5 hours while stirring. The reaction solution was filtered, and the filtrate was concentrated, and then recrystallized from a slow-purified-methanol-ether, and crystals were dried to give pale yellow compound 284 156591.doc - 141 - 201202390 mg. [化52]

以下示出所得之錯合物之NMR資料。 NMR (300 MHz, CDC13) δ (ppm)=7.69-7.61 (m, 4H), 7.31-6.98 (m, 25H), 6.92-6.86 (m, 4H); 31P NMR (122 MHz, CDC13) δ (ppm)=-4.4-8.9 (m), -24.3--28.9 (m) 以下示出所得之錯合物之元素分析測定之結果。The NMR data of the resulting complex are shown below. NMR (300 MHz, CDC13) δ (ppm) = 7.69-7.61 (m, 4H), 7.31-6.98 (m, 25H), 6.92-6.86 (m, 4H); 31P NMR (122 MHz, CDC13) δ (ppm) ==4.4-8.9 (m), -24.3--28.9 (m) The results of elemental analysis of the resulting complex are shown below.

Anal. Calcd for C42H33ClP3Ag (%): C，65.18; H，4.30; N, 0·00; Cl，4.58· Found: C，65.37; H，4.28; Ν&lt;0·3; Cl, 4.59。 以下示出所得之錯合物之DART-MS測定之結果。 DART-MS (M/Z): found; 772.06. calcd; 772_05 (M)+ ° 根據DART-MS確認為下述組成之錯合物。 [化 53]Anal. Calcd for C42H33ClP3Ag (%): C, 65.18; H, 4.30; N, 0·00; Cl, 4.58· Found: C, 65.37; H, 4.28; Ν &lt;0·3; Cl, 4.59. The results of the DART-MS measurement of the resulting complex are shown below. DART-MS (M/Z): found; 772.06. calcd; 772_05 (M)+ ° A complex of the following composition was confirmed according to DART-MS. [化53]

所得之錯合物之組成比係由4 NMR、31P NMR、產量、 DART-MS測定、及元素分析值決定。The composition ratio of the resulting complex was determined by 4 NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis values.

156591.doc -142- S 201202390 合成例4(表ι_ι中之化合物編號37) 於合成例3中所得之錯合物13.6 mg之二氯甲烷1.5 mL溶 液中添加1，2,4,5-四曱基π米嗤2.17 mg(0.0175 mmol)之二氯 甲烧0.5 mL溶液，並於40°c下攪拌1〇分鐘。將反應液濃縮 後真空乾燥’獲得淡黃色結晶之錯合物15.8 mg。 [化 54]156591.doc -142- S 201202390 Synthesis Example 4 (Compound No. 37 in Table ι_) Add 1, 2, 4, 5 - 4 to a solution of the complex 13.6 mg of methylene chloride 1.5 mL obtained in Synthesis Example 3. A solution of 2.17 mg (0.0175 mmol) of dichloromethane in 0.5 mL of hydrazino π m. and stirred at 40 ° C for 1 Torr. The reaction solution was concentrated and dried in vacuo to give a pale yellow crystal compound. [化54]

所得之錯合物之組成比係由混合比決定。 合成例5(表1-1中之化合物編號36) 於合成例3中所得之錯合物9 85 mg之二氣甲烷丨5 mL溶 液中添加2,6-二曱基吡啶i 36 mmol)之二氣甲烷 0.5 mL溶液’並於4(rc下攪拌1〇分鐘。將反應液濃縮後真 空乾燥，獲得淡黃色結晶之錯合物丨丨2 mg。 [化 55]The composition ratio of the resulting complex is determined by the mixing ratio. Synthesis Example 5 (Compound No. 36 in Table 1-1) To a solution of 9 85 mg of dioxane methane in 5 mL of the complex obtained in Synthesis Example 3, 2,6-dimercaptopyridine i 36 mmol) was added. Dioxane methane 0.5 mL solution' and stirred at 4 (rc for 1 Torr). The reaction solution was concentrated and dried in vacuo to give a pale yellow crystal of the compound 丨丨 2 mg.

所得之錯合物之址成比係由混合比決定。 實施例1 (Aal，之合成） 利用以下方法合成8_[[鄰（二笨基膦基）苯基]苯基膦基]-喹啉（Aal·)。 g 於5〇紅舒倫克管中裝入1·漠-2-二苯基膦基苯（3.12 156591.doc -143- 201202390 9.14 mmol)、脫水THF 15 mL ’ 冷卻至 _65。〇，一面槐摔一 面用5分鐘滴加正丁基鋰之正己烷溶液（16 m〇i/L，5.5 mL ’正丁基鋰8.8 mmol)。將變色為紅色之反應液升溫至 -30C為止並擾拌2小時（反應液A)。於5〇 mL之四口祐形燒 瓶中裝入本基一氣膦（1.58 g’ 8.83 mmol)、及脫水THF 8 mL，冷卻至-5(TC，藉由套管送液而混合反應液將反 應液緩緩地升溫至室溫（23t)為止，攪拌12小時。反應液 白濁化（反應液B)。於200 mL之四口茄形燒瓶中裝入8_溴 喹啉（1.85 g，8.89 mmol)、脫水THF 90 mL，冷卻至·65^， 一面攪拌一面用5分鐘滴加正丁基鋰之正己烷溶液（16 Μ，5·5 mL，8.8 mmol) ’升溫至-40t為止並攪拌2小時。 將變色為紅色之反應液再冷卻至-60t(反應液〇。將上述 反應液B冷卻至-60t：並藉由套管送液混合入反應液C*。 將反應液緩緩地升溫至室溫（饥）為止，並攪拌18小時。 於反應液中添加氣化銨水溶液、氯仿，以氣仿進行萃取， 將所得之有機層以無水硫酸鈉乾燥，過濾、濃縮後，使用 氯仿作為展開溶劑進行2次矽膠管柱層析儀之純化，乾燥 後獲得黃色固體之Aal1 33 5 mg(產率7.64。/〇)。 [化 56]The resulting ratio of the resulting complex is determined by the mixing ratio. Example 1 (Synthesis of Aal) 8-[[o(diphenylphosphino)phenyl]phenylphosphino]-quinoline (Aal.) was synthesized by the following method. g In a 5 〇 red Schlenk tube, I. dimethyl-2-diphenylphosphinobenzene (3.12 156591.doc -143 - 201202390 9.14 mmol), dehydrated THF 15 mL ′ was cooled to _65. For example, a n-hexane solution of n-butyllithium (16 m〇i/L, 5.5 mL of 'n-butyllithium 8.8 mmol) was added dropwise over 5 minutes. The reaction liquid discolored in red was heated to -30 C and spoiled for 2 hours (reaction liquid A). The 5 〇mL four-shaped flask was charged with the base monophosphine (1.58 g' 8.83 mmol) and dehydrated THF 8 mL, cooled to -5 (TC, mixed with the reaction solution by cannula feeding solution The solution was gradually warmed to room temperature (23 t), and stirred for 12 hours. The reaction solution was cloudy (reaction solution B). A 4-mL eggplant-shaped flask was charged with 8-bromoquinoline (1.85 g, 8.89 mmol). ), dehydrated THF 90 mL, cooled to ·65^, while adding a solution of n-butyllithium in n-hexane (16 Μ, 5·5 mL, 8.8 mmol) with stirring for 5 minutes, warming to -40 t and stirring 2 The reaction liquid which was discolored to red was further cooled to -60 t (reaction liquid 〇. The above reaction liquid B was cooled to -60 t: and mixed into the reaction liquid C* by a cannula liquid supply. The reaction liquid was gradually heated. The mixture was stirred for 18 hours at room temperature (hungry). An aqueous solution of ammonium chloride and chloroform were added to the reaction mixture, and the mixture was extracted with a methylene chloride. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The solvent was developed and purified twice by a silica gel column chromatography. After drying, Aal1 33 5 mg (yield 7.6) was obtained as a yellow solid. 4. /〇). [Chem. 56]

156591.doc156591.doc

S -144 201202390 以下示出Aal'之NMR、DART-MS資料。 'H NMR (300 MHz, CDC13) δ (ppm)=8.77 (brd, 1H), 8.11 (d, J=8.3 Hz, 1H), 7.74 (d, J=8.1 Hz, 1H), 7.36-7.09 (m, 21H), 6.90 (br, 1H); 3,P NMR (122 MHz, CDC13) δ (ppm) = -12.5 (d, J=167 Hz), -20.1 (d, J=167 Hz); DART-MS (M/Z): found; 498.15. calcd; 498.15 (M+H)、 以下示出Aal’之元素分析測定之結果》S-144 201202390 The NMR and DART-MS data of Aal' are shown below. 'H NMR (300 MHz, CDC13) δ (ppm) = 8.77 (brd, 1H), 8.11 (d, J = 8.3 Hz, 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.36-7.09 (m , 21H), 6.90 (br, 1H); 3,P NMR (122 MHz, CDC13) δ (ppm) = -12.5 (d, J=167 Hz), -20.1 (d, J=167 Hz); DART- MS (M/Z): found; 498.15. calcd; 498.15 (M+H), the results of the elemental analysis of Aal' are shown below

Anal· Calcd for C33H25NP20.5H2O (%)·· C，78.25; H，5.17; N，2.77. Found: C，78.12; H，5.14; N，2.83 ° 實施例2 (表1-1中之化合物編號6) 於六氟峨酸銀（1)(4.20 mg，0.0166 mmol)之二氣甲烧1 mL溶液中添加 Aal'(8.26 mg，0.0166 mmol)，並於 40°C 下 攪拌10分鐘。將反應液濃縮，使其乾燥後獲得橙色固體之 錯合物12.5 mg。 [化 57]Anal· Calcd for C33H25NP20.5H2O (%)·· C,78.25; H,5.17; N,2.77. Found: C,78.12; H,5.14; N,2.83 ° Example 2 (Compound No. in Table 1-1) 6) Aal' (8.26 mg, 0.0166 mmol) was added to a 1 mL solution of silver hexafluoroantimonate (1) (4.20 mg, 0.0166 mmol) in dioxane and stirred at 40 ° C for 10 min. The reaction solution was concentrated to dryness to give a white solid. [化57]

AgPF6AgPF6

所得之錯合物之組成比係由混合比決定。 實施例3 (表1-1中之化合物編號1) 於氟化銀（1)(3.12 mg，0.0246 mmol)之二氣甲烷1 mL溶 液中添加 Aal'(12.2 mg，0.0246 mmol)，並於 4〇。(：下授摔 1 〇分鐘。將反應液濃縮，使其乾燥後獲得橙色固體之錯合 156591.doc -145· 201202390 物 15.3 mg。 [化 58]The composition ratio of the resulting complex is determined by the mixing ratio. Example 3 (Compound No. 1 in Table 1-1) Aal' (12.2 mg, 0.0246 mmol) was added to a solution of silver fluoride (1) (3.12 mg, 0.0246 mmol) in di-methane methane, and at 4 Hey. (:The next drop is 1 〇 minutes. Concentrate the reaction solution and dry it to obtain the orange solid. 156591.doc -145· 201202390 15.3 mg. [Chem. 58]

所得之錯合物之組成比係由混合比決定。 實施例4 (Bc9,之合成） 利用以下方法合成2-(2-溴-4-第三丁基苯氧基）苯甲醛。 將2-溴-4-第三丁基苯酚（20.0 g，87.3 mmol)、2_氟笨曱 醛（10.8 g，87.3 mmol)、碳酸鈉（9.60 g，87·3 mm〇1)及二 曱基乙醯胺120 mL之混合物於190°C下攪拌2小時。放置冷 卻後於反應液中添加水及氣仿，以氯仿進行萃取，將所得 之有機層以1 m〇l/L之氫氧化鈉水溶液及水進行清洗。將 有機層濃縮後，以展開溶劑氣仿：己烷=1:1(體積比）進行 矽膠管柱層析儀之純化，將溶出液濃縮後以氣仿-己烷進 行再結晶，使其乾燥後獲得無色結晶之2_(2•溴_4_第三丁 基笨氧基）苯甲醛22.0 g(產率75.6%)。 [化 59]The composition ratio of the resulting complex is determined by the mixing ratio. Example 4 (Synthesis of Bc9) 2-(2-Bromo-4-t-butylphenoxy)benzaldehyde was synthesized by the following method. 2-Bromo-4-tert-butylphenol (20.0 g, 87.3 mmol), 2-fluorobenzaldehyde (10.8 g, 87.3 mmol), sodium carbonate (9.60 g, 87·3 mm〇1) and diterpene A mixture of base acetamide 120 mL was stirred at 190 ° C for 2 hours. After standing to cool, water and a gas mixture were added to the reaction mixture, and extraction was carried out with chloroform, and the obtained organic layer was washed with a 1 m 〇l/L aqueous sodium hydroxide solution and water. After concentrating the organic layer, the solvent was purified by a solvent-like gas: hexane = 1:1 (volume ratio), and the eluate was concentrated and recrystallized by gas-hexane to dry. 2_(2•Bromo-4_t-butylphenyloxy)benzaldehyde 22.0 g (yield 75.6%) was obtained as colorless crystals. [化59]

利用以下方法合成2-(2-溴-4·第三丁基苯氧基）苯酚。 I56591.doc2-(2-Bromo-4·t-butylphenoxy)phenol was synthesized by the following method. I56591.doc

S •146· 201202390 將30重量％過氧化氫（i〇 mL，90 mmol)與二氯曱烧20 mL之混合物一面於〇。(：下攪拌一面用3〇分鐘添加三氟乙酸S • 146· 201202390 A mixture of 30% by weight of hydrogen peroxide (i〇 mL, 90 mmol) and 20 mL of dichlorohydrazine was placed on the crucible. (: Add trifluoroacetic acid for 3 minutes with stirring

酐（94.5 g，450 mmol) ’並於(TC下攪拌1小時，製備TFpA 溶液。於2-(2-溴_4·第三丁基苯氧基）苯甲醛（2〇 〇 g，6〇 〇 mmol)之二氯甲烷300 mL溶液中添加磷酸二氫鉀（163 g， 1200 mmol) ’冰浴冷卻至（TC，一面攪拌一面用3〇分鐘滴 加上述TFPA溶液。於〇。(：下攪拌2小時後於反應液中添加 20重量％之亞硫酸氫鈉水溶液，以二氣甲烷進行萃取，將 所得之有機層以飽和碳酸氫鈉水及水進行清洗。將有機層 濃縮後將殘渣溶解於甲醇300 mL*，添加濃鹽酸丨滴，於 室溫（23°C)下靜置3天。將反應混合物濃縮後，以展開溶劑 乙酸乙酯：己烷=1:4(體積比）進行矽膠管柱層析儀之純 化，使其乾燥後獲得無色結晶之2_(2_溴_4•第三丁基苯氧 基）苯酚19·0 g(產率98.6%)。 [化 60]Anhydride (94.5 g, 450 mmol) 'and stirred at TC for 1 hour to prepare TFpA solution. 2-(2-bromo-4·t-butylphenoxy)benzaldehyde (2〇〇g, 6〇) Potassium dihydrogen phosphate (163 g, 1200 mmol) was added to a solution of 〇mmol) in 300 mL of dichloromethane. The mixture was cooled to (TC, and the above TFPA solution was added dropwise over 3 minutes while stirring. After stirring for 2 hours, a 20% by weight aqueous solution of sodium hydrogen sulfite was added to the reaction mixture, and the mixture was extracted with dioxane, and the obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. Adding concentrated guanidine hydrochloride to methanol, 300 mL*, and allowing to stand at room temperature (23 ° C) for 3 days. After concentrating the reaction mixture, the solvent was evaporated to ethyl acetate:hexane = 1:4 (volume ratio). Purification by a ruthenium column chromatography and drying to obtain 2_(2_bromo-4)t-butylphenoxy)phenol 19·0 g (yield 98.6%) as colorless crystals.

基]-5-第三丁基溴苯。Base]-5-tert-butylbromobenzene.

