JP2003113246A - Polymerizable compound and method for producing the same - Google Patents

Polymerizable compound and method for producing the same

Info

Publication number
JP2003113246A
JP2003113246A JP2001306282A JP2001306282A JP2003113246A JP 2003113246 A JP2003113246 A JP 2003113246A JP 2001306282 A JP2001306282 A JP 2001306282A JP 2001306282 A JP2001306282 A JP 2001306282A JP 2003113246 A JP2003113246 A JP 2003113246A
Authority
JP
Japan
Prior art keywords
formula
group
polymerizable compound
chemical
hydrogen atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2001306282A
Other languages
Japanese (ja)
Other versions
JP4035976B2 (en
Inventor
Yoshiaki Takahashi
良明 高橋
Hiroo Shirane
浩朗 白根
Motoaki Kamaike
元昭 蒲池
Naoko Ito
直子 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2001306282A priority Critical patent/JP4035976B2/en
Priority to TW91113391A priority patent/TW584661B/en
Priority to CNB028123123A priority patent/CN100440568C/en
Priority to PCT/JP2002/006139 priority patent/WO2003001616A2/en
Priority to AT02743651T priority patent/ATE431970T1/en
Priority to EP02743651A priority patent/EP1407501B1/en
Priority to US10/481,442 priority patent/US7396598B2/en
Priority to DE60232415T priority patent/DE60232415D1/en
Priority to KR1020037016625A priority patent/KR100925409B1/en
Priority to AU2002345362A priority patent/AU2002345362A1/en
Publication of JP2003113246A publication Critical patent/JP2003113246A/en
Application granted granted Critical
Publication of JP4035976B2 publication Critical patent/JP4035976B2/en
Priority to US12/026,877 priority patent/US7736757B2/en
Priority to US12/026,798 priority patent/US7763365B2/en
Priority to US12/026,854 priority patent/US7635527B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a polymeric light-emitting material for obtaining an organic light-emitting element having high light-emitting efficiency, facilitating the enlargement of area and capable of being mass-produced. SOLUTION: This polymerizable compound has a bis(2-phenylpyridine) iridium complex part and a polymerizable functional group (e.g. a vinyl group).

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、平面表示パネルや
これに用いられるバックライト用の有機発光素子（ＯＬ
ＥＤ）に用いられる高分子系発光材料の前駆体である重
合性化合物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat display panel and an organic light emitting device (OL) for a backlight used in the flat display panel.
The present invention relates to a polymerizable compound that is a precursor of a polymeric light emitting material used for ED).

【０００２】[0002]

【従来の技術】有機発光素子は、１９８７年にコダック
社のＣ．Ｗ．Ｔａｎｇらにより高輝度の発光が示されて
（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，５１巻，９１３
頁，１９８７年）以来、材料開発、素子構造の改良が急
速に進み、最近になってカーオーディオや携帯電話用の
ディスプレイなどから実用化が始まった。この有機ＥＬ
の用途を更に拡大するために、発光効率向上、耐久性向
上のための材料開発、フルカラー表示の開発などが現在
活発に行われている。特に、中型パネルや大型パネル、
あるいは照明用途への展開を考える上では発光効率の向
上による更なる高輝度化と、大面積化に適した量産方法
の確立が必要である。2. Description of the Related Art Organic light emitting devices were manufactured by Kodak Corporation in C.I. W. Tang et al. Showed high-intensity luminescence (Appl. Phys. Lett., 51, 913.
(Page, 1987), the development of materials and the improvement of the device structure have progressed rapidly, and the practical application has recently started with displays for car audio systems and mobile phones. This organic EL
In order to further expand the applications of the above, development of materials for improving luminous efficiency and durability, development of full-color display, etc. are currently being actively conducted. Especially for medium and large size panels,
Alternatively, when considering expansion to lighting applications, it is necessary to establish higher mass production methods suitable for larger areas and higher brightness by improving luminous efficiency.