於室溫（23。〇下攪拌18小時。 1 g，146.4 石夕燒（11.0 g ’ 73.2 mmol)並 於反應液中添加水，以己烷 156591.doc -147· 201202390 進行萃取，將所得之有機層以飽和食鹽水進行彳洗。將有 機層濃縮後，使用乙酸己烷作為展開溶劑進行矽膠管柱層 析儀之純化，使其乾燥後獲得無色油狀之2_[2•(第三丁基 一甲基矽烷氧基）苯氧基]-5-第三丁基溴苯25〇 g(產率 94.1〇/〇) 〇 [化 61]Stir at room temperature (23. under stirring for 18 hours. 1 g, 146.4 Shi Xi Shao (11.0 g '73.2 mmol) and add water to the reaction solution, and extract with hexane 156591.doc -147· 201202390, which will be obtained. The organic layer was washed with saturated brine, and the organic layer was concentrated, and then purified using a hexane hexane as a solvent for purification, and then dried to obtain a colorless oil. 2_[2•(3rd Alkylmethyl alkoxy)phenoxy]-5-tert-butylbromobenzene 25〇g (yield 94.1〇/〇) 〇[化61]

以下示出2-[2-(第三丁基二甲基矽烷氧基）苯氧基]_5第 三丁基溴苯之NMR資料》 !H NMR (400 MHz, CDC13) δ (ppm)=7.57 (d, J=2.3 Hz, lH)，7.15(dd，J=8.6,2.3Hz，lH)，7.07-7.03 (m，lH)，6.96-6.90 (m，3H)，1.12 (s，9H)，0.84 (s，9H)，0.16 (s，6H)。 利用Chem. Commun. 333-334 (2000)中記載之方法合成 (4-溴-2,7-二·第三丁基-9,9-二曱基-5-二苯基膦基p山口星β 利用以下方法合成TBS-Bc9·及Bc9’（〇H體）。 於氬氣環境下，將（4_溴-2,7-二-第三丁基_9,9_二曱基-5-二苯基膦基咄邊(3.50 g，6.83 mmol)與THF 25 mL之混合物 冷卻至-65°C，一面搜拌一面滴加2.76 mol/L之正丁基經己 院溶液（2.5〇1111^，正丁基經為6.83 111111〇1)’於-65。(^下搜拌 1小時製備鋰體1。於另一容器中於氬氣環境下，將三氣化 填（470 mg，3.42 mmol)與THF之混合物於-65 °c下搜拌，利 -148- 156591.docThe NMR data of 2-[2-(t-butyldimethylsilyloxy)phenoxy]-5 pentabutyl bromide is shown below. !H NMR (400 MHz, CDC13) δ (ppm) = 7.57 (d, J=2.3 Hz, lH), 7.15 (dd, J=8.6, 2.3 Hz, lH), 7.07-7.03 (m, lH), 6.96-6.90 (m, 3H), 1.12 (s, 9H), 0.84 (s, 9H), 0.16 (s, 6H). Synthesis by using the method described in Chem. Commun. 333-334 (2000) (4-bromo-2,7-di-tert-butyl-9,9-didecyl-5-diphenylphosphino) β The following methods were used to synthesize TBS-Bc9· and Bc9' (〇H body). Under argon atmosphere, (4_bromo-2,7-di-t-butyl _9,9-didecyl-5) - a mixture of diphenylphosphino beryllium (3.50 g, 6.83 mmol) and THF 25 mL was cooled to -65 ° C, while adding 2.76 mol / L of n-butyl hexyl solution (2.5 〇 1111) ^, n-butyl group is 6.83 111111 〇 1) ' at -65. (1) mixing 1 hour to prepare lithium body 1. In another container under argon, three gasification fill (470 mg, 3.42 Mixture of mmol) with THF at -65 °c, ali-148-156591.doc

S 201202390 用套管將上述鋰體1移送至其中。於_65°C下攪拌2小時 後’移去冷卻浴並升溫至〇°C為止❶將其冷卻至-45°C，進 而授拌2小時，製備氣膦中間物。於另一容器中於氬氣環 境下’將2-[2-(第三丁基二甲基矽烷氧基）苯氧基]_5_第三 丁基溴笨（4.46 g，10.2 mmol)與THF 25 mL之混合物冷卻 至-65°C，一面攪拌一面滴加2.76 mol/L之正丁基鋰己坑溶 液（3.70 mL，正丁基鋰為10.2 mmol)，於-65°C下攪拌1小 時製備鋰體2。利用套管將鋰體2移送至氣膦中間物中。 於-65°C下攪拌2小時後’移去冷卻浴，攪拌一夜並升溫至 室溫（23 C)為止。於反應混合物中添加飽和氣化錄水溶 液，以氣仿進行卒取’將所得之有機層以飽和食鹽水進行 清洗，將有機層以硫酸錢乾燥’以展開溶劑乙酸己院：乙 酸乙S旨=10:1 (體積比）、然後以己燒：乙酸乙醋=5:2 (體積 比）進行矽膠管柱層析儀之純化。於管柱中進行第三丁基 二曱基矽烧基之脫離反應。將溶出液濃縮後，獲得無色固 體之TBS-Bc9' 320 mg(產率6.69%)、及無色黏性體之 Bc9'(OH體）2.31 g(產率 52.6%)。 [化 62]S 201202390 Transfer the above lithium body 1 to it with a sleeve. After stirring at _65 ° C for 2 hours, the cooling bath was removed and the temperature was raised to 〇 ° C, which was cooled to -45 ° C, and then mixed for 2 hours to prepare a gas phosphine intermediate. '[2-(Tertiary butyl dimethyl decyloxy) phenoxy]_5_t-butyl bromide (4.46 g, 10.2 mmol) with THF in a separate vessel under argon The 25 mL mixture was cooled to -65 ° C, and a 2.76 mol/L n-butyllithium pentoxide solution (3.70 mL, n-butyllithium 10.2 mmol) was added dropwise while stirring, and stirred at -65 ° C for 1 hour. Lithium body 2 was prepared. The lithium body 2 is transferred to the gas phosphine intermediate using a sleeve. After stirring at -65 ° C for 2 hours, the cooling bath was removed, stirred overnight and allowed to warm to room temperature (23 C). A saturated gasification aqueous solution was added to the reaction mixture, and the obtained organic layer was washed with a saturated saline solution, and the organic layer was dried with sulfuric acid money to develop a solvent acetic acid. 10:1 (volume ratio), and then purified by krypton column chromatography with hexane: ethyl acetate = 5:2 (volume ratio). The decoupling reaction of the third butyl fluorenyl fluorenyl group was carried out in a column. After concentration of the eluate, TBS-Bc9' 320 mg (yield 6.69%) of colorless solid and 2.31 g (yield 52.6%) of Bc9' (OH) of colorless viscous body were obtained. [化 62]

以下示出TBS-Bc9’之NMR資料。 156591.doc -149· 201202390 31P NMR (122 MHz, CDCI3) δ (ppm)=-15.0 (d, J=30 Hz), •20.3 (d，J=24 Hz)，-30.6--31.1 (m)。 以下示出TBS-Bc9’之DART-MS測定之結果。 DART-MS (M/Z): found; 1397.6. calcd; 1397.7 (M+H)+。 以下示出Bc9，（OH體）之NMR資料。 31P NMR (122 MHz, CDC13) δ (ppm)=-15.0-17.0 (brd), -16.8 (dd，J=3, 34 Hz)，-34.2--34.8 (br) » 以下示出Bc9'(OH體）之DART-MS測定之結果。 DART-MS (M/Z): found; 1283.5. calcd; 1283.6 (M+H)+ 0 以下示出Bc9i(OH體）之元素分析測定之結果》The NMR data of TBS-Bc9' are shown below. 156591.doc -149· 201202390 31P NMR (122 MHz, CDCI3) δ (ppm) = -15.0 (d, J = 30 Hz), • 20.3 (d, J = 24 Hz), -30.6 - -31.1 (m) . The results of the DART-MS measurement of TBS-Bc9' are shown below. DART-MS (M/Z): found; 1397.6. calcd; 1397.7 (M+H)+. The NMR data of Bc9, (OH body) are shown below. 31P NMR (122 MHz, CDC13) δ (ppm) = -15.0-17.0 (brd), -16.8 (dd, J=3, 34 Hz), -34.2--34.8 (br) » Bc9' (OH) The results of the DART-MS assay. DART-MS (M/Z): found; 1283.5. calcd; 1283.6 (M+H)+ 0 The results of elemental analysis of Bc9i (OH body) are shown below.

Anal. Calcd for C86H93〇4P3.〇-3H2〇 (〇/〇): C，79.91; H， 7.33; N，〇.〇〇. Found: C，80.13; H，7.32; N，&lt;0.3。 實施例5 (表1-2中之化合物編號97) 於漠化銀（1)(1.90 mg，0.0101 mmol)之乙腈1 mL溶液中 添加 Bc9'(〇H 體）（13.0 mg，0.0101 mmol)並於 45°C 下揽拌 15 分鐘，添加甲醇鉀（0.71 mg，0.0101 mmol)之甲醇溶液〇 45 mL並於45°C下攪拌15分鐘，將反應液濃縮，乾燥並固化 後，添加水並進行懸浮過濾，藉由真空乾燥獲得無色固體 之錯合物14.1 mg。 •150- 156591.docAnal. Calcd for C86H93〇4P3.〇-3H2〇 (〇/〇): C,79.91; H, 7.33; N,〇.〇〇. Found: C,80.13; H,7.32; N,&lt;0.3. Example 5 (Compound No. 97 in Table 1-2) Bc9' (〇H body) (13.0 mg, 0.0101 mmol) was added to a 1 mL solution of desertified silver (1) (1.90 mg, 0.0101 mmol) in acetonitrile. After stirring at 45 ° C for 15 minutes, add 45 mL of potassium methoxide (0.71 mg, 0.0101 mmol) in methanol and stir at 45 ° C for 15 minutes. Concentrate the reaction solution, dry and solidify, add water and carry out The suspension was filtered, and dried in vacuo to give 14.1 mg as a colorless solid. •150- 156591.doc

S 201202390 [化 63]S 201202390 [化 63]

所得之錯合物之組成比係由CHN元素分析值決定。以下 示出元素分析測定之結果。The composition ratio of the resulting complex is determined by the CHN elemental analysis value. The results of the elemental analysis measurements are shown below.

Anal. Calcd for C86H92O4P3Ag.0.67AgBr-llH2O (%): C， 60.17; H，6.71; N，0.00. Found: C，60.12; H，6.61; N，&lt;0.3。 實施例6 (表l-i中之化合物編號72) 於四氟硼酸銀（1)(3.72 mg，0.0191 mmol)之二氯甲烷1 mL溶液中添加2,2，_6,6，_四曱氧基_4,4，-雙（二（3,5-二甲苯基） 膦基）-3,3’-聯吡啶（3&amp;19|)(14_5 11^，〇.〇191111111〇1)，於室溫 (23°C)下攪拌1〇分鐘。於反應液中添加2,9-二氣-l，l〇-啡啉 (4.76 mg ’ 〇.019i mm〇l)，於40°C下攪拌1〇分鐘。將反應 液濃縮後進行真空乾燥，獲得淡黃色結晶之錯合物22.9 mg。 [化 64]Anal. Calcd for C86H92O4P3Ag.0.67AgBr-llH2O (%): C, 60.17; H, 6.71; N, 0.00. Found: C, 60.12; H, 6.61; N, &lt;0.3. Example 6 (Compound No. 72 in Table li) Add 2,2,_6,6,_tetradecyloxy group to a 1 mL solution of silver tetrafluoroborate (1) (3.72 mg, 0.0191 mmol) in dichloromethane. 4,4,-bis(bis(3,5-dimethylphenyl)phosphino)-3,3'-bipyridine (3&amp;19|) (14_5 11^, 〇.〇191111111〇1) at room temperature Stir at (23 ° C) for 1 minute. 2,9-di-n-l,l-phenanthroline (4.76 mg' 〇.019i mm〇l) was added to the reaction mixture, and the mixture was stirred at 40 ° C for 1 minute. The reaction solution was concentrated and dried in vacuo to give a pale yellow crystal compound (22.9 mg). [化 64]

所得之錯合物之組成係由混合比決定。 156591.doc -151 - 201202390 實施例21 (Aa3,之合成） 利用以下方法合成Aa3,。 利用 Org· Biomol. Chem. 3297-3302 (2006)中記載之方法 合成N-曱基-2-(2-溴苯基）苯并咪唑。 於50 mL舒倫克管中裝入^溴·？-二苯基膦基苯（2.93 g， 8.59 mmol)、及脫水THF 15 mL，冷卻至-65。。，一面搜拌 一面用5分鐘滴加正丁基鋰之正己烷溶液（1 6 m〇i/L，5.5 mL，正丁基鋰為8.8 mmol)。將變化為紅色之反應液升溫 至-35°C為止並攪拌1小時（反應液d)。於5〇 mL茄形燒瓶中 裝入苯基二氯膦（1.57 g ’ 8.77 mmol)、及脫水THF 8 mL， 冷卻至-65°C，藉由套管送液而混合反應液D。將反應液一 面緩緩地升溫至室溫（23 °C )為止一面攪拌12小時，結果反 應液白濁化（反應液E)。於200 mL之四口莊形燒瓶中裝入 N-甲基-2-(2-溴苯基）苯并咪唑（2·52 g , 8 77 mm〇1)、及脫 水THF 130 mL並冷卻至-65。(：，一面攪拌一面用5分鐘滴加 正丁基經之正己院溶液（1.6 mol/L，5.5 mL，正丁基經為 8.8 mmol)，升溫至-40°C為止並攪拌2小時。將變色為紅色 之反應液冷卻至-60°C(反應液F)。將上述反應液E冷卻至 -60°C並藉由套管送液而混合至反應液。將反應液一面 緩緩地升溫至室溫（23。〇為止一面攪拌整夜後，於5〇。〇下 攪拌1小時。於反應液中添加氣化銨水溶液及氣仿後，以 氣仿進行萃取，將有機層以無水硫酸鈉乾燥，進行過濾、 濃縮後，藉由分離用GPC獲得無色固體之二膦二氧化物 675 mg(產率 12·9°/〇)。 -152- 15659 丨.docThe composition of the resulting complex is determined by the mixing ratio. 156591.doc -151 - 201202390 Example 21 (Synthesis of Aa3) Aa3 was synthesized by the following method. N-mercapto-2-(2-bromophenyl)benzimidazole was synthesized by the method described in Org. Biomol. Chem. 3297-3302 (2006). Loading bromine in a 50 mL Schlenk tube? Diphenylphosphinobenzene (2.93 g, 8.59 mmol), and dehydrated THF 15 mL, cooled to -65. . On the one hand side, a n-hexane solution of n-butyllithium (1 6 m〇i/L, 5.5 mL, 8.8 mmol of n-butyllithium) was added dropwise over 5 minutes. The reaction mixture which changed to red was heated to -35 ° C and stirred for 1 hour (reaction liquid d). To a 5 〇 mL eggplant-shaped flask, phenyldichlorophosphine (1.57 g ' 8.77 mmol) and dehydrated THF 8 mL were placed, and the mixture was cooled to -65 ° C, and the reaction liquid D was mixed by liquid feeding through a cannula. The reaction solution was stirred for 12 hours while gradually raising the temperature to room temperature (23 ° C), and the reaction solution was cloudy (reaction liquid E). N-methyl-2-(2-bromophenyl)benzimidazole (2·52 g, 8 77 mm〇1) and dehydrated THF 130 mL were placed in a 200 mL four-neck flask and cooled to -65. (:, while stirring, add n-butyl broth solution (1.6 mol/L, 5.5 mL, n-butyl 8.8 mmol) over 5 minutes, warm to -40 ° C and stir for 2 hours. The reaction liquid which was discolored to red was cooled to -60 ° C (reaction liquid F). The reaction liquid E was cooled to -60 ° C and mixed by a cannula to the reaction liquid. The reaction liquid was gradually warmed up. After stirring at room temperature (23. 整 overnight, the mixture was stirred at room temperature for 5 hours. After adding an aqueous solution of ammonium carbonate and gas to the reaction mixture, the mixture was extracted with a gas mixture, and the organic layer was treated with anhydrous sulfuric acid. After drying with sodium, filtration and concentration, 675 mg of diphosphine dioxide (yield 12·9 ° / 〇) was obtained as a colorless solid by GPC. -152 - 15659 丨.doc

S 201202390 [化 65]S 201202390 [Chem. 65]

以下示出所得之二膦二氧化物之NMR資料。 ]H NMR (3〇〇 MHz, CDC13) δ (ppm)=7.57-6.98 (m, 27H), 3.43 (s, 3H); 31p NMR (122 MHz, CDC13) δ (ppm)=32.8 (dd， J=90, 7 Hz) 〇 以下示出所得之二膦二氧化物之dart-ms測定之結果。 DART-MS (M/Z): found; 609.24. calcd; 609.18 (M+H)+ ° 於氬氣環境下，於100 mL之四口燒瓶中添加上文中合成 之一膦一氧化物（500 mg，0.822 mmol)、三乙基胺3.94 g、 及脫水二甲苯1 〇 mL ’冷卻至〇。〇，用丨〇分鐘滴加三氣矽烷 (5·00 g，37.0 mmol)。藉由自然升溫回到室溫（23。〇後， 於130 C下攪拌12小時。使反應液回到室溫（23。〇，滴加3〇 重里/〇之氫氧化納水溶液5 mL後，添加二甲苯進行萃取， 將有機層濃縮’進行乾燥而固化。對殘渣利用展開溶劑氯 仿之矽膠管柱層析儀而獲得無色固體之Aa3, 2〇2 mg(產率 47.3%) 〇 156591.doc -153- 201202390 [化 66]The NMR data of the obtained diphosphine dioxide are shown below. ]H NMR (3〇〇MHz, CDC13) δ (ppm)=7.57-6.98 (m, 27H), 3.43 (s, 3H); 31p NMR (122 MHz, CDC13) δ (ppm)=32.8 (dd, J =90, 7 Hz) The results of the dart-ms measurement of the obtained diphosphine dioxide are shown below. DART-MS (M/Z): found; 609.24. calcd; 609.18 (M+H)+ ° Add one of the above synthesized phosphine monooxides (500 mg in a 100 mL four-necked flask under argon) , 0.822 mmol), triethylamine 3.94 g, and dehydrated xylene 1 〇 mL 'cooled to 〇. 〇, trioxane (5·00 g, 37.0 mmol) was added dropwise over a few minutes. After returning to room temperature by natural heating (23. After stirring, the mixture was stirred at 130 C for 12 hours. The reaction solution was returned to room temperature (23. After 3 minutes of dropwise addition of 3 mL of a 3 N aqueous solution of sodium hydroxide) Adding xylene for extraction, and concentrating the organic layer to dryness and solidifying. The residue was subjected to a solvent chloroform-purifying column chromatography to obtain Aa3, 2 〇 2 mg (yield 47.3%) of colorless solid 〇 156591.doc -153- 201202390 [化66]

以下示出Aa3·之NMR資料。 NMR (300 MHz，CDC13) δ (ppm)=7.62-6.80 (m，27H)， 3.67 (s, 3H); 3,P NMR (122 MHz, CDC13) δ (ppm)=-12.7 (d, J=156 Hz)，-15.1 (d，J=156 Hz)。 以下示出Aa3'之DART-MS測定之結果。 DART-MS (M/Z): found; 577.17. calcd; 577.19 (M+H)+ ° 以下示出Aa3·元素分析測定之結果。The NMR data of Aa3· is shown below. NMR (300 MHz, CDC13) δ (ppm) = 7.62-6.80 (m, 27H), 3.67 (s, 3H); 3, P NMR (122 MHz, CDC13) δ (ppm) = -12.7 (d, J = 156 Hz), -15.1 (d, J = 156 Hz). The results of the DART-MS assay of Aa3' are shown below. DART-MS (M/Z): found; 577.17. calcd; 577.19 (M+H)+ ° The results of the Aa3· elemental analysis were shown below.