【０００３】先ず、発光効率に関しては、現在の発光材
料で利用されているのは励起一重項状態からの発光、す
なわち蛍光であり、月刊ディスプレイ，１９９８年１０
月号別冊「有機ＥＬディスプレイ」，５８頁によれば、
電気的励起における励起一重項状態と励起三重項状態の
励起子の生成比が１：３であることから、有機ＥＬにお
ける発光の内部量子効率は２５％が上限である。First, regarding the luminous efficiency, it is the light emission from the excited singlet state, that is, the fluorescence that is used in the present light emitting materials. Monthly display, 1998, 10
According to the monthly issue “Organic EL Display”, page 58,
Since the generation ratio of excitons in the excited singlet state and the excited triplet state in electric excitation is 1: 3, the upper limit of the internal quantum efficiency of light emission in organic EL is 25%.

【０００４】これに対し、Ｍ．Ａ．Ｂａｌｄｏらは励起
三重項状態から燐光発光するイリジウム錯体を用いるこ
とにより外部量子効率７．５％を得、これは外部取り出
し効率を２０％と仮定すると内部量子効率３７．５％に
相当し、蛍光色素を利用した場合の上限値である２５％
という値を上回ることが可能なことを示した（Ａｐｐ
ｌ．Ｐｈｙｓ．Ｌｅｔｔ．，７５巻，４頁，１９９９
年、ＷＯ00/70655）。On the other hand, M. A. Baldo et al. Obtained an external quantum efficiency of 7.5% by using an iridium complex that emits phosphorescence from an excited triplet state, which corresponds to an internal quantum efficiency of 37.5% assuming an external extraction efficiency of 20%. 25%, which is the upper limit when dyes are used
It is possible to exceed the value of (App
l. Phys. Lett. , 75, p. 4, 1999
Year, WO00 / 70655).

【０００５】次に、パネルの量産方法に関しては、従来
から真空蒸着法が用いられてきた。しかし、この方法は
真空設備を必要とする点、大面積になるほど有機薄膜を
均一の厚さに成膜することが困難になる点などの問題点
を有しており、必ずしも大面積パネルの量産に適した方
法とは言えない。Next, as a mass production method of panels, a vacuum vapor deposition method has been conventionally used. However, this method has problems such as the need for vacuum equipment and the difficulty of forming an organic thin film with a uniform thickness as the area increases. Is not a suitable method for.

【０００６】これに対し、大面積化が容易な方法として
高分子系発光材料を用いた製造方法、すなわちインクジ
ェット法や印刷法が開発されている。特に、印刷法は連
続して長尺の成膜が行え、大面積化と量産性に優れてい
る。On the other hand, as a method for easily increasing the area, a manufacturing method using a polymer light emitting material, that is, an ink jet method or a printing method has been developed. In particular, the printing method is capable of continuously forming a long film and is excellent in large area and mass productivity.

【０００７】上記のように、発光効率が高くかつ大面積
の有機発光素子を得るためには、燐光発光性の高分子材
料が必要となる。このような燐光発光性の高分子材料と
しては、ルテニウム錯体を高分子の主鎖または側鎖に組
み込んだものがある（Ng, P.K. et al., Polymer Prepr
ints., 40(2), 1212 (1999)）。しかし、これらはイオ
ン性化合物であるため、電圧を印加した場合に電極での
酸化還元反応による電気化学発光が起こる。これは応答
速度が分オーダーと極めて遅く、通常のディスプレイパ
ネルとしては使用できない。As described above, in order to obtain an organic light emitting device having a high luminous efficiency and a large area, a phosphorescent polymer material is required. As such a phosphorescent polymer material, there is one in which a ruthenium complex is incorporated into the main chain or side chain of the polymer (Ng, PK et al., Polymer Prepr).
ints., 40 (2), 1212 (1999)). However, since these are ionic compounds, electrochemiluminescence due to the redox reaction at the electrodes occurs when a voltage is applied. This has a very slow response speed on the order of minutes and cannot be used as a normal display panel.

【０００８】また、厳密な意味では高分子材料とは言え
ないが、ポリ（Ｎ−ビニルカルバゾール）に燐光発光性
の低分子化合物であるイリジウム錯体を混合したものが
ある（P. J. Djurovich et al., Polymer Preprints,
41(1), 770 (2000)）。しかし、これは均質な高分子材
料に較べて熱安定性が劣り、相分離や偏析を起こす可能
性がある。Although not a polymer material in a strict sense, there is a material obtained by mixing poly (N-vinylcarbazole) with an iridium complex which is a low molecular weight compound having phosphorescence (PJ Djurovich et al., Polymer Preprints,
41 (1), 770 (2000)). However, this is inferior in thermal stability to a homogeneous polymer material and may cause phase separation or segregation.

【０００９】[0009]

【発明が解決しようとする課題】上記のように、発光効
率が高くかつ大面積の有機発光素子を量産するために必
要とされる実用的な高分子系の燐光発光性材料は未だ存
在しない。そこで、本発明は上記のような従来技術の問
題点を解決し、高発光効率で大面積化が可能であり、か
つ量産可能な有機発光素子を得るための高分子系発光材
料を提供することを課題とする。As described above, there is still no practical high molecular weight phosphorescent material which is required for mass production of organic light emitting devices having high luminous efficiency and large area. Therefore, the present invention solves the problems of the prior art as described above, and provides a polymer light-emitting material for obtaining an organic light-emitting device capable of increasing the area with high luminous efficiency and being mass producible. Is an issue.

【００１０】[0010]

【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく種々検討した結果、有機発光素子の発光
材料として有用なイリジウム錯体部分を有する重合性化
合物を得ることに成功し、本発明を完成するに至った。As a result of various investigations for solving the above problems, the present inventors succeeded in obtaining a polymerizable compound having an iridium complex portion useful as a light emitting material for an organic light emitting device. The present invention has been completed.

【００１１】すなわち、本発明は以下の［１］〜［４
２］で示される新規化合物である重合性化合物とこれら
重合性化合物の合成に必要な新規化合物である中間体、
及びこれら重合性化合物の製造方法に関する。That is, the present invention provides the following [1] to [4]
2] a polymerizable compound which is a novel compound and an intermediate which is a novel compound necessary for the synthesis of these polymerizable compounds,
And a method for producing these polymerizable compounds.

【００１２】［１］ 式（１）で示される重合性化合
物。[1] A polymerizable compound represented by the formula (1).

【化２５】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基を表し、Ｘ1、Ｙ1、Ｚ1のうちの残り
はそれぞれ独立に水素原子ヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。Ｒ1〜Ｒ12はそれぞれ独
立に水素原子、ハロゲン原子、ニトロ基、アミノ基、ス
ルホン酸基、スルホン酸エステル基またはヘテロ原子を
有してもよい炭素数１〜２０の有機基を表す。〕[Chemical 25] Wherein, X 1, Y 1, at least one of Z 1 represents a substituent having a polymerizable functional group, have the X 1, Y 1, each remaining independently a hydrogen atom hetero atoms of the Z 1 It may represent an organic group having 1 to 20 carbon atoms. R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

【００１３】［２］ 前記式（１）におけるＸ1または
Ｚ1のいずれか一方が重合性官能基を有する置換基であ
る［１］に記載の重合性化合物。[2] The polymerizable compound according to [1], wherein either X 1 or Z 1 in the formula (1) is a substituent having a polymerizable functional group.

【００１４】［３］式（２）で示される重合性化合物。[3] A polymerizable compound represented by the formula (2).

【化２６】 〔式中、Ｘ1は重合性官能基を有する置換基を表し、Ｑ1
およびＱ2はそれぞれ独立に水素原子またはヘテロ原子
を有してもよい炭素数１〜２０の有機基を表す。〕[Chemical formula 26] [In the formula, X 1 represents a substituent having a polymerizable functional group, and Q 1
And Q 2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

【００１５】［４］ 重合性官能基が炭素−炭素二重結
合である［１］〜［３］のいずれか一つに記載の重合性
化合物。[4] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is a carbon-carbon double bond.

【００１６】［５］ 式（３）で示される重合性化合
物。[5] A polymerizable compound represented by the formula (3).