Anal. Calcd for C38H30N2P2.0.33H2O (%): C，79.15; H， 5_24; N，4.86. Found : C，78.16; H，5·43; N, 4.69。 實施例22 (表1-1中之化合物編號13) 於峨化銀（1)(2.70 mg，0.0115 mmol)之乙腈0.5 mL懸浮 液中添加Aa3'(6.63 mg，0.0115 mmol)並攪拌3分鐘後，添 加二氣曱烷1 mL並於40。(：下攪拌5分鐘《將反應液濃縮， 使其乾燥而獲得固體之錯合物9.33 mg。 [化 67]Anal. Calcd for C38H30N2P2.0.33H2O (%): C, 79.15; H, 5_24; N, 4.86. Found: C,78.16; H,5·43; N, 4.69. Example 22 (Compound No. 13 in Table 1-1) Aa3' (6.63 mg, 0.0115 mmol) was added to a 0.5 mL suspension of silver (1) (2.70 mg, 0.0115 mmol) in acetonitrile and stirred for 3 minutes. Add 1 mL of dioxane at 40. (: stirring for 5 minutes) The reaction solution was concentrated and dried to give a solid compound 9.33 mg.

所4于之錯合物之組成係由混合比決定 156591.docThe composition of the complex is determined by the mixing ratio. 156591.doc

S •154· 201202390 實施例23 (表1-1中之化合物編號11) 於氣化銀（1)(2.10 mg，0.0147 mmol)之乙腈〇·5 mL懸浮 液中添加Aa3'(8.45 mg，0.0147 mmol)並檀拌3分鐘後，添 加二氣甲烷1 mL並於40°C下攪拌5分鐘。將反應液濃縮， 使其乾燥而獲得固體之錯合物10.6 mg。 . [化 68]S • 154· 201202390 Example 23 (Compound No. 11 in Table 1-1) Add Aa3' (8.45 mg, 0.0147) to a 5 mL suspension of acetonitrile (5.10 mg, 0.0147 mmol) in acetonitrile. After mmol and sandalwood for 3 minutes, 1 mL of di-methane was added and stirred at 40 ° C for 5 minutes. The reaction solution was concentrated and dried to give a solid compound. [Chem. 68]

所得之錯合物之組成係由混合比決定。 實施例24 (表1-3中之化合物編號124) 於四氟硼酸銀（1)(2.20 mg，0.0113 mmol)之二氣曱烷1.5 mL懸浮液中添加 Aa3'(6.52 mg，0.0113 mmol)並於 40°C下 攪拌5分鐘。將反應液濃縮，使其乾燥而獲得固體之錯合 物 8.72 mg。 [化 69]The composition of the resulting complex is determined by the mixing ratio. Example 24 (Compound No. 124 in Tables 1-3) Aa3' (6.52 mg, 0.0113 mmol) was added to a 1.5 mL suspension of silver tetrafluoroborate (1) (2.20 mg, 0.0113 mmol) in dioxane. Stir at 40 ° C for 5 minutes. The reaction solution was concentrated and dried to give a solid compound, 8.72 mg. [化69]

所得之錯合物之組成係由混合比決定。 實施例25 (Aal，-2及Bal6,之合成） 利用以下方法合成含有Bal6,的粗製物，利用以下方法 合成8-[[鄰（二笨基膦基）笨基]苯基膦基]-2_甲基喹啉（Aal，- 15659l.doc -155- 201202390 2)。 於氮氣環境下’將8-溴-2-甲基喹啉（1.62 g，7.29 mmol) 之THF 11 mL溶液冷卻至_70°C，用10分鐘滴加正丁基鋰之 正己烧溶液（1.57 mol/L，5.6 mL，正丁基經為7.29 mmol)，於-70 C下檟;拌2小時製備經鹽溶液。、於另一容器 中於風氣環i兄下裝入鄰-雙（二氣膦基）苯（1.01 g，3.61 mmol)之THF 25 mL溶液，冷卻至_7〇cc，用15分鐘滴加預 先製備之鋰鹽溶液。於-70°C下進而攪拌35分鐘後，用2小 時升溫至室溫（23°C)為止。於室溫（23。〇下進而攪拌45分 鐘後’冷卻至-65°C ’用10分鐘滴加苯基鋰之正己烷溶液 (1.06 mol/L，7.2 mL，笨基經為 7.58 mmol),於-65°C 下進 而攪拌10分鐘。自然升溫至室溫（23。〇)為止後，攪拌2 5 天。將反應液冷卻至〇C ’滴加1 mol/L之氯化敍水溶液30 mL。於減壓下進行濃縮’添加氣仿丨25 mL進行萃取，將 有機層以無水硫酸鈉進行乾燥。過濾後進行減壓濃縮而獲 得粗產物2.33 g。藉由DART-MS測定粗產物，結果觀測到 (M/Z)=577.17之較強波峰。由於Bal6i於（M+H)+之狀態下 為（M/Z)=5 77.20 ’故粗產物中含有大量之^16'。 對上述粗產物使用氯仿作為展開溶劑進行矽膠管柱層析 儀之純化，使其乾燥而獲得無色固體之Aal,_2 12〇 mg(產 率 6.50%)。The composition of the resulting complex is determined by the mixing ratio. Example 25 (Synthesis of Aal, -2, and Bal6) The crude product containing Bal6 was synthesized by the following method, and 8-[[o-(diphenylphosphino)phenyl]phenylphosphino]- 2-methylquinoline (Aal, - 15659l.doc -155- 201202390 2). [8-Bromo-2-methylquinoline (1.62 g, 7.29 mmol) in THF 11 mL solution was cooled to _70 ° C under nitrogen atmosphere, and n-butyl lithium n-hexane solution (1.57) was added dropwise over 10 minutes. Mol/L, 5.6 mL, n-butyl group 7.29 mmol), sputum at -70 C; mix for 2 hours to prepare a salt solution. In a separate vessel, a solution of o-bis(diphosphonyl)benzene (1.01 g, 3.61 mmol) in THF 25 mL was placed in a separate vessel, cooled to _7 〇 cc, and added in advance over 15 minutes. Prepared lithium salt solution. After further stirring at -70 ° C for 35 minutes, the temperature was raised to room temperature (23 ° C) over 2 hours. After stirring at room temperature (23. under stirring for 45 minutes, 'cooling to -65 ° C', a solution of phenyllithium in n-hexane (1.06 mol/L, 7.2 mL, 7.58 mmol) was added dropwise over 10 minutes. Stir for 10 minutes at -65 ° C. After heating to room temperature (23 ° 〇), stir for 25 days. Cool the reaction solution to 〇C ' drop 1 mol / L of chlorinated aqueous solution 30 mL The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the crude product 2.33 g. The crude product was determined by DART-MS. A strong peak of (M/Z)=577.17 was observed. Since Bal6i is (M/Z)=5 77.20 in the state of (M+H)+, the crude product contains a large amount of ^16'. The product was purified by a silica gel column chromatography using chloroform as a solvent, and dried to afford Aal, 1-2 12 mg (yield 6.50%) as a colorless solid.

156591.doc _丨56_ S 201202390 [化 70]156591.doc _丨56_ S 201202390 [化70]

以下示出Aal'-2之NMR、DART-MS資料。 lK NMR (300 MHz, CDC13) δ (ppm)=7.96 (d, J=8.3 Hz, 1H), 7.67 (d, J=8.3 Hz, 1H), 7.43-7.40 (m, 1H), 7.33-7.00 (m, 20H), 6.89-6.81 (m, 1H), 2.50 (s, 3H); 31P NMR (122 MHz, CDC13) δ (ppm)=-12.7 (d, J=168 Hz), -19.3 (d, J=168 Hz); DART-MS (M/Z): found; 512.17. calcd; 512.17 (M+H).。 實施例26 (表1-3中之化合物編號132) 於埃化銀（1)(7.30 mg’ 0.0311 mmol)之氣仿2.0 mL懸浮 液中添加 Aal’-2(15_9 mg，0.0311 mmol)，於 40°C下攪拌 5 分鐘。將反應液濃縮，進行乾燥而獲得固體之錯合物23.2 mg。 [化 71]The NMR and DART-MS data of Aal'-2 are shown below. lK NMR (300 MHz, CDC13) δ (ppm) = 7.96 (d, J = 8.3 Hz, 1H), 7.67 (d, J = 8.3 Hz, 1H), 7.43-7.40 (m, 1H), 7.33-7.00 ( m, 20H), 6.89-6.81 (m, 1H), 2.50 (s, 3H); 31P NMR (122 MHz, CDC13) δ (ppm) = -12.7 (d, J = 168 Hz), -19.3 (d, J=168 Hz); DART-MS (M/Z): found; 512.17. calcd; 512.17 (M+H). Example 26 (Compound No. 132 in Table 1-3) Aal'-2 (15_9 mg, 0.0311 mmol) was added to a 2.0 mL suspension of silver (1) (7.30 mg '0.0311 mmol). Stir at 40 ° C for 5 minutes. The reaction solution was concentrated and dried to give a solid compound. [化71]

AglAgl

H, U浮)(， 1.0 所得之錯合物之組成係由混合比決定 實施例27 (表i_3中之化合物編號133) 於四氟硼酸銀（1)(5.60 mg，0.0288 mmol)之二氣曱烷2 156591.doc •157· 201202390H, U float) (, 1.0 The composition of the resulting complex is determined by the mixing ratio of Example 27 (Compound No. 133 in Table i_3) to the second gas of silver tetrafluoroborate (1) (5.60 mg, 0.0288 mmol)曱 2 2 156591.doc •157· 201202390

mL懸浮液中添加 Aal，_2(14·7 mg ’ 0.0288 mmol)，於 4(TC 下柷拌5分鐘。將反應液濃縮，使其乾燥而獲得固體之錯 合物 20.3 mg。 [化 72]Aal, _2 (14·7 mg '0.0288 mmol) was added to the mL suspension, and the mixture was stirred at 4 (TC) for 5 minutes. The reaction solution was concentrated and dried to give a solid compound 20.3 mg.

所得之錯合物之組成係由混合比決定。 &lt;比較例1 &gt; 於氬氣環境下’於四氟硼酸銀（1)(27.0 mg，0.13 9 mmol) 中添加THF 4 mL、1,2-雙（二苯基膦基）苯（61 9 mg，〇 139 mmol) ’加熱1小時並回流後，將反應液冷卻至_6〇。〇。另 外，於氬氣環境下，將利用J. Am. Chem. Soc. 126，2300_ 2301 (2004)記載之方法合成的l〇-溴苯并喹啉（28 2 mg，0.0487 mmol)溶解於THF 4 mL 中，於-60°C 下添加 1·66 Μ之正丁基裡之己烧溶液（83.7 μΐ^’ 0.139 mmol)，揽拌30 分鐘後，滴加上述冷卻至- 60°C的反應液，回到室溫（23°C ) 並攪拌2小時。將反應液濃縮，於氯仿中懸浮並過濾，將 濾液濃縮，以氯仿-醚進行慢速擴散之再結晶，將結晶真 空乾燥而獲得無色固體之錯合物61.5 mg。 -158· 156591.docThe composition of the resulting complex is determined by the mixing ratio. &lt;Comparative Example 1 &gt; 4 mL of THF and 1,2-bis(diphenylphosphino)benzene (61) were added to silver tetrafluoroborate (1) (27.0 mg, 0.13 9 mmol) under argon atmosphere. 9 mg, 〇139 mmol) ' After heating for 1 hour and refluxing, the reaction solution was cooled to _6 Torr. Hey. Further, l-bromobenzoquinoline (28 2 mg, 0.0487 mmol) synthesized by the method described in J. Am. Chem. Soc. 126, 2300_301 (2004) was dissolved in THF 4 under an argon atmosphere. In mL, add 1.66 Μ of n-butyl hexane solution (83.7 μΐ^' 0.139 mmol) at -60 °C. After mixing for 30 minutes, add the above reaction solution cooled to -60 °C. Return to room temperature (23 ° C) and stir for 2 hours. The reaction solution was concentrated, suspended in chloroform and filtered, and the filtrate was concentrated, and then recrystallized from chloroform-ether, and the crystals were dried to give 61.5 mg as a colorless solid. -158· 156591.doc

S 201202390 [化 73]S 201202390 [化73]

以下示出錯合物之NMR資料。由於NMR光譜為與Chem. Commun. 6384-6386 (2008)記載之錯合物相同之圖案，故 為上文中所示之結構的錯合物。 !H NMR (300 MHz, CDC13) δ (ppm)=7.57 (br, 8H), 7.39-7.34 (m, 8H), 7.14-7.12 (m, 32H); 31P NMR (122 MHz, CDC13) δ (ppm)=l_25 (d，J (31P-107Ag，109Ag)=231，267 Hz)。 [錯合物於固體狀態下之發光特性] 固體發光量子效率：以如下方式使用量子效率測定裝置 (Sumitomo Heavy Industries Mechatronics公司製造）測定於 室溫（23°C)空氣下之固體發光量子效率。 樣品製備係以如下方式進行。於室溫（23°C)空氣下於兩 片18 mm見方、厚度0.3 mm之石英板間，夾入僅包含上述 實施例及比較例中合成之錯合物的試樣約1.5 mg，擠壓並 拉伸為10 mmX5 mm左右之橢圓形，以膠帶將四邊堵住， 進行密封。The NMR data of the complex are shown below. Since the NMR spectrum is the same pattern as the complex described in Chem. Commun. 6384-6386 (2008), it is a complex of the structure shown above. !H NMR (300 MHz, CDC13) δ (ppm) = 7.57 (br, 8H), 7.39-7.34 (m, 8H), 7.14-7.12 (m, 32H); 31P NMR (122 MHz, CDC13) δ (ppm) ) = l_25 (d, J (31P-107Ag, 109Ag) = 231, 267 Hz). [Luminescence characteristics of the complex in a solid state] Solid-state luminescence quantum efficiency: The solid-state luminescence quantum efficiency at room temperature (23 ° C) air was measured using a quantum efficiency measuring apparatus (manufactured by Sumitomo Heavy Industries Mechatronics Co., Ltd.) as follows. Sample preparation was carried out as follows. Between the two quartz plates of 18 mm square and 0.3 mm thick at room temperature (23 ° C), a sample containing only 1.5 mg of the complex synthesized in the above examples and comparative examples was sandwiched, and extruded. And stretched to an oval shape of about 10 mmX5 mm, and the four sides are blocked with tape to seal.

該機器構成如下。光源係使用Kimmon公司製造之Class 3B之He-Cd式CW雷射。於出射部插入OFR公司製造之ND 156591.doc •159- 201202390The machine is constructed as follows. The light source was a He-Cd type CW laser of Class 3B manufactured by Kimmon Corporation. Inserted into the ND 156591.doc made by OFR at the exit department •159- 201202390

Filter FDU0.5，並以光纖導向積分球。經由Sumitomo Heavy Industries Mechatronics公司製造之Optel部之積分 球、多色儀、及CCD(Charge-coupled Device，電荷耦合元 件）多通道檢測器而連結KEYTHLEY公司製造之2400型電 源電錶，並以筆記型PC(Pesonal Computer，個人電腦）取 入資料。 該測定之順序如下。於室溫（23°C)空氣中，於積分球内 配置以上述條件製備之樣品，將雷射激發光設為325 nm， 於CW(Continuous Wave，連續波）光下將積分時間設為3.00 ms、激發光積分範圍設為315~335 nm、PL(Photoluminescence， 光致發光）波長積分範圍設為390〜800 nm。然後’依據 Sumitomo Heavy Industries Mechatronics 公司製造之測 定、分析軟體之順序算出量子效率。 固體發光波長：將利用與上述固體發光量子效率測定相 同之方法製備的試樣設置於螢光分光光度計（J〇BINYVON_ SPEX公司製造，Fluorolog-Tau3)之樣品固定部位’將激發 波長設為3 5 0 nm而測定固體發光波長。 固體發光壽命：測定、分析係以如下方式進行。 將利用與上述固體發光量子效率測定相同之方法製備的 試樣設置於螢光分光光度計（J〇BINYVON-SPEX公司製 造，Fluorolog-Tau3)之未知試樣用樣品固定部位，並於參 照樣品固定部位設置發光壽命0 ns之含有LUD0X(Aldrich 製造，colloidal silica suspension in water ’ 水中石夕溶膠懸 浮液）的純水。將上述LUDOX之發光壽命設定為0 ’於利用 15659l.docFilter FDU0.5 and guide the integrating sphere with fiber. Connected to KEYTHLEY's Model 2400 Power Meter via Optel's integrating sphere, polychromator, and CCD (Charge-coupled Device) multi-channel detector manufactured by Sumitomo Heavy Industries Mechatronics, Inc. (Pesonal Computer, personal computer) access data. The order of the measurements is as follows. The sample prepared under the above conditions was placed in the integrating sphere at room temperature (23 ° C) in air, and the laser excitation light was set to 325 nm, and the integration time was set to 3.00 under CW (Continuous Wave) light. The integration range of ms and excitation light is set to 315 to 335 nm, and the wavelength integration range of PL (Photoluminescence) is set to 390 to 800 nm. Then, the quantum efficiency was calculated in accordance with the order of measurement and analysis software manufactured by Sumitomo Heavy Industries Mechatronics. Solid-state light-emitting wavelength: A sample prepared by the same method as the solid-state quantum efficiency measurement described above was placed in a sample fixing portion of a fluorescent spectrophotometer (manufactured by J〇BINYVON_SPEX, Fluorolog-Tau3) to set the excitation wavelength to 3 The solid emission wavelength was measured at 50 nm. Solid-state luminescence lifetime: Measurement and analysis were carried out in the following manner. A sample prepared by the same method as the solid-state quantum efficiency measurement described above was placed on a sample fixing site for an unknown sample of a fluorescence spectrophotometer (Fluorolog-Tau3, manufactured by J〇BINYVON-SPEX Co., Ltd.), and fixed in a reference sample. A pure water having a luminous lifetime of 0 ns containing LUD0X (manufactured by Aldrich, colloidal silica suspension in water). Set the luminescence lifetime of the above LUDOX to 0 ’ using 15659l.doc

S -160 - 201202390 相同裝置預先測定之銀錯合物之最大發光波長及最大激發 波長下進行頻率調變法之壽命測定。測定結果係依據 Anal. Chem. 68, 9-17 (1996)中記載之理論式進行分析。 將合成例1~5、實施例2、3、5、6、22、23、24、26及 27以及比較例1之錯合物的固體發光量子效率、固體發光 波長、固體發光壽命之值示於表2中。 [表2] 〈表2&gt; 化合物編號 固體發光量子效率 固體發光波長 固體發光壽命 (%) (nm) (μδ) 合成例1 52 504 12 合成例2 75 512 13 合成例3 3.5 520 _ 合成例4 39 528 _ 合成例5 28 542 _ 實施例2 1.0 586 _ 實施例3 1.2 530 _ 實施例5 2.2 477 • 實施例6 20 535 • 實施例22 7 512 實施例23 8 531 _ 實施例24 9 500 _ 實施例26 2.8 574 _ 實施例27 1.8 590 比較例1 16 440 - (表中，-表示未測定） [錯合物之Sl-Tl·能量] &lt;計算例1&gt; 156591.doc -161 - 201202390 ，八作為合成例1中所得之錯合物的模型，使用!個銀原子、 '子的雙(鄰二苯基膦基苯基)苯基膦(Aa60，)、1個碘原 1作為初期配置’將雙_(鄰二苯基膦基苯基）苯基鱗中所 3之可配位於Ag之3個碟原子、及丄個峨原子全部設置為 距離銀原子3.0 A以内的距離，使用—程式(版本 Gaussian Inc.製造）之密度泛函數法進行結構最適化 計算、。對所得之經最適化的結構同樣地使用Gaussian03程 式’並使㈣間相關密度泛函數法進行單電子激發狀態之 4算π構最適化#算及單電子激發狀態之計算均係作為 計算方法而泛函數使用B3LYp，基底函數對於Ag+及函素 原子使用LANL2DZ，對於其他原子使用6_31G⑷。計算之 結果為，錯合物之S1能量為3 〇7 eV，T1能量為3 〇ι… si能量與T1能量之差為〇 06 ev。 &lt;計算例2&gt; 作為實施例5中所得之錯合物的模型，使用丨個銀原子、 1分子的Bc9、作為初期配置，將Bc9i中所含之可配位於 Ag之3個磷原子及1個氧陰離子全部設置為距離銀原子3〇 A以内之距離（化合物95'之結構），使用Gaussian〇3程式（版 本D.02，Gaussian Inc.製造）之密度泛函數法進行結構最適 化計算》對於所得之經最適化的結構，同樣地使用 Gaussian03程式，並使用時間相關密度泛函數法進行單電 子激發狀態之計算。結構最適化計算及單電子激發狀態之 計算均係作為計算方法而泛函數使用B3LYP，基底函數對 於Ag+及鹵素原子使用LANL2DZ，對於其他原子使用6- 156591.doc · 162-S -160 - 201202390 The lifetime of the frequency modulation method is measured at the maximum emission wavelength of the silver complex and the maximum excitation wavelength measured in advance by the same device. The measurement results were analyzed in accordance with the theoretical formula described in Anal. Chem. 68, 9-17 (1996). The values of the solid-state luminescence quantum efficiency, the solid-state luminescence wavelength, and the solid luminescence lifetime of the complexes of Synthesis Examples 1 to 5, Examples 2, 3, 5, 6, 22, 23, 24, 26, and 27 and Comparative Example 1 are shown. In Table 2. <Table 2> <Table 2> Compound No. Solid-state Luminescence Quantum Efficient Solid-Emission Luminescence Solid-state Luminescence Lifetime (%) (nm) (μδ) Synthesis Example 1 52 504 12 Synthesis Example 2 75 512 13 Synthesis Example 3 3.5 520 _ Synthesis Example 4 39 528 _ Synthesis Example 5 28 542 _ Example 2 1.0 586 _ Example 3 1.2 530 _ Example 5 2.2 477 • Example 6 20 535 • Example 22 7 512 Example 23 8 531 _ Example 24 9 500 _ Example 26 2.8 574 _ Example 27 1.8 590 Comparative Example 1 16 440 - (in the table, - indicates not measured) [Sl-Tl·energy of the complex] &lt;Calculation Example 1&gt; 156591.doc -161 - 201202390 As a model of the complex obtained in Synthesis Example 1, a silver atom, a bis (o-diphenylphosphinophenyl)phenylphosphine (Aa60), and an iodine 1 were used as an initial stage. It is configured to set the distance between the three disc atoms of Ag in the bis(o-diphenylphosphinophenyl)phenyl scale and the distance of all the rhodium atoms within 3.0 A from the silver atom. - The program (optimized by the Gaussian Inc.) density general function method for structural optimization calculation. For the obtained optimized structure, the Gaussian03 program is used in the same way, and the (four) correlation density function method is used to perform the single-electron excitation state. The calculation of the single-electron excitation state is used as the calculation method. The general function uses B3LYp, the base function uses LANL2DZ for Ag+ and atomic atoms, and 6_31G(4) for other atoms. The result of the calculation is that the S1 energy of the complex is 3 〇7 eV, and the T1 energy is 3 〇ι... The difference between the energy of Si and the energy of T1 is 〇 06 ev. &lt;Calculation Example 2&gt; As a model of the complex obtained in Example 5, one silver atom and one molecule of Bc9 were used as an initial arrangement, and three phosphorus atoms which were contained in Bc9i and which were coordinated to Ag and All of the oxyanions were set to a distance of 3 〇A from the silver atom (structure of the compound 95'), and the structure was optimized using the density ubiquitous function method of the Gaussian 〇3 program (version D.02, manufactured by Gaussian Inc.). Calculations For the optimized structure obtained, the Gaussian03 program was used in the same way, and the time-dependent density-Fan function method was used to calculate the single-electron excitation state. The calculation of the structure optimization and the calculation of the single-electron excitation state are used as the calculation method and the general function uses B3LYP, the basis function uses LANL2DZ for Ag+ and the halogen atom, and the other atom uses 6-156591.doc · 162-

S 201202390 31G(d)。§十异之結果為，錯合物之S1能量為2 61 ，Τι 能量為2.61 eV，S1能量與τΐ能量之差為〇.〇〇 ev。 〈計算例3&gt; 作為實施例6中所得之錯合物的模型，使用丨個銀原子、 • 1分子的Bal9’、1分子的2,9-二氯-l，l〇-啡啉，且使用去掉 - 抗衡離子的結構。作為初期配置，將Bal9,中所含之可配 位於Ag+之2個磷原子、及2,9_二氣_丨，1〇•啡啉中所含之可 配位於Ag之2個氮原子全部設置成距離銀原子3 〇人以内 的距離，使用GaUssian03程式（版本D 〇2，Gaussian Ιη。製 造）之密度泛函數法進行結構最適化計算。對於所得之經 最適化的結構，同樣地使用Gaussian〇3程式，並使用時間 相關密度泛函數法進行單電子激發狀態之計算。結構最適 化計算及單電子激發狀態之計算均係作為計算方法而泛函 數使用B3LYP，基底函數對於Ag+及鹵素原子使用 LANL2DZ，對於其他原子使用6_31G(d)。計算之結果為， 錯合物之S1能量為2.29 eV，T1能量為2.29 eV，S1能量與 T1能量之差為〇.〇〇 ev。 &lt;計算例4&gt; 作為實施例22中所得之錯合物的模型，使用！個銀原 子、1分子的Aa3’、1個碘原子。作為初期配置，將Α&amp;3，中 所3之可配位於Ag之2個磷原子、Aa3'中所含之可配位於 Ag+之1個氮原子、及丨個碘原子全部設置成距離銀原子3 〇 A以内的距離，使用Gaussian〇3程式（版本D 〇2，S 201202390 31G(d). § The result of the difference is that the S1 energy of the complex is 2 61 , the energy of Τι is 2.61 eV, and the difference between the energy of S1 and the energy of τΐ is 〇.〇〇 ev. <Calculation Example 3> As a model of the complex obtained in Example 6, one silver atom, one molecule of Bal9', one molecule of 2,9-dichloro-l,l-phenoline, and Use to remove the structure of the counter ion. As an initial configuration, Bal9, which is contained in two phosphorus atoms of Ag+, and 2,9_digas_丨, 1 〇 phenanthine, can be assigned to all of the two nitrogen atoms of Ag. Set the distance to within 3 银 of the silver atom, and use the density general function method of the GaUssian03 program (version D 〇2, manufactured by Gaussian Ιη) to perform structural optimization calculation. For the resulting optimized structure, the Gaussian 〇 3 program was used similarly, and the calculation of the single-electron excitation state was performed using the time-dependent density ubiquitous function method. The structural optimization calculation and the calculation of the single-electron excitation state are used as calculation methods and the functional function uses B3LYP. The basis function uses LANL2DZ for Ag+ and halogen atoms, and 6_31G(d) for other atoms. The result of the calculation is that the S1 energy of the complex is 2.29 eV, the T1 energy is 2.29 eV, and the difference between the S1 energy and the T1 energy is 〇.〇〇 ev. &lt;Calculation Example 4&gt; As a model of the complex obtained in Example 22, use! One silver atom, one molecule of Aa3', and one iodine atom. As an initial arrangement, Α&amp;3, 3 can be assigned to two phosphorus atoms of Ag, Aa3' can be assigned to one nitrogen atom of Ag+, and one iodine atom is all set to be a silver atom. 3 以A within the distance, using the Gaussian 〇 3 program (version D 〇 2,

Inc.製造）之密度泛函數法進行結構最適化計算。對於所得 156591.doc -163- 201202390 之’·!最適化的結構’同樣地使用Gaussian〇3程式，並使用 時間相關密度泛函數法進行單電子激發狀態之計算。結構 最適化計算及單電子激發狀態之計算均係作為計算方法而 泛函數使用B3LYP，基底函數對於Ag+及鹵素原子使用 LANL2DZ ’對於其他原子使用6_31G(d)。計算之結果為， 錯合物之^能量為2.81 eV，T1能量為2.78 eV，S1能量與 T1能量之差為0.03 eV。銀與配位於銀之氮原子間的距離 為 2.54 A。 &lt;計算例5&gt; 作為實施例26中所得之錯合物的模型，使用1個銀原 子、1分子的8-[[鄰（二苯基膦基）苯基]苯基膦基]2曱基喹 啉（Aal’-2)、1個碘原子。作為初期配置，將Aal，_2中所含 之可配位於Ag之2個磷原子、AaΓ-2中所含之可配位於 Ag+之1個氮原子、及丨個碘原子全部設置成距離銀原子3〇 A以内的距離，使用Gaussian〇3程式（版本D 〇2，时 Inc.製造）之密度泛函數法進行結構最適化計算。對於所得 之經最適化的結構，同樣地使用Gaussian〇3程式，並使用 時間相關密度泛函數法進行單電子激發狀態的計算。結構 最適化計算及單電子激發狀態之計算均係作為計算方法而 泛函數使用B3LYP，基底函數對於銀原子及鹵素原子使用 LANL2DZ，對於其他原子使用6_31G(d)。計算之結果為， 錯合物之S1能量為2.54 eV，T1能量為2.47 eV，S1能量與 T1能量之差為0.07 eV。銀與配位於銀之氮原子間的距離 為 3.12 A » 156591.docThe density-general function method manufactured by Inc. performs structural optimization calculations. The Gaussian 〇 3 program was similarly used for the obtained 156591.doc - 163 - 201202390 'optimized structure', and the calculation of the single electron excitation state was performed using the time-dependent density ubiquitous function method. The structure optimization calculation and the calculation of the single-electron excitation state are used as calculation methods. The general function uses B3LYP, and the basis function uses LANL2DZ for Ag+ and halogen atoms. 6_31G(d) is used for other atoms. The result of the calculation is that the energy of the complex is 2.81 eV, the energy of T1 is 2.78 eV, and the difference between the energy of S1 and the energy of T1 is 0.03 eV. The distance between silver and the nitrogen atom assigned to silver is 2.54 A. &lt;Calculation Example 5&gt; As a model of the complex obtained in Example 26, one molecule of 8-[[o-(diphenylphosphino)phenyl]phenylphosphino]2曱 was used as one silver atom. A quinoline (Aal'-2), one iodine atom. As an initial arrangement, a phosphorus atom which is contained in Aal, _2, which can be coordinated to two phosphorus atoms, a nitrogen atom which can be coordinated to Ag+, and one iodine atom contained in AaΓ-2 are all disposed at a distance from a silver atom. For the distance within 3〇A, the structural optimization calculation is performed using the density general function method of the Gaussian〇3 program (version D 〇2, manufactured by Inc.). For the resulting optimized structure, the Gaussian〇3 program was used in the same manner, and the time-dependent density-Fan function method was used to calculate the single-electron excitation state. The structure optimization calculation and the calculation of the single-electron excitation state are used as calculation methods. The general function uses B3LYP, the base function uses LANL2DZ for silver atoms and halogen atoms, and 6_31G(d) for other atoms. The result of the calculation is that the S1 energy of the complex is 2.54 eV, the T1 energy is 2.47 eV, and the difference between the S1 energy and the T1 energy is 0.07 eV. The distance between silver and the nitrogen atom assigned to silver is 3.12 A » 156591.doc

S •164· 201202390 〈實施例7&gt; 將於氣仿：1，2-二氯乙院=2:1重量比之溶劑中溶解有1重 量0/〇之合成例2之錯合物的溶液約2〇〇 mg載置於2 cm見方 之玻璃基板上。對其使用旋塗機（押鐘有限公司製造，SC-150) 以 l，0〇〇rpm 旋塗 15 秒鐘 ，以 15〇〇rpm旋塗 6〇秒鐘 ，結 果獲得厚度70 nm之薄膜。於uV(Ultraviolet，紫外線）燈下 照射’結果觀測到發光。再者，薄膜厚度係使用高精度微 細形狀測定機（小阪研究所股份有限公司，SURFCORDER ET3000)進行測定’以下之實施例8〜14及比較例1亦相同。 〈實施例8&gt; 將於氣仿：1,2-二氯乙烷=2:1重量比之溶劑中溶解有 0.16重量°/〇之合成例2之錯合物、〇.78重量％之1，3-雙（三苯 基矽烷基）苯的溶液約200 mg載置於2 cm見方之玻璃基板 上。對其使用旋塗機（押鐘有限公司製造，SC-150)以1，〇〇〇 rpm旋塗15秒鐘，以i，5〇〇 rpm旋塗60秒鐘，結果獲得厚度 80 nm之薄膜。於UV燈下照射，結果觀測到發光。 &lt;實施例9&gt; 將於氯仿.1，2 - 一氯乙院=2:1重量比之溶劑中溶解有 〇. 14重量％之合成例2之錯合物、〇·69重量❶/。之1，3-雙（三苯 基矽烷基）苯、〇.14重量％之2,4,6-三（4-第三丁基苯基）_ 1，3,5-二ρ井的溶液約200 mg載置於2 cm見方之玻璃基板 上。對其使用旋塗機（押鐘有限公司製造，SC_15〇)a rpm旋塗15秒鐘，以i，5〇〇 rpm旋塗60秒鐘，結果獲得厚度 80 nm之薄膜。MUV燈下照射，結果觀測到發光。 15659I.doc -165- 201202390 &lt;實施例ιο&gt; 將於氣仿：1，2-二氣乙烧=2:1重量比之溶劑中溶解有 0.12重量％之合成例2之錯合物、0.58重量％之聚（9_乙烯基 咔唾）（Aldrich公司製造’目錄記載之Mn=3,5000，Mw&lt; 70,000)、0_15 重量 ％之2,4,6-三（4-第三丁 基笨基）_1，3,5·三 畊的溶液約200 mg載置於2 cm見方的玻璃基板上。對其使 用旋塗機（押鐘有限公司製造，SC-150)以l，〇〇〇 rpm旋塗15 秒鐘，以1，500 rpm旋塗60秒鐘，結果獲得厚度8〇 nm的薄 膜。於UV燈下照射’結果觀測到發光。 〈實施例11~19、實施例28〜32、比較例2&gt; 將合成例1、2、3、4及5、實施例2、3、5、6、22、 23、24、26及27以及比較例1之錯合物各i重量％、pMMA 6.2重量％之氣仿溶液約150 mg載置於i cmx2 〇爪方形之石 英基板上。對其使用旋塗機（押鐘有限公司製造，sc_i5〇) 以1,000 rpm旋塗15秒鐘，以i’500 rpm旋塗6〇秒鐘獲得薄 膜。使用實施例2、3、5、6、26、及27之錯合物之薄膜的 厚度分別為0.98 μπι、1.2㈣、2·8 μηι、2 3叩、i 7叫及 1.7 μιη。 [錯合物與聚合物之組成物於薄膜狀態下之發光特性] 將薄膜設置於量子效率測定裝置（Sumh〇m〇 Ha”S 164·201202390 <Example 7> A solution of a complex of Synthesis Example 2 in which 1 wt% of hydrazine is dissolved in a solvent of 1,2-dichloroethane = 2:1 by weight is about 2 〇〇 mg was placed on a glass substrate of 2 cm square. It was spin-coated at 1,0 rpm for 15 seconds, and spin-coated at 15 rpm for 6 seconds using a spin coater (manufactured by Beacon Co., Ltd., SC-150), and a film having a thickness of 70 nm was obtained. Illumination was observed as a result of irradiation under a uV (Ultraviolet) lamp. In addition, the thickness of the film was measured using a high-precision micro-shape measuring machine (Shoji Co., Ltd., SURFCORDER ET3000). The following Examples 8 to 14 and Comparative Example 1 are also the same. <Example 8> A complex of Synthesis Example 2, 〇78% by weight, dissolved in a solvent of 1,2-dichloroethane = 2:1 by weight in a solvent of 0.16 wt%/〇 A solution of 3-bis(triphenyldecyl)benzene was placed on a 2 cm square glass substrate with a solution of about 200 mg. It was spin-coated with a spin coater (manufactured by Chess Co., Ltd., SC-150) at 1, rpm for 15 seconds, and spin-coated at i, 5 rpm for 60 seconds to obtain a film having a thickness of 80 nm. . Irradiation was carried out under a UV lamp, and as a result, luminescence was observed. &lt;Example 9&gt; 14 wt% of the complex of Synthesis Example 2, 〇·69 wt❶/, was dissolved in a solvent having a weight ratio of chloroform to 1,2-dichloroethane = 2:1. a solution of 1,3-bis(triphenylsulfanyl)benzene, ruthenium. 14% by weight of 2,4,6-tris(4-t-butylphenyl)-1,3,5-di-p. Approximately 200 mg was placed on a 2 cm square glass substrate. It was spin-coated for 15 seconds at a rpm using a spin coater (manufactured by Chess Co., Ltd., SC_15 ,), and spin-coated at i, 5 rpm for 60 seconds, and as a result, a film having a thickness of 80 nm was obtained. Irradiation under a MUV lamp resulted in the observation of luminescence. 15659I.doc -165- 201202390 &lt;Example ιο&gt; 0.12% by weight of the complex of Synthesis Example 2, 0.58, dissolved in a solvent of 1,2-diethyleneethane = 2:1 by weight % by weight of poly(9-vinyl oxime) (Mn=3,5000, Mw&lt;70,000, as described in the catalogue of Aldrich), 0-15% by weight of 2,4,6-tris(4-tert-butyl stupid Approximately 200 mg of a solution of 1-3, 3, 5, and three ploughs was placed on a 2 cm square glass substrate. This was spin-coated with a spin coater (manufactured by Chess Co., Ltd., SC-150) at 1, rpm for 15 seconds, and spin-coated at 1,500 rpm for 60 seconds, and as a result, a film having a thickness of 8 〇 nm was obtained. Illumination was observed as a result of irradiation under a UV lamp. <Examples 11 to 19, Examples 28 to 32, and Comparative Example 2> Synthesis Examples 1, 2, 3, 4 and 5, Examples 2, 3, 5, 6, 22, 23, 24, 26 and 27 and A complex solution of i% by weight of each of the complexes of Comparative Example 1 and 6.2% by weight of pMMA was placed on a quartz substrate of i cmx2 square. It was spin-coated at 1,000 rpm for 15 seconds using a spin coater (manufactured by Chess Co., Ltd.), and spin-coated at i'500 rpm for 6 seconds to obtain a film. The thicknesses of the films using the complexes of Examples 2, 3, 5, 6, 26, and 27 were 0.98 μm, 1.2 (four), 2·8 μηι, 2 3叩, i 7 and 1.7 μηη, respectively. [Luminescence characteristics of a composition of a complex and a polymer in a thin film state] The film is placed on a quantum efficiency measuring device (Sumh〇m〇 Ha)