【化２７】 [Chemical 27]

【００１７】［６］ 重合性官能基がスチリル基である
［１］〜［３］のいずれか一つに記載の重合性化合物。[6] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is a styryl group.

【００１８】［７］ 式（４）で示される重合性化合
物。[7] A polymerizable compound represented by the formula (4).

【化２８】 [Chemical 28]

【００１９】［８］ 重合性官能基がアクリレート基ま
たはメタクリレート基である［１］〜［３］のいずれか
一つに記載の重合性化合物。[8] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is an acrylate group or a methacrylate group.

【００２０】［９］ 式（５）で示される重合性化合
物。[9] A polymerizable compound represented by the formula (5).

【化２９】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 29] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２１】［１０］ 式（６）で示される重合性化合
物。[10] A polymerizable compound represented by the formula (6).

【化３０】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 30] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２２】［１１］ 式（７）で示される重合性化合
物。[11] A polymerizable compound represented by the formula (7).

【化３１】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 31] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２３】［１２］式（８）で示される重合性化合
物。[12] A polymerizable compound represented by the formula (8).

【化３２】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 32] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２４】［１３］ 式（９）で示される重合性化合
物。[13] A polymerizable compound represented by the formula (9).

【化３３】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 33] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２５】［１４］ 式（１０）で示される重合性化
合物。[14] A polymerizable compound represented by the formula (10).

【化３４】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 34] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２６】［１５］ 式（１１）で示される重合性化
合物。[15] A polymerizable compound represented by the formula (11).

【化３５】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 35] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２７】［１６］ 式（１２）で示される重合性化
合物。[16] A polymerizable compound represented by the formula (12).

【化３６】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 36] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００２８】［１７］ 式（１３）で示される重合性化
合物。[17] A polymerizable compound represented by the formula (13).

【化３７】 [Chemical 37]

【００２９】［１８］ 前記式（１）におけるＹ1が重
合性官能基を有する置換基である［１］に記載の重合性
化合物。[18] The polymerizable compound according to [1], wherein Y 1 in the formula (1) is a substituent having a polymerizable functional group.

【００３０】［１９］ 式（１４）で示される重合性化
合物。[19] A polymerizable compound represented by the formula (14).

【化３８】 〔式中、Ｙ1は重合性官能基を有する置換基を表し、Ｑ2
およびＱ3はそれぞれ独立に水素原子またはヘテロ原子
を有してもよい炭素数１〜２０の有機基を表す。〕[Chemical 38] [In the formula, Y 1 represents a substituent having a polymerizable functional group, and Q 2
And Q 3 each independently represent an organic group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. ]

【００３１】［２０］ 重合性官能基が炭素−炭素二重
結合である［１８］または［１９］に記載の重合性化合
物。 ［２１］ 重合性官能基がスチリル基である［１８］ま
たは［１９］に記載の重合性化合物。 ［２２］ 重合性官能基がアクリレート基またはメタク
リレート基である［１８］または［１９］に記載の重合
性化合物。[20] The polymerizable compound according to [18] or [19], wherein the polymerizable functional group is a carbon-carbon double bond. [21] The polymerizable compound according to [18] or [19], wherein the polymerizable functional group is a styryl group. [22] The polymerizable compound according to [18] or [19], wherein the polymerizable functional group is an acrylate group or a methacrylate group.

【００３２】［２３］ 式（１５）で示される重合性化
合物。[23] A polymerizable compound represented by the formula (15).

【化３９】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical Formula 39] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００３３】［２４］ 式（１６）で示される重合性化
合物。[24] A polymerizable compound represented by the formula (16).

【化４０】 〔式中、Ｒは水素原子またはメチル基を表す。〕[Chemical 40] [In the formula, R represents a hydrogen atom or a methyl group. ]

【００３４】［２５］ 式（１７）で示されるイリジウ
ム二核錯体と式（１８）で示される重合性官能基を有す
る化合物を反応させることを特徴とする単核イリジウム
錯体部分を含む重合性化合物の製造方法。[25] A polymerizable compound containing a mononuclear iridium complex moiety characterized by reacting the iridium binuclear complex represented