Industries Mechatronics公司製造）的積分球内並以與上 述固體發光量子效率之測定相同的故 〜仰叫的條件測定雷射光照射後 約5秒及約15秒時之發光量子效率，求出雷射光照射前後 之發光量子效率衰減率之差除以經過時間的值作為氧劣化 •166· 156591.docIn the integrating sphere of Industries Mechatronics, the luminescence quantum efficiency of about 5 seconds and about 15 seconds after the laser light irradiation is measured in the same manner as the measurement of the solid-state luminescence quantum efficiency, and the laser light irradiation is determined. The difference between the decay rate of the quantum efficiency of the luminescence before and after is divided by the value of the elapsed time as the oxygen degradation. 166·156591.doc

S 201202390 速度。將於氮氣環境下同樣地測定雷射光照射後約5秒時 之發光量子效率的值作為薄膜發光量子效率。將結果示於 表3中。 [表3] 〈表3&gt; 薄膜 錯合物 薄膜發光量子效率 (%) 氧劣化速度 (min1) 實施例11 合成例1 14 0.60 實施例12 合成例2 14 0.63 實施例13 合成例3 13 0.48 實施例14 合成例4 14 0.80 實施例15 合成例5 17 0.96 實施例16 實施例2 9.3 0.25 實施例17 實施例3 3.3 0.47 實施例18 實施例5 2.4 0.30 實施例19 實施例6 30 0.19 實施例28 實施例22 9.1 0.49 實施例29 實施例23 8.8 0.70 實施例30 實施例24 5.8 0.08 實施例31 實施例26 3.0 0.34 實施例32 實施例27 13 0.28 比較例2 比較例1 16 1.46 〈實施例20&gt; 於附著有150 nm之ITO膜的玻璃基板上，藉由旋塗以70 nm之厚度將聚（乙烯二氧噻吩）/聚苯乙烯磺酸（Bayer製造， 商品名：Bytron P AI4083)之懸浮液成膜，於加熱板上以 200°C乾燥10分鐘。於其上，將對合成例2之錯合物以氣 仿：1,2-二氣乙烷=2:1重量比之溶液將錯合物製備成0.90 156591.doc -167- 201202390 重量°/〇濃度的溶液以1，000 rpm旋塗15秒鐘，以15〇〇 rpm旋 塗60秒鐘’藉此成膜，於n(rc下乾燥1〇分鐘。繼而，作 為陰極’蒸鍍氟化鋰約3 nm，繼而蒸鍍鋁約8〇 nm，製作 發光疋件。對所得之元件施加18 V之電壓，由此確認到亮 度 42 cd/m2、絲.玄.，J/A „ . Λ 欢率1.0 cd/A之黃色發光。 156591.docS 201202390 Speed. The value of the luminescence quantum efficiency at about 5 seconds after the laser light irradiation was measured in the same manner as the thin film luminescence quantum efficiency in a nitrogen atmosphere. The results are shown in Table 3. <Table 3> <Table 3> Thin film complex film luminescence quantum efficiency (%) Oxygen degradation rate (min1) Example 11 Synthesis Example 1 14 0.60 Example 12 Synthesis Example 2 14 0.63 Example 13 Synthesis Example 3 13 0.48 Implementation Example 14 Synthesis Example 4 14 0.80 Example 15 Synthesis Example 5 17 0.96 Example 16 Example 2 9.3 0.25 Example 17 Example 3 3.3 0.47 Example 18 Example 5 2.4 0.30 Example 19 Example 6 30 0.19 Example 28 Example 22 9.1 0.49 Example 29 Example 23 8.8 0.70 Example 30 Example 24 5.8 0.08 Example 31 Example 26 3.0 0.34 Example 32 Example 27 13 0.28 Comparative Example 2 Comparative Example 1 16 1.46 <Example 20> A suspension of poly(ethylenedioxythiophene)/polystyrenesulfonic acid (manufactured by Bayer, trade name: Bytron P AI4083) was spin-coated on a glass substrate to which a 150 nm ITO film was attached by spin coating at a thickness of 70 nm. The film was formed and dried on a hot plate at 200 ° C for 10 minutes. On the above, the complex of Synthesis Example 2 was prepared as a solution of 0.91 156591.doc -167-201202390 by weight of a solution of 1:2, dioxaethane = 2:1 by weight. The solution of cerium concentration was spin-coated at 1,000 rpm for 15 seconds and spin-coated at 15 rpm for 60 seconds to form a film, which was dried at n (rc for 1 minute. Then, as a cathode) Lithium is about 3 nm, and then aluminum is evaporated to about 8 〇 nm to produce a light-emitting element. A voltage of 18 V is applied to the obtained element, thereby confirming a brightness of 42 cd/m2, silk. Xuan., J/A „. A yellow glow of 1.0 cd/A. 156591.doc

Claims (1)

201202390 七、申請專利範圍： 1. 一種含銀錯合物之膜，其係以下述組成式（1)所表示， (Ag )(L1)a(L2)b(L3)c(X1)d ⑴ (組成式（.1)中， L1為具有選自磷原子、氮原子、氧原子、硫原子砷 原子、氧陰離子及硫陰離子中之原子或離子作為可配位 於Ag+之原子或離子的分子，Ll所具有之可配位於之 原子及離子的總數為3個以上且6個以下，並且l1所具有 之可配位於Ag+之原子中1個以上為磷原子； L2為具有選自磷原子、氮原子、氧原子、硫原子、砷 原子、氧陰離子及硫陰離子中之原子或離子作為可配位 於Ag之原子或離子的分子，且L2所具有之可配位於 之原子及離子的總數為2個； L3為具有1個選自磷原子、氮原子、氧原子、硫原 子坤原子、氧陰離子及硫陰離子中之原子或離子作為 可配位於Ag+之原子或離子的分子； X1為陰離子； a為大於〇.5之數，b、c及d分別獨立為0以上之數）。 2·如請求項1之膜，其中於上述組成式（1)中， L1為 具有4個以上且6個以下之可配位於Ag+之磷原子的分 子，或 具有1個以上之磷原子以及選自氮原子、氧原子、硫 原子、砷原子、氧陰離子及硫陰離子中之丨個以上作為 156591.doc 201202390 可配位於Αέ+之原子、或原子及離子的分子。 3·如請求項1之膜，其中於上述組成式中，&quot;所具有之 可配位於Ag+之原子及離子的總數為3個或4個^ 4·如請求項1之膜，其中於上述組成式（1)中，L1所具有之 可配位於Ag+之磷原子之數為2個以上，且該磷原子未鍵 結sp3碳原子。 5. 如請求項1之膜，其中於上述組成式（丨）中， L1具有1個可配位於Ag+之氧陰離子或硫陰離子。 6. 如請求項1之膜’其中於上述組成式（〇中，Li為下述式 (Aa)、（Ab)、（Ba)、（Bb)、（Be)及（Bd)中之任一個所表示 之分子， [化1] Q1Aa^\Q2Aa-R\QlAa (Aa) (式（Aa)中， Q1A1 -P(RnAa)2、-As(R12Aa)2、自可具有取代基之含 氣原子之雜環式化合物中去掉！個氫原子而成的基、 _N(R )(R14Aa)、·〇、-S·、-S(=0)20·、-C(=0)CT、_p(=〇) (R，5Aa)2 &gt; -As(=0)(R16Aa)2，-P(=S)(R17Aa)2 . -As(=S) (R18Aa)2、_CN、-OH ' -SH、-C(=0)0H、-S(=〇)2〇h、 -SR19Aa、或-C( = 〇)N(R21Aa)2 ; R11Aa、R!2Aa、Rl3Aa、 RUAa、Rl6Aa、Rl7Aa、…―及“…分別獨立為氫原子或 可具有取代基之碳原子數1〜50之烴基，R〗4Aa&amp;Rl9Aa分別 獨立為可具有取代基之碳原子數1~30之烧基，R&quot;Aa、 156591.doc S 201202390 Ri2Aa、Rl3Aa、Rl4Aa、Rl5Aa、Rl6Aa、Ri7Aa、Ri8Aa、Riw 及R21 Aa可分別相同亦可不同； Q2Aa為·_，·、. As(r23，、自可具有取代基之含 氮原子之雜環式化合物中去掉2個氫原子而成的基、 -N(R24Aa)-、_P(=〇)(R25Aa)…_As(=〇)(R26Aa)-、p卜s) (R27Aal·、或 _AS( = S)(R28Aa)- ; R22Aa、R23Aa、R25Aa、 R26^、R27A1 Ml別獨立為氫原子或可具有取代基 之碳原子數1〜50之烴基，R24Aa為可具有取代基之碳原子 數 1〜30 之烷基，R22Aa、R23Aa、R24Aa、R25Aa、R26Aa R 及汉28^可分別相同亦可不同； R2Aa為碳原子數50以下之2價基，然而，於所鍵結之 卩^為自含氮原子之雜環式化合物中去掉 的基之情形，或所鍵結之Q-為自含氮原子之二 = 〇物中去掉2個氫原子而成的基之情形時，亦可為直 鍵結； ~ 選自R〗 R1 R' R j^l6Aa R’、R丨 8心、Rl9Aa、R21Aa、R22Aa、r、、、 R25Aa 、 R26Aa 、 R27Aa、R28Aa p 2Aa « ώ __ R R 、R及自可具有取代基之含 氮原子之雜環式化合物中去掉丨個〜2個氫原子而成的基 中的2個以上之基亦可任意鍵結而形成環）； [化2] I 22Aa Q1' R^QlAb QlAb (Ab) 156591.doc 201202390 (式（Ab)中， Q1Ab&amp; -P(R11Ab)2、-As(R12Ab)2 ' 自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Ab)(Ri4Ab)、-〇-、s-、_s(=〇)2〇·、_c(=〇)〇-、_p(=〇) (R15Ab)2、-As(=0)(R16Ab)2、-P(=S)(R17Ab)2、-As(=S) (R18Ab)2、-CN、-OH、-SH、-C(=0)0H、-S(=0)20H、 •SR19Ab、或 _C(=0)N(R21Ab)2 ; RnAb、R12Ab、R13Ab、 RMAb、Rl6Ab、Rl7Ab、Rl8Aw]Ab分別獨立為氫原子或 可具有取代基之碳原子數1〜50之烴基，RMAb及Rl9Ab分別 獨立為可具有取代基之碳原子數^30之烷基，RllAb、 Rl2Ab、Ri3Ab、R14Ab、R】5Ab、R16Ab、R17Ab、Rl8Ab、Ri9Ab 及尺21^可分別相同亦可不同； R3Ab為碳原子數5 0以下之3價基； 選自 RllAb 、 Rl2Ab 、 Ri3Ab 、 Rl4Ab 、 Rl5Ab 、 Rl6Ab 、 R丨一、、R19Ab、r2丨Ab、R3Ab及自可具有取代基之 含氮原子之雜環式化合物中去掉1個氫原子而成的基中 的2個以上之基亦可任意鍵結而形成環）； [化3] Q1B’R、aQ‘R2々Q2B，R2々QlBa (Ba) (式（Ba)中， Q1Ba為-P(R丨丨，2、_As(R丨2Ba)2、自可具有取代基之含 氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -N(R )(R )、·〇、-S·、-S(=0)2〇-、-C(=0)CT、-P(=0) 156591.doc 201202390 (R15Ba)2、-As(=0)(R16Ba)2、_P(=s)(R 丨 7Ba)2、-As(=S) (R18Ba)2、-CN、·〇Η、-SH、-C(=0)0H、-S(=0)20H、 -SR19Ba、或-C( = 0)N(R21Ba)2，· R11Ba、Rl2Ba、R13Ba、 R15Ba、Rl6Ba、Rl7Ba、Rl8Ba&amp;R：MBa分別獨立為氫原子或 可具有取代基之碳原子數1〜5〇之烴基，RHBa及RMBa分別 獨立為可具有取代基之碳原子數^30之烷基，RnBa、 R 丨2Ba、Rl3Ba、R14Ba、R15Ba、R16Ba、Rl7Ba、Rl8Ba、r19B2 及R21Ba可分別相同亦可不同； 可具有取代基之含 Q2B1-P(R22Ba)-、·Α8(Κ23Β”_、 氮原子之雜環式化合物中去掉2個氫原子而成的基、 N(R )-、-P( = 〇)(R25Ba)_、_As(=〇)(R26Ba)_、_p( = s) (R27Ba)-、或-As( = S)(R28Ba)_ ; R22Ba、R23Ba、R25Ba、 m及R28Ba分別獨立為氫原子或可具有取代基之 碳原子數丨〜“之烴基，R24Ba為可具有取代基之碳原子數 1 〜30之烷基，R廳、R23Ba、R24Ba、R25Ba、R26Ba、r27b 及尺28心可分別相同亦可不同； ’於所鍵結之 1個氫原子而成 子之雜環式化 ’亦可為直接 R2Ba為碳原子數50以下之2價基，然而 (^心為自含氮原子之雜環式化合物中去掉 的基之情形，或所鍵結之Q2Ba為自含氮原 合物中去掉2個氫原子而成的基之情形時 鍵結； 選自 RUBa、R12Ba R17Ba、RlSBa、R19Ba R25Ba、R26Ba、R27Ba、 、R13Ba 、 Rl4Ba ' R2，Ba &gt; R22Ba R28Ba、R2Ba及自可 R15Ba ' Ri6Ba、 R23Ba、R24Ba、 具有取代基之含 156591.doc 201202390 氮原子之雜環式化合物中去掉1個〜2個氫原子而成的基 中的2個以上之基亦可任意鍵結而形成環）； [化4] (Bb) QlBb (式（Bb)中， Q1Bb4-P(RUBb)2、_As(Ri2Bb)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Bb)(R嶋）、_〇-、_s·、8(=〇)2〇_、c(=〇)〇·、斧〇 /r&gt; 1 5Bb\ (R )2、-AS( = 〇)(R“Bb)2、_p( = s)(Rl7Bb)2、_As( = s (R18Bb)2、-CN、-OH、-SH、-C( = 0)0H、-S(=〇)2〇h、 -SR19Bb、或 _C( = 〇)N(R21Bb)2 ; RllBb、R12Bb 、^I3Bb ^ R，R丨-、严、R咖及r2，別獨立為氫原子或 獨立為可具有取代基之碳原子數1〜30之烷基，R R】2Bb、R⑽、R】4Bb、Rl5Bb、Rl6Bb、r17b 嶋、 可具有取代基之碳原子數i〜5〇之烴基，R丨彳抑及尺丨9Bb分別 efs a· a π α ^____.. HBb 17Bb、R18Bb、Rm 及R2丨則可分別相同亦可不同； Q2、·_，_、_As(R23Bb)·、自可具有取代基之 氮原子之雜環式化合物中去掉2個氫原子而成的基 ·Ν:Γ,·、_p(=0)(R25Bb)-、_As(=o)(R26Bb)-、-p(=丨 (R27Bb)-、或-As(=S)(R28Bb)_ ; R22Bb、R23Bb、R25Bb 及R聰分別獨立為氣原子或可具有取❸ 之碳原子數U0之烴基’ R_為可具有取代基之碳原4 數1〜30之烷基，R_、R23Bb、以抑、心抑、、 15659 丨.doc s -6 201202390 r27:,r28b、分別相同亦可不同； 原子數5。以下之2價基，然而，於所鍵結之 =為自3氮原子之雜環式化合物中去⑹個氫原子而成 ::: 或所鍵結之Q2Bb為自含氮原子之雜環式化 合物中去掉2個氫原子而成的基之情形時，亦可為直接 鍵結； R 為碳原子數50以下之3僧其. 選自R_、、R⑽Λ⑽、R職、R廳、 R-、RUBb、R職、R21Bb、R22Bb、R23Bb、R鳩、 R25Bb、R26Bb、R27Bb、R28Bb、R2Bb、R3Bb及自可具有取代 基之含氮原子之雜環式化合物中去W個〜2個氫原子而 成的基中的2個以上之基亦可任意鍵結而形成環）； [化5] Qlvd，Q1BC (BC) (式（Be)中， Q1BC為-P(R&quot;b。)2、_As(R丨他h、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Bc)(R14Bc)、_〇-、_s-、·8(=〇)2〇-、c(=〇)〇_、_p(=〇) (R )2、_As(=〇)(R16Bc)2、-P(=S)(R17Be)2、_As(=S) (R )2、_CN、-OH、-SH、-C(=0)0H、-S(=0)2〇H、 -SR19Bc、或 _C( = 〇)N(R21Bc)2 ; R&quot;Bc、R12Bc、Rl3Bc、 R_、Rl6Be、Rl7Bc、r18Bir21Bc分別獨立為氫原子或 156591.doc 201202390 可具有取代基之碳原子數卜5〇之烴基，RMB&lt;^Ri9Be分別 獨立為可具有取代基之碳原子數1〜30之烷基，riibc、 R12Bc、R13Bc、rMBc、Rl5Be、Rl6Bc、Rl7Bc、r18Bc、Ri9Bc 及11218&lt;:可分別相同亦可不同； &lt;53以為卩、八3、自可具有取代基之含氮原子之雜環式 化合物中去掉3個氫原子而成的基、Ν、、 As(=0)、P(=S)、4As(=s); R2Bc為碳原子數50以下之2價基，然而，於所鍵結之 Q1Be為自含氮原子之雜環式化合物中去掉丨個氫原子而成 的基之情形，或所鍵結之Q3Be為自含氮原子之雜環式化 合物中去掉3個氫原子而成的基之情形時，亦可為直接 鍵結； 選自 R11Be、R12BC、RnBc、R】4Bc、Rl5Bc、Ri6Bc、 R17Bc、r18Bc l9Bc 21Bc、 K K 及自含氮原子之雜環式 化合物中去掉1個或3個氫原子而成的基中的2個以上之 基亦可任意鍵結而形成環）； [化6] Q1Bd (Bd) QlBd_p4Bd_QlBd QlBd (式（Bd)中， Q1B&lt;^ -P(R丨1Bd)2、-As(R丨2Bd)2 '自可具有取代基之含 氮原子之雜環式化合物中去掉丨個氫原子而成的基、 _N(Rl3Bd)(Rl4Bd)、_〇.、_S-、_S( = 〇)2〇.、_c( = 〇)〇·、 156591.doc 201202390 (τ) 1 5Bd\ )2、-As(=〇)(Ri6Bd)2、_p(=s)(Rl7Bd)2、_As(=s) /1¾ 1 8Bd\ 、 ）2、，CN、_〇H、-SH、-C(=0)0H、-S(=0)2〇H、 -SR19Bd、或·c(=〇)N(R21Bd)2 ; RllBd、Rl2Bd、Rl3Bd、 Rl6Bd、Rl7Bd、^哪及^⑻分別獨立為氫原子或 可具有取代基之碳原子數卜5〇之烴基，RMBd及Rl9Bd分別 ' 獨立為可具有取代基之碳原子數1〜30之烷基，R11Bd、 Rl2Bd、R13Bd、R14Bd、Rl5Bd、R16Bd、R17Bd、R18Bd、R19Bd 及R Bd可分別相同亦可不同； R 為碳原子數70以下之4價基； 選自 RUBd、、R13Bd、R14Bd、R15Bd、R16B(1、 R17Bd、R_、R_、R21Bd、R4Bd及自可具有取代基之含 氣原子之雜環式化合物中去掉1個氫原子而成的基中的2 個以上之基亦可任意鍵結而形成環）。 7·如請求項6之膜，其中於上述式（Aa)中， Q為-P(RUAa)2、-As(R12Aa)2、自可具有取代基之含 氣原子之雜環式化合物中去掉1個氫原子而成的基、-〇· 、-S、-S(=〇)2〇-、或·€(=〇)〇-， Q為-P(R22Aa)_、-As(R23Aa)-、或自可具有取代基之 含氣原子之雜環式化合物中去掉2個氫原子而成的基， R 、R 2Aa、R22Aa&amp; R23Aa分別獨立為可具有取代基 之本基， 式（Aa)所表示之分子含有i個以上之·ρ(κηΑ3)2、或 -P(R22Aa)_。 8.如凊求項6之膜，其中於上述式（Aa)中，尺2心為直接鍵結 156591.doc 201202390 或可具有取代基之下述式rl〜rl2中之任一個所表示之 基， [化7]201202390 VII. Patent application scope: 1. A film containing silver complex, which is represented by the following composition formula (1), (Ag )(L1)a(L2)b(L3)c(X1)d (1) (In the composition formula (.1), L1 is a molecule having an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom arsenic atom, an oxyanion, and a sulfur anion as a molecule or ion which can be coordinated to Ag+, The total number of atoms and ions that Ll has can be assigned is 3 or more and 6 or less, and 1 or more of the atoms which can be assigned to Ag+ of l1 are phosphorus atoms; L2 is selected from phosphorus atoms and nitrogen. An atom, an atom of an oxygen atom, a sulfur atom, an arsenic atom, an oxyanion, or a sulfur anion is a molecule that can be coordinated to an atom or ion of Ag, and the total number of atoms and ions that L2 has can be assigned is two. L3 is a molecule having one atom or ion selected from the group consisting of a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an oxyanion, and a sulfur anion as a molecule or ion that can be coordinated to Ag+; X1 is an anion; More than 〇.5, b, c and d are independent of 0 On the number). 2. The film according to claim 1, wherein in the above composition formula (1), L1 is a molecule having 4 or more and 6 or less phosphorus atoms which can be coordinated to Ag+, or has one or more phosphorus atoms and is selected One or more of nitrogen atoms, oxygen atoms, sulfur atoms, arsenic atoms, oxyanions, and sulfur anions are 156591.doc 201202390 molecules that can be assigned to atoms of Αέ+, or atoms and ions. 3. The film according to claim 1, wherein in the above composition formula, the total number of atoms and ions which can be assigned to Ag+ is 3 or 4, and the film of claim 1 is as described above. In the composition formula (1), the number of phosphorus atoms which can be coordinated to Ag+ in L1 is two or more, and the phosphorus atom is not bonded to the sp3 carbon atom. 5. The membrane according to claim 1, wherein in the above composition formula ( L), L1 has one oxyanion or sulfur anion which can be coordinated to Ag+. 6. The film of claim 1, wherein in the above composition formula, Li is any one of the following formulas (Aa), (Ab), (Ba), (Bb), (Be), and (Bd) The molecule represented, [Chemical 1] Q1Aa^\Q2Aa-R\QlAa (Aa) (in the formula (Aa), Q1A1 -P(RnAa)2, -As(R12Aa)2, gas containing a substituent In the heterocyclic compound of the atom, the group of a hydrogen atom is removed, _N(R)(R14Aa), ·〇, -S·, -S(=0)20·, -C(=0)CT, _p (=〇) (R,5Aa)2 &gt; -As(=0)(R16Aa)2,-P(=S)(R17Aa)2 . -As(=S) (R18Aa)2, _CN, -OH ' -SH, -C(=0)0H, -S(=〇)2〇h, -SR19Aa, or -C( = 〇)N(R21Aa)2 ; R11Aa, R!2Aa, Rl3Aa, RUAa, Rl6Aa, Rl7Aa And ... and "... each independently a hydrogen atom or a hydrocarbon group having a substituent having 1 to 50 carbon atoms, and R 4Aa &amp; Rl9Aa are each independently a carbon atom having 1 to 30 carbon atoms which may have a substituent, R&quot Aa, 156591.doc S 201202390 Ri2Aa, Rl3Aa, Rl4Aa, Rl5Aa, Rl6Aa, Ri7Aa, Ri8Aa, Riw and R21 Aa may be the same or different; Q2Aa is ·_, ·,. As(r23, self-replaceable Nitrogen-containing atom A group in which two hydrogen atoms are removed from a heterocyclic compound, -N(R24Aa)-, _P(=〇)(R25Aa)..._As(=〇)(R26Aa)-, p s) (R27Aal·, or _AS( = S)(R28Aa)- ; R22Aa, R23Aa, R25Aa, R26^, R27A1 Ml are independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and R24Aa is a carbon which may have a substituent The alkyl group having an atomic number of 1 to 30, R22Aa, R23Aa, R24Aa, R25Aa, R26Aa R and Han 28^ may be the same or different; R2Aa is a divalent group having 50 or less carbon atoms, however, after bonding ^ In the case of a group removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q- is a group in which two hydrogen atoms are removed from a nitrogen-containing atom; Can be a direct bond; ~ from R〗 R1 R' R j^l6Aa R', R丨8 heart, Rl9Aa, R21Aa, R22Aa, r,, R25Aa, R26Aa, R27Aa, R28Aa p 2Aa « ώ __ RR , R and two or more substituents in which a heterocyclic compound having a nitrogen atom capable of having a substituent has one or two hydrogen atoms removed may be arbitrarily bonded to form a ring); [Chemical 2] I 22Aa Q 1' R^QlAb QlAb (Ab) 156591.doc 201202390 (In the formula (Ab), Q1Ab&amp;-P(R11Ab)2, -As(R12Ab)2' is a heterocyclic compound having a nitrogen atom which may have a substituent A group in which one hydrogen atom is removed, -N(R13Ab)(Ri4Ab), -〇-, s-, _s(=〇)2〇·, _c(=〇)〇-, _p(=〇) ( R15Ab)2, -As(=0)(R16Ab)2, -P(=S)(R17Ab)2, -As(=S)(R18Ab)2, -CN, -OH, -SH, -C(= 0) 0H, -S(=0)20H, •SR19Ab, or _C(=0)N(R21Ab)2; RnAb, R12Ab, R13Ab, RMAb, Rl6Ab, Rl7Ab, Rl8Aw]Ab are independently hydrogen atoms or a hydrocarbon group having a substituent having 1 to 50 carbon atoms, and RMAb and Rl9Ab are each independently an alkyl group having 30 atomic number of carbon atoms, R11Ab, Rl2Ab, Ri3Ab, R14Ab, R]5Ab, R16Ab, R17Ab, Rl8Ab Ri9Ab and 尺21^ may be the same or different; R3Ab is a trivalent group having a carbon number of 50 or less; and is selected from the group consisting of RllAb, Rl2Ab, Ri3Ab, Rl4Ab, Rl5Ab, Rl6Ab, R丨1, R19Ab, r2丨Ab And R3Ab and two or more of the groups in which one hydrogen atom is removed from the heterocyclic compound having a nitrogen atom which may have a substituent The base may also be arbitrarily bonded to form a ring); [Chemical 3] Q1B'R, aQ'R2々Q2B, R2々QlBa (Ba) (In the formula (Ba), Q1Ba is -P(R丨丨, 2, _As (R丨2Ba) 2. A group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom having a substituent, -N(R )(R ), ·〇, -S·, -S (=0)2〇-, -C(=0)CT, -P(=0) 156591.doc 201202390 (R15Ba)2, -As(=0)(R16Ba)2, _P(=s)(R 丨7Ba)2, -As(=S) (R18Ba)2, -CN, ·〇Η, -SH, -C(=0)0H, -S(=0)20H, -SR19Ba, or -C( = 0 N(R21Ba)2, · R11Ba, Rl2Ba, R13Ba, R15Ba, Rl6Ba, Rl7Ba, Rl8Ba&amp;R:MBa are each independently a hydrogen atom or a hydrocarbon group having a substituent of 1 to 5 carbon atoms, RHBa and RMBa respectively An alkyl group having independently a carbon atom number of 30, RnBa, R 丨 2Ba, Rl3Ba, R14Ba, R15Ba, R16Ba, Rl7Ba, Rl8Ba, r19B2 and R21Ba may be the same or different, and may have a substituent Q2B1-P(R22Ba)-,·Α8(Κ23Β"_, a group in which two hydrogen atoms are removed from a heterocyclic compound of a nitrogen atom, N(R)-, -P(= 〇)(R25Ba)_, _As(=〇)(R26 Ba)_, _p(= s)(R27Ba)-, or -As( = S)(R28Ba)_ ; R22Ba, R23Ba, R25Ba, m and R28Ba are each independently a hydrogen atom or a carbon atom which may have a substituent 丨~""hydrocarbyl group, R24Ba is an alkyl group having 1 to 30 carbon atoms which may have a substituent, and R, R23Ba, R24Ba, R25Ba, R26Ba, r27b and ul. 28 may be the same or different; The heterocyclic ring formation of one hydrogen atom can also be a case where the direct R 2 Ba is a divalent group having 50 or less carbon atoms, but (the core is a group removed from a heterocyclic compound containing a nitrogen atom, Or the bonded Q2Ba is bonded in the case where two hydrogen atoms are removed from the nitrogen-containing compound; and is selected from the group consisting of RUBa, R12Ba R17Ba, RlSBa, R19Ba R25Ba, R26Ba, R27Ba, R13Ba, Rl4Ba' R2,Ba &gt; R22Ba R28Ba, R2Ba and R15Ba ' Ri6Ba, R23Ba, R24Ba, substituted 156591.doc 201202390 nitrogen atom heterocyclic compound in which one to two hydrogen atoms are removed Two or more groups may be arbitrarily bonded to form a ring); [Chemical 4] (Bb) QlBb (in the formula (Bb), Q 1Bb4-P(RUBb)2, _As(Ri2Bb)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom having a substituent, -N(R13Bb)(R嶋), _ 〇-, _s·, 8(=〇)2〇_, c(=〇)〇·, axe/r&gt; 1 5Bb\ (R )2, -AS( = 〇)(R “Bb)2, _p ( = s)(Rl7Bb)2, _As( = s (R18Bb)2, -CN, -OH, -SH, -C( = 0)0H, -S(=〇)2〇h, -SR19Bb, or _ C( = 〇)N(R21Bb)2 ; RllBb, R12Bb, ^I3Bb ^ R, R丨-, Yan, R, and r2, independently of a hydrogen atom or independently a carbon atom having a substituent of 1 to 30 Alkyl group, RR] 2Bb, R(10), R] 4Bb, Rl5Bb, Rl6Bb, r17b 嶋, a hydrocarbon group having a substituent having a carbon number of i~5〇, R丨彳 and 丨9Bb respectively efs a· a π ^ ^____.. HBb 17Bb, R18Bb, Rm and R2丨 may be the same or different; Q2, _, _, _As (R23Bb) ·, removed from the heterocyclic compound of the nitrogen atom which may have a substituent A group of two hydrogen atoms: Γ, ·, _p(=0)(R25Bb)-, _As(=o)(R26Bb)-, -p(=丨(R27Bb)-, or -As(= S)(R28Bb)_ ; R22Bb, R23Bb, R25Bb and R Cong are independent The gas atom or the hydrocarbon group 'R_ which may have the number of carbon atoms U0 taken from ❸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent, R_, R23Bb, suppressing, suppressing, 15659 丨.doc s -6 201202390 r27:, r28b, the same or different; the number of atoms is 5. The following divalent group, however, is obtained by deriving (6) a hydrogen atom from a heterocyclic compound of 3 nitrogen atoms::: or the bonded Q2Bb is a heterocyclic ring derived from a nitrogen atom In the case where a compound in which two hydrogen atoms are removed from a compound, it may be a direct bond; R is a carbon atom having a carbon number of 50 or less. It is selected from the group consisting of R_, R(10)Λ(10), R, R, R-, RUBb, R, R21Bb, R22Bb, R23Bb, R鸠, R25Bb, R26Bb, R27Bb, R28Bb, R2Bb, R3Bb and a heterocyclic compound containing a nitrogen atom which may have a substituent, and W to 2 hydrogen atoms are Two or more groups in the group may be arbitrarily bonded to form a ring); [Chemical 5] Qlvd, Q1BC (BC) (In the formula (Be), Q1BC is -P(R&quot;b.) 2, _As (R丨h, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom having a substituent, -N(R13Bc)(R14Bc), _〇-, _s-, ·8 ( =〇)2〇-, c(=〇)〇_, _p(=〇) (R )2, _As(=〇)(R16Bc)2, -P(=S)(R17Be)2, _As(=S ) (R )2, _CN, -OH, -SH, -C(=0)0H, -S(=0)2〇H, -SR19Bc, or _C( = 〇)N(R21Bc)2 ; R&quot; Bc, R12B c, Rl3Bc, R_, Rl6Be, Rl7Bc, r18Bir21Bc are each independently a hydrogen atom or 156591.doc 201202390 may have a substituent of a carbon atom number of 5 〇 hydrocarbon group, and RMB &lt; ^Ri9Be are independently a carbon atom which may have a substituent The alkyl group of 1 to 30, riibc, R12Bc, R13Bc, rMBc, Rl5Be, Rl6Bc, Rl7Bc, r18Bc, Ri9Bc and 11218&lt;: may be the same or different; &lt;53 is 卩, 八3, may have a substituent a group of a heterocyclic compound containing a nitrogen atom, wherein three hydrogen atoms are removed, Ν, As (= 0), P (= S), and 4As (= s); R 2 Bc is a valence of 50 or less carbon atoms a group, however, in the case where the bonded Q1Be is a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q3Be is a heterocyclic compound derived from a nitrogen atom. When the base of three hydrogen atoms is removed, it may be a direct bond; it is selected from the group consisting of R11Be, R12BC, RnBc, R]4Bc, Rl5Bc, Ri6Bc, R17Bc, r18Bc l9Bc 21Bc, KK and self-containing nitrogen atoms. Two or more of the groups in which one or three hydrogen atoms are removed from the cyclic compound may also be used. It is a bond to form a ring); [Chemical 6] Q1Bd (Bd) QlBd_p4Bd_QlBd QlBd (in the formula (Bd), Q1B&lt;^-P(R丨1Bd)2, -As(R丨2Bd)2' can be substituted a group in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, _N(Rl3Bd)(Rl4Bd), _〇., _S-, _S(= 〇)2〇., _c( = 〇) 〇·, 156591.doc 201202390 (τ) 1 5Bd\ )2, -As(=〇)(Ri6Bd)2, _p(=s)(Rl7Bd)2, _As(=s) /13⁄4 1 8Bd\ , )2 , CN, _〇H, -SH, -C(=0)0H, -S(=0)2〇H, -SR19Bd, or ·c(=〇)N(R21Bd)2 ; RllBd, Rl2Bd, Rl3Bd , Rl6Bd, Rl7Bd, ^ and ^(8) are each independently a hydrogen atom or a hydrocarbon group having a carbon atom number of 5', and the respective groups of carbon atoms having a substituent of 1 to 30 may be independently represented by RMBd and Rl9Bd. Further, R11Bd, Rl2Bd, R13Bd, R14Bd, Rl5Bd, R16Bd, R17Bd, R18Bd, R19Bd and R Bd may be the same or different; R is a tetravalent group having 70 or less carbon atoms; and is selected from RUBd, R13Bd, R14Bd, R15Bd, R16B (1, R17Bd, R_, R_, R21Bd, R4Bd and a heterocyclic compound derived from a gas atom which may have a substituent In removing one hydrogen atom from a group of two or more of any group may be bonded to form a ring). 7. The film of claim 6, wherein in the above formula (Aa), Q is -P(RUAa)2, -As(R12Aa)2, and is removed from a heterocyclic compound having a gas atom capable of having a substituent a group of hydrogen atoms, -〇·, -S, -S(=〇)2〇-, or ·€(=〇)〇-, Q is -P(R22Aa)_, -As(R23Aa) - or a group obtained by removing two hydrogen atoms from a heterocyclic compound having a gas atom having a substituent, and R, R 2Aa, R22Aa &amp; R23Aa are each independently a group which may have a substituent, and the formula (Aa) The molecule represented by i contains more than one of ρ(κηΑ3)2 or -P(R22Aa)_. 8. The film according to claim 6, wherein in the above formula (Aa), the ruler 2 is a group represented by any one of the following formulas rl to rl2 which may have a substituent 156591.doc 201202390 or may have a substituent; , [Chem. 7] Γ4 r1Γ4 r1 -0(CH2)n-、或_〇(CH2)n〇-所表示之基，Y、_(CH2)n_、_〇 、-S-、或- Si(R51)2_所表示之基；η為1〜3之整數；R50為可 具有取代基之碳原子數〗〜50的芳基，為可具有取代基 之碳原子數1〜50之烴基）。 9.如請求項6之膜，其中於上述式（Ba)中， (^183為邛(111183)2、自可具有取代基之含氮原子之雜環 式化合物中去掉1個氫原子而成的基、-〇-、_c(=〇)〇_、 或-S·， Q為-P(R )-或自可具有取代基之含氮原子之雜環 式化合物中去掉2個氫原子而成的基， RllBa及R22Ba分別獨立為可具有取代基之苯基，尺2以為 直接鍵結或可具有取代基之上述式H〜rl2中之任一個所 表示之基。 156591.doc -10· 201202390 10. 如請求項6之膜’其中於上述式（bc)中， Q1BC為-P(Ri、、自可具有取代基之含氮原子之雜環 式化合物中去掉1個氫原子而成的基、-〇-、C卜⑺〇_、 或-S.， Q3BcibP或自可具有取代基之含氮原子之雜環式化合物 中去掉3個氫原子而成的基， R&quot;Be為可具有取代基之苯基， R 。為直接鍵結或可具有取代基之上述式rl〜rl2中之 任一個所表示之基。 11. 如請求们之膜，其中上述組成式⑴中之χ1為齒化物離 子。 12_如請求項1之膜，其中上述組成式（1)中之a、b、c&amp;d滿 足下述數式（2)， 7-〇^(zxa) + (2xb) + c+d&gt;2.0 (2) (數式（2)中’ z為Li中之可配位於Ag+之原子及離子的總 數）。 13. 如請求項丨之膜，其中上述銀錯合物之“能量與η能量 之差為0.3 ev以下。 14. 如明求項1之膜’其中上述銀錯合物之含量相對於膜整 體之重量為0.01〜100重量％。 15. 如請求項丨之膜，其進而含有高分子化合物。 士 ”月求項1 5之膜，其中上述高分子化合物為聚味唾衍生 物、含有聚芳香族三級胺化合物之殘基的聚合物、多芳 基烷烴衍生物、聚乙烯咔唑衍生物、聚呤二唑衍生物、 I56591.doc -11 - 201202390 聚二《•井衍生物、聚g衍生物、或該等之組合。 17. 18. 19. 一種發光元件，其含有如請求項丨之膜。 -種銀錯合物’其係以下述組成式⑺所表示， (Ag+)(L4)e(L5)f(L6)g(X2)h (3) (組成式（3)中， L4為 具有4個以上且6個以下之可配位於八§+之磷原子的分 子，或者 具有1個以上之磷原子以及選自氛原子、氧原子、硫 原子、钟原子、氧陰離子及硫陰離子中之丨個以上作為 可配位於Ag+之原子或原子及離子，並且l4所具有之可 配位於Ag之原子及離子的總數為3個以上且6個以下的 分子； L5為具有選自磷原子、氮原子、氧原子、硫原子、砷 原子、氧陰離子及硫陰離子中之原子或離子作為可配位 於Ag+之原子或離子的分子，且L5所具有之可配位於Ag+ 之原子及離子的總數為2個； L6為具有1個選自磷原子、氮原子、氧原子、硫原 子砷原子、氧陰離子及硫陰離子中之原子或離子作為 可配位於Ag+之原子或離子的分子； X2為陰離子； e為大於〇.5的數，f、g&amp;h分別獨立為〇以上之數）。 種刀子，其含有2個以上之二芳基膦基，且含有丨個或 2個之選自從含氮原子之雜環式化合物中去掉^個〜3個氫 156591.doc 201202390 原子而成的基、-Ο-、-C(=0)CT、及-S.中之基，並且係以 下述式（Aa)、（Ab)、（Ba')、（Bb)、（Be)或（Bd)所表示， [化8] Q1Aa \Q2Aa〆 \QiAa (Aa) (式（Aa)中， Q1AaS -P(R11Aa)2、_As(Ri2Aa)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 ，N(R13Aa)(R14Aa)、-〇_、_s-、_s(=〇)2〇-、_c(=〇)〇-、_p(=〇) 1 β A, q . (R )2 ' -As(=〇)(R16Aa)2 , -P(=S)(R17Aa)2 ' -As(=S) (R18Aa)2、-CN、-〇H、-SH、-C(=0)OH、-S(=0)20H、 -SR19Aa、或-C(=〇)N(R21Aa)2 ; R11Aa、R12Aa、R13Aa、 R15Aa、Rl6Aa、Rl7Aa、Rl8Aa&amp; R2IAa分別獨立為氫原子或 可具有取代基之碳原子數1〜5〇之烴基，RMA^RBAa分別 獨立為可具有取代基之碳原子數^30之烷基，RllAa、 R12Aa、Rl3Aa、Rl4Aa、Rl5Aa、Rl6Aa、Rl7Aa、Rl8Aa、Rl9Aa 及尺21^可分別相同亦可不同； Q2A1 -P(R22Aa)-、-As(R23Aa)_、自可具有取代基之含 氮原子之雜環式化合物中去掉2個氫原子而成的基、 -N(R )、-p(=〇)(R25Aa)-、-As(=〇)(R26Aa)-、-P(=S) (R27Aa)-、或-As( = S)(R28Aa)_ ; R22Aa、R23Aa、R25Aa、 R 、R27Aa&amp;R28Aa分別獨立為氫原子或可具有取代基 之碳原子數1〜50之烴基，R24Aa為可具有取代基之碳原子 數 1 〜30 之烧基，R22Aa、R23Aa、R24Aa、R25Aa、R26Aa、 156591.doc •13· 201202390 R 及厌28^可分別相同亦可不同； R2Aa為碳原子數50以下之2價基，# O.Aa. , 1貝I然而，於所鍵結之 Q為自3氮原子之雜環式化合物中去w個氣原子而成 的基之情形’或所鍵結之Q2Aa為自含氮原子之雜環式化 合物中去掉2個氫原子而成的基之情形時亦可為直接 鍵結； ~ 選自 R11 Aa 、Ri2Aa r 1 7 A a ^ 8Aa 、R19Aa R13Aa、Rl4Aa、R15Aa R21Aa、R22Aa、R23Aa R】6Aa 、 j^24Aa、 R/w、R26Aa 27Aa 28 R及自可具有取代基之含 氮原子之雜環式化合物中去掉i個〜2個氫原子而成的基 中的2個以上之基亦可任意鍵結而形成環）； [化9] Q1 焚 /QlAb (Ab) 'R3Ab I Q1Ab (式（Ab)中， Q *^_p(RllAb)2、_As(R12Ab)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Ab)(R14Ab)、·〇_、_S-、-S(=0)20.、-C(=〇)〇-、_P(=〇) (R15Ab)2、-As(=0)(R 丨 6Ab)2、-P(=S)(R 丨 7Ab)2、-As(=s) (R18Ab)2、-CN、-OH、-SH、-C(=0)0H、-S(=〇)2〇h、 -SR19Ab、或-C(=0)N(R21Ab)2 ; R&quot;Ab、R12Ab、RnAb、 R15Ab、R16Ab、Rl7Ab、R18Ab&amp;R21Ab分別獨立為氫原子或 可具有取代基之碳原子數1〜50之烴基，R14Ab及R19Ab分別 獨立為可具有取代基之碳原子數1〜30之烷基，R&quot;Ab、 156591.doc .14- 201202390 R12Ab、R13Ab、R14Ab、R15Ab、Ri6Ab、Ri7Ab、RUAb、R19Ab 及R2lAb可分別相同亦可不同； R 為碳原子數5 0以下之3價基； 選自 R11Ab ' Rl2Ab、R13Ab、R14Ab、Rl5Ab、Rl6Ab、 . R17Ab、Rl8Ab、Rl9Ab、R2iAb、R3Ab及自可具有取代基之 ^ 含氮原子之雜環式化合物中去掉1個氫原子而成的基中 的2個以上之基亦可任意鍵結而形成環）； [化 10] QlBa’R、Q2BrR2々Q2B，R2々QlBa(Ba.) (式（Ba')中， Q為-P(RllBa)2、-As(R12Ba)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 •N(R13Ba)(R14Ba)、_〇-、_s.、_s(=〇)2〇·、_c(=〇)〇·、_p(=〇) (R15Ba)2 ' -As(=〇)(R^Ba)2 ^ .P(=S)(R17Ba)2 &gt; -As(=S) (R18Ba)2、-CN、_〇H、-SH、-C(=0)OH、-S(=0)20H、 -SR19Ba、或-C( = 〇)N(R21Ba)2 ; R&quot;Ba、R12Ba、R13Ba、 R Ba、Rl6Ba、Rl7Ba、Rl8Ba&amp;R2iBa分別獨立為氫原子或 * 可具有取代基之碳原子數1〜50之烴基，R14Ba&amp;R19Ba分別 * 獨立為可具有取代基之碳原子數1〜30之烷基，R11Ba、 Rl2Ba、Rl3Ba、Rl4Ba、Rl5Ba、R16Ba、R17Ba、尺丨 8Ba、r丨 9Ba 及112183可分別相同亦可不同； Q為_p(R22Ba)_、-As(R23Ba)-、自可具有取代基之含 氮原子之雜環式化合物中去掉2個氫原子而成的基、 156591.doc -15· 201202390 -N(R )- ' -P( = 〇)(R25Ba)- x -As( = 〇)(R26Ba^ (R27Ba)-、或 _As(=s)(R_)· ; R22Ba、r23b; -P(=S) j^25Ba 1〜30之燒基，R22Ba、R23Ba、R24B; R肠、严分別獨立為氫原子或可具有取代基之 碳原子數㈣之烴基，為可具有取代基之碳原子數 R26Ba、R27Ba R 25Βί 及尺28~可分別相同亦可不同； ^R2Ba’為碳原子數50以下之2價基，然而，於所鍵結之 Q丨、自含氮原子之雜環式化合物中去掉i個氫原子而成 的基之情形，或所鍵結之Q2h為自含氮原子之雜環式化 合物中去掉2個氫原子而成的基之情形時，亦可為直接 鍵結；3個R2Ba'之中1個以上並非直接鍵結； R 選自 R&quot;Ba、R】2Ba、R13B: 17Ba T^18Ba r«19Ba . r»21Bi R1 R1 R R MBa R 15Ba 22B: R 23Ba 6Ba j^24Ba R 25Ba R26Ba、R27Ba、R28Ba、R2Ba’及自可具有取代基之含 氮原子之雜環式化合物中去掉1個〜2個氫原子而成的基 中的2個以上之基亦可任意鍵結而形成環）； [化 11] (Bb) QlBb (式（Bb)中， Q1Bb4 -P(RUBb)2、-As(R12Bb)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R13Bb)(R14Bb)、·〇·、-S·、_s(=〇)2〇-、_c(=〇)〇.、_p(=〇) (R15Bb)2、-As(=0)(R16Bb)2、_p(=s)(Rl7Bb)2、-As(=s) 156591.doc 16 s 201202390 (R18Bb)2、_CN、_〇H、-SH、-C(=0)0H、-S(=〇)2〇h、 -SR19Bb、或 _C( = 〇)N(R21Bb)2 ; R11Bb、R12Bb、Rl3Bb、 Rl5Bb、Rl6Bb、Rl7Bb、R18B1^ R21Bb分別獨立為氫原子或 可具有取代基之碳原子數丨〜％之烴基，Rl4Bb&amp;Rl9Bb分別 獨立為可具有取代基之碳原子數1〜30之烷基，R&quot;Bb、 j^l9Bb R12Bb、R1JBD、Rl4Bb、尺15抑 ' 尺16抑 及尺21抑可分別相同亦可不同； Q2B4 -P(R22Bb)- ' _As(R23Bb)_、可具有取代基之自含 氛原子之雜環式化合物中去掉2個氫原子而成的基、 、-p(=〇)(R25Bb)_、As(=〇)(R26Bb)、p㈣ (R27Bb)-、或-As( = S)(R28Bb)- ; R22Bb、R23Bb、R25Bb、 R 、R27Bb&amp;R28Bb分別獨立為氫原子或可具有取代基 之碳原子數1〜50之烴基，R24Bb為可具有取代基之碳原子 數 1 〜30 之烧基 ’ 、R23Bb、R24Bb、R25Bb、R26Bb、 R Bb及112881&gt;可分別相同亦可不同； 為碳原子數50以下之2價基，然而，於所鍵結之Q為自含氮原子之雜環式化合物中去掉i個氫原子而成 的基之情形’或所鍵結之Q2Bb為自含氮原子之雜環式化 合物中去掉2個氫原子而成的基之情形時，亦可為直接 鍵結； R3Bb為碳原子數5〇以下之3價基； R 17Bb R 18Bb 選自R_、R鬧、R隱、Rl4Bb、…的、 l7Bb ^ t% 1 8Rh ^ 1 QRK Tint. R 16Bb R”Bb、Rl8Bb、Rl9Bb ⑽ 卟 K 、R23Bb、R24Bb、R25Bb、R26Bb、R27Bb、R28Bb、心 3 R及自可具有取代 156591.doc •17- 201202390 基之含氮原子之雜環式化合物中去掉1個〜2個氫原子而 成的基中的2個以上之基亦可任意鍵結而形成環）； [化 12] qIBc Q 18c 、 R2BcT R2B&lt;Ta group represented by -0(CH2)n-, or _〇(CH2)n〇-, a group represented by Y, _(CH2)n_, _〇, -S-, or -Si(R51)2_; η is an integer of 1 to 3; R50 is an aryl group having a substituent having a carbon number of from 00 to 50, and is a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent. 9. The film of claim 6, wherein in the above formula (Ba), (^183 is fluorene (111183) 2, and one hydrogen atom is removed from a heterocyclic compound having a nitrogen atom which may have a substituent; The base, -〇-, _c(=〇)〇_, or -S·, Q is -P(R)- or two hydrogen atoms are removed from the heterocyclic compound having a nitrogen atom which may have a substituent The group represented by RllBa and R22Ba is independently a phenyl group which may have a substituent, and the rule 2 is a group represented by any one of the above formulas H to rl2 which may be directly bonded or may have a substituent. 156591.doc -10· 201202390 10. The film of claim 6 wherein in the above formula (bc), Q1BC is -P (Ri, a hydrogen atom is removed from a heterocyclic compound having a nitrogen atom which may have a substituent; a group in which three hydrogen atoms are removed from a heterocyclic compound having a nitrogen atom capable of having a substituent, and R&quot;Be is present in the group of -, -, -, C, (7), _, or -S., Q3BcibP or a heterocyclic compound having a nitrogen atom which may have a substituent. a phenyl group of the substituent, R is a group represented by any one of the above formulas rl to rl2 which may have a substituent or may have a substituent. The χ1 in the formula (1) is a dentate ion. The film of claim 1, wherein a, b, c&amp;d in the above composition formula (1) satisfy the following formula (2), 7-〇^( Zxa) + (2xb) + c+d&gt;2.0 (2) (in the equation (2), 'z is the total number of atoms and ions in Li that can be assigned to Ag+.) 13. As requested in the film, The difference between the energy and the η energy of the silver complex is 0.3 ev or less. 14. The film of the invention 1 wherein the content of the silver complex is 0.01 to 100% by weight based on the total weight of the film. The film of the request item, which further contains a polymer compound. The film of the above-mentioned polymer compound is a polymerization of a polysodium sulphate derivative and a residue containing a polyaromatic tertiary amine compound. , polyarylalkane derivatives, polyvinylcarbazole derivatives, polyoxadiazole derivatives, I56591.doc -11 - 201202390 poly 2 "well derivatives, poly g derivatives, or a combination of these." 18. A light-emitting element comprising a film as claimed in claim 1. A silver complex compound is represented by the following composition formula (7), (Ag+ (L4)e(L5)f(L6)g(X2)h (3) (In the composition formula (3), L4 is a molecule having 4 or more and 6 or less phosphorus atoms which can be coordinated to eight §+ Or one or more phosphorus atoms and one or more selected from the group consisting of an atmosphere atom, an oxygen atom, a sulfur atom, a clock atom, an oxyanion, and a sulfur anion as atoms or atoms and ions that can be coordinated to Ag+, and have The total number of atoms and ions of Ag may be three or more and six or less molecules; L5 is an atom having a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxyanion, and a sulfur anion. Or an ion as a molecule which can be assigned to an atom or ion of Ag+, and L5 has a total of two atoms and ions which can be coordinated to Ag+; L6 has one selected from a phosphorus atom, a nitrogen atom, an oxygen atom, and sulfur. An atom or an ion of an atomic arsenic atom, an oxyanion or a sulfur anion is a molecule that can be coordinated to an atom or ion of Ag+; X2 is an anion; e is a number greater than 〇.5, and f, g&amp;h are each independently number). a knife comprising two or more arylphosphino groups, and containing one or two selected from the group consisting of atomic compounds containing nitrogen atoms 156591.doc 201202390 atoms , -Ο-, -C(=0)CT, and -S., and are expressed by the following formula (Aa), (Ab), (Ba'), (Bb), (Be) or (Bd) It is indicated that Q1Aa \Q2Aa〆\QiAa (Aa) (in the formula (Aa), Q1AaS -P(R11Aa)2, _As(Ri2Aa)2, a heterocyclic ring containing a nitrogen atom which may have a substituent a group in which one hydrogen atom is removed from the compound, N(R13Aa)(R14Aa), -〇_, _s-, _s(=〇)2〇-, _c(=〇)〇-, _p(=〇) 1 β A, q . (R ) 2 ' -As(=〇)(R16Aa)2 , -P(=S)(R17Aa)2 ' -As(=S) (R18Aa)2, -CN, -〇H , -SH, -C(=0)OH, -S(=0)20H, -SR19Aa, or -C(=〇)N(R21Aa)2; R11Aa, R12Aa, R13Aa, R15Aa, Rl6Aa, Rl7Aa, Rl8Aa& R2IAa is independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and RMA^RBAa is independently an alkyl group having 30 atomic number of carbon atoms which may have a substituent, R11Aa, R12Aa, Rl3Aa, Rl4Aa, Rl5Aa, Rl6Aa, Rl7A a, Rl8Aa, Rl9Aa and 尺21^ may be the same or different; Q2A1 -P(R22Aa)-, -As(R23Aa)_, 2 hydrogen is removed from the heterocyclic compound containing a nitrogen atom having a substituent A radical, -N(R), -p(=〇)(R25Aa)-, -As(=〇)(R26Aa)-, -P(=S) (R27Aa)-, or -As( = S)(R28Aa)_; R22Aa, R23Aa, R25Aa, R, R27Aa&amp;R28Aa are each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and R24Aa is a carbon atom which may have a substituent of 1~ The base of 30, R22Aa, R23Aa, R24Aa, R25Aa, R26Aa, 156591.doc •13· 201202390 R and versa 28^ may be the same or different; R2Aa is a valence of 50 or less carbon atoms, #O.Aa . . . 1 , However, in the case where the bonded Q is a group in which a gas atom is removed from a heterocyclic compound of 3 nitrogen atoms, or the bonded Q 2 Aa is a heterocyclic ring derived from a nitrogen atom. In the case where a group of two hydrogen atoms is removed, a direct bond may be used; ~ selected from R11 Aa, Ri2Aa r 1 7 A a ^ 8Aa , R19Aa R13Aa, Rl4Aa, R15Aa R21Aa, R22Aa, R23Aa R] 6Aa, j^24Aa, Two or more groups in which R/w, R26Aa 27Aa 28 R and a heterocyclic compound having a nitrogen atom capable of having a substituent have one or two hydrogen atoms removed may be bonded arbitrarily. Ring); [Chemical 9] Q1 Burning / QlAb (Ab) 'R3Ab I Q1Ab (in the formula (Ab), Q *^_p (RllAb) 2, _As (R12Ab) 2, a nitrogen-containing atom having a substituent A group in which one hydrogen atom is removed from a heterocyclic compound, -N(R13Ab)(R14Ab), ·〇_, _S-, -S(=0)20., -C(=〇)〇-, _P (=〇) (R15Ab)2, -As(=0)(R 丨6Ab)2, -P(=S)(R 丨7Ab)2, -As(=s) (R18Ab)2, -CN,- OH, -SH, -C(=0)0H, -S(=〇)2〇h, -SR19Ab, or -C(=0)N(R21Ab)2; R&quot;Ab, R12Ab, RnAb, R15Ab, R16Ab , Rl7Ab, R18Ab &amp; R21Ab are each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and R14Ab and R19Ab are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, R&quot;Ab 156591.doc .14- 201202390 R12Ab, R13Ab, R14Ab, R15Ab, Ri6Ab, Ri7Ab, RUAb, R19Ab and R2lAb may be the same or different; R is 3 or less of carbon atoms a group selected from the group consisting of R11Ab 'Rl2Ab, R13Ab, R14Ab, Rl5Ab, Rl6Ab, R17Ab, Rl8Ab, Rl9Ab, R2iAb, R3Ab and a heterocyclic compound having a nitrogen atom which may have a substituent Two or more groups in the base may be arbitrarily bonded to form a ring); [Chemical 10] QlBa'R, Q2BrR2々Q2B, R2々QlBa(Ba.) (In the formula (Ba'), Q is -P (RllBa) 2, -As(R12Ba)2, a group obtained by removing one hydrogen atom from a heterocyclic compound having a nitrogen atom having a substituent, • N(R13Ba)(R14Ba), _〇-, _s., _s(=〇)2〇·, _c(=〇)〇·, _p(=〇) (R15Ba)2 ' -As(=〇)(R^Ba)2 ^ .P(=S)( R17Ba)2 &gt; -As(=S) (R18Ba)2, -CN, _〇H, -SH, -C(=0)OH, -S(=0)20H, -SR19Ba, or -C( = 〇)N(R21Ba)2; R&quot;Ba, R12Ba, R13Ba, R Ba, Rl6Ba, Rl7Ba, Rl8Ba&R2iBa are each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, R14Ba&amp;R19Ba Respectively * independently as an alkyl group having 1 to 30 carbon atoms which may have a substituent, R11Ba, Rl2Ba, Rl3Ba, Rl4Ba, Rl5Ba, R16Ba, R17Ba, 丨8Ba, r 9Ba and 112183 may be the same or different; Q is a group in which _p(R22Ba)_, -As(R23Ba)-, a heterocyclic compound having a nitrogen atom capable of having a substituent, wherein two hydrogen atoms are removed , 156591.doc -15· 201202390 -N(R )- ' -P( = 〇)(R25Ba)- x -As( = 〇)(R26Ba^ (R27Ba)-, or _As(=s)(R_) · R22Ba, r23b; -P(=S) j^25Ba 1~30 alkyl group, R22Ba, R23Ba, R24B; R intestinal, strictly independent of a hydrogen atom or a hydrocarbon group having a substituent (four), The number of carbon atoms which may have a substituent, R26Ba, R27Ba R 25Β, and the size 28~, may be the same or different; ^R2Ba' is a divalent group having 50 or less carbon atoms, however, in the bonded Q丨, In the case where a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q2h is a group in which two hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom. It may also be a direct bond; one or more of the three R2Ba's are not directly bonded; R is selected from the group consisting of R&quot;Ba, R] 2Ba, R13B: 17Ba T^18Ba r«19Ba. r»21Bi R1 R1 RR MBa R 15Ba 22B: R 23Ba 6 Ba j^24Ba R 25Ba R26Ba, R27Ba, R28Ba, R2Ba' and two or more groups in which a heterocyclic compound having a nitrogen atom capable of having a substituent has one to two hydrogen atoms removed Any ring can be bonded to form a ring); [11] (Bb) QlBb (in the formula (Bb), Q1Bb4 -P(RUBb)2, -As(R12Bb)2, a nitrogen-containing atom having a substituent a group in which a hydrogen atom is removed from a cyclic compound, -N(R13Bb)(R14Bb), ·〇·, -S·, _s(=〇)2〇-, _c(=〇)〇., _p( =〇)) (R15Bb)2, -As(=0)(R16Bb)2, _p(=s)(Rl7Bb)2, -As(=s) 156591.doc 16 s 201202390 (R18Bb)2, _CN, _〇 H, -SH, -C(=0)0H, -S(=〇)2〇h, -SR19Bb, or _C(= 〇)N(R21Bb)2; R11Bb, R12Bb, Rl3Bb, Rl5Bb, Rl6Bb, Rl7Bb R18B1^ R21Bb are each independently a hydrogen atom or a hydrocarbon group having a substituent having a carbon number of 丨~%, and Rl4Bb&Rl9Bb are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, R&quot;Bb, j ^l9Bb R12Bb, R1JBD, Rl4Bb, ruler 15 and 'foot 16 and ruler 21 can be the same or different; Q2B4 -P(R22Bb)- ' _As(R23Bb)_ a group obtained by removing two hydrogen atoms from a heterocyclic compound having a substituent atom, -p(=〇)(R25Bb)_, As(=〇)(R26Bb), p(tetra)(R27Bb) -, or -As( = S)(R28Bb)-; R22Bb, R23Bb, R25Bb, R, R27Bb&amp;R28Bb are each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and R24Bb may have The alkyl group of the substituent having 1 to 30 carbon atoms, R23Bb, R24Bb, R25Bb, R26Bb, R Bb and 112881&gt; may be the same or different, and may be a divalent group having 50 or less carbon atoms, however, The Q is a case in which a hydrogen atom is removed from a heterocyclic compound containing a nitrogen atom, or the bonded Q2Bb is obtained by removing two hydrogen atoms from a heterocyclic compound containing a nitrogen atom. In the case of a base, it may be a direct bond; R3Bb is a trivalent group having a carbon number of 5 Å or less; R 17Bb R 18Bb is selected from the group consisting of R_, R, R, R1, Bb, ..., l7Bb^t% 1 8Rh ^ 1 QRK Tint. R 16Bb R"Bb, Rl8Bb, Rl9Bb (10) 卟K, R23Bb, R24Bb, R25Bb, R26Bb, R27Bb, R28Bb, heart 3 R and self-replaceable 156591.do c • 17- 201202390 The heterocyclic compound containing a nitrogen atom in the group may have two or more groups in which one to two hydrogen atoms are removed, and may be arbitrarily bonded to form a ring); [Chemical 12] qIBc Q 18c , R2BcT R2B&lt;T R2BcT q1Bc (Be) (式（Be)中， QIBe4 -P(RnBc)2、_As(R12Be)2、自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基、 -N(R，3Bc)(R,4Bc) ' -Ο* ^ -S' &gt; -S(=0)2〇- ' -C(=0)〇- ' -P(=0) (R15Bc)2 &gt; -As(=〇)(R16Bc)2 . -P(=S)(R17Bc)2 ' -As(=S) (R丨8Bc)2、_CN、-〇H、-SH、-C(=0)〇H、-S(=0)2〇h、 -SR 、或-C(=〇)N(R21Bc)2 ; RnBc、r12Bc、R13Bc、 d R_、Rl7Be、dR21Be分別獨立為氫原子或 可具有取代基之碳原子數丨〜兄之烴基，Rl4BC&amp;Rl9Be分別 獨立為可具有取代基之碳原子數1〜30之烷基，R&quot; Be、 R丨2BC、rUBc、RHBc、R15Bc、R16Bc、R丨7Bc、Ri8BC、r]9Bc 及尺218{:可分別相同亦可不同； Q3Be&amp;P'As、自可具有取代基之含氮原子之雜環式 化合物中去掉3個氫原子而成的基、N、、 As(=0)、p(=s)、或 As(=s); R為碳原子數50以下之2價基，然而，於所鍵結之 Q1Bt^自含氮原子之雜環式化合物中去掉1個氫原子而成 的基之情形，或所鍵結之Q3Be為自含氮原子之雜環式化 156591.doc S •18· 201202390 亦可為直接 合物中去掉3個氫原子而成的基之情形時 鍵結； 選自Ri K K r&quot;Bc、r18Bc、r19Bc、r21Bc、r2B 曰3氮原子之雜環式 化合物中去掉1個或3個氫原子而成的基中的2個以上之 基亦可任意鍵結而形成環）； [化 13] Q1Bd Q1Bd_R4Bd_QlBd (Bd) Q1Bd (式（Bd)中， Q1、-P(R11Bd)2、-As(R12Bd)2、自可具有取代基之含 氮原子之雜環式化合物中去掉丨個氫原子而成的基、 -N(R13Bd)(R14Bd)、-〇· ' -S·、-S(=0)2〇-、-C(=0)〇·、_p(=〇) (R15Bd)2 . -As(=0)(R16Bd)2 &gt; -P(=S)(R17Bd)2 . -As(=S) (R18Bd)2、-CN、-〇H、-SH、-C(=0)0H、_S(=〇)2〇H、 -SR19Bd、或 _C(=0)N(R21Bd)2 ; RllBd、Rl2Bd、Rl3Bd、 Rl5Bd、R16Bd、R17Bd、尺刪及112咖分別獨立為氫原子或 可具有取代基之碳原子數1〜50之烴基，Rl4Bd&amp;Rl9Bd分別 獨立為可具有取代基之碳原子數1〜30之烷基，RiiBd、 R12Bd、Rl3Bd、Rl4Bd、Rl5Bd、Rl6Bd、Rl7Bd、Ri8Bd、y⑽ 及11218(1可分別相同亦可不同； R4Bd為碳原子數50以下之4價基； 選自 RHBd、Rl2Bd、Rl3Bd、R丨4Bd、R丨 5Bd、Rl6Bd、 156591.doc •19· 201202390 R17Bd、R18Bd、R19Bd、R21Bd、R4Bd及自可具有取代基之含 氮原子之雜環式化合物中去掉1個氫原子而成的基中的2 個以上之基亦可任意鍵結而形成環）。 20- 156591.doc 201202390 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 156591.docR2BcT q1Bc (Be) (in the formula (Be), QIBe4 -P(RnBc)2, _As(R12Be)2, a group in which one hydrogen atom is removed from a heterocyclic compound having a nitrogen atom capable of having a substituent , -N(R,3Bc)(R,4Bc) ' -Ο* ^ -S' &gt; -S(=0)2〇- ' -C(=0)〇- ' -P(=0) (R15Bc ) 2 &gt; -As(=〇)(R16Bc)2 . -P(=S)(R17Bc)2 ' -As(=S) (R丨8Bc)2, _CN, -〇H, -SH, -C (=0)〇H, -S(=0)2〇h, -SR, or -C(=〇)N(R21Bc)2; RnBc, r12Bc, R13Bc, d R_, Rl7Be, dR21Be are each independently a hydrogen atom Or a hydrocarbon group having a substituent having a carbon number of 丨~Brown, and Rl4BC&amp;Rl9Be are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, R&quot; Be, R丨2BC, rUBc, RHBc, R15Bc, R16Bc, R丨7Bc, Ri8BC, r]9Bc and 尺218{: may be the same or different; Q3Be&amp;P'As, three hydrogen atoms are removed from a heterocyclic compound containing a nitrogen atom having a substituent a group of N, N, As (=0), p (= s), or As (= s); R is a divalent group having a carbon number of 50 or less, however, the bonded Q1Bt ^ self-containing nitrogen One hydrogen atom is removed from a heterocyclic compound of an atom The case of the bond, or the bonded Q3Be is a heterocyclic ring of a self-containing nitrogen atom. 156591.doc S •18· 201202390 It can also be a bond in the case where the three hydrogen atoms are removed from the direct compound. Two or more groups selected from the group consisting of Ri KK r &quot; Bc, r18Bc, r19Bc, r21Bc, and r2B 氮3 nitrogen atoms, wherein one or three hydrogen atoms are removed, may be arbitrarily bonded And forming a ring); [Chemical 13] Q1Bd Q1Bd_R4Bd_QlBd (Bd) Q1Bd (in the formula (Bd), Q1, -P(R11Bd)2, -As(R12Bd)2, a heterocyclic ring containing a nitrogen atom which may have a substituent a group in which a hydrogen atom is removed from the compound, -N(R13Bd)(R14Bd), -〇· ' -S·, -S(=0)2〇-, -C(=0)〇·,_p (=〇) (R15Bd)2 . -As(=0)(R16Bd)2 &gt; -P(=S)(R17Bd)2 . -As(=S) (R18Bd)2, -CN, -〇H, -SH, -C(=0)0H, _S(=〇)2〇H, -SR19Bd, or _C(=0)N(R21Bd)2; RllBd, Rl2Bd, Rl3Bd, Rl5Bd, R16Bd, R17Bd, rule And 112 coffees are each independently a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and Rl4Bd &amp; Rl9Bd are each independently a carbon atom which may have a substituent a number of 1 to 30 alkyl groups, RiiBd, R12Bd, Rl3Bd, Rl4Bd, Rl5Bd, Rl6Bd, Rl7Bd, Ri8Bd, y(10) and 11218 (1 may be the same or different; R4Bd is a tetravalent group having 50 or less carbon atoms; RHBd, Rl2Bd, Rl3Bd, R丨4Bd, R丨5Bd, Rl6Bd, 156591.doc •19· 201202390 R17Bd, R18Bd, R19Bd, R21Bd, R4Bd and a heterocyclic compound containing a nitrogen atom which may have a substituent Two or more groups of the hydrogen atom-based groups may be bonded to each other to form a ring. 20- 156591.doc 201202390 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display invention. Characteristic chemical formula: (none) 156591.doc
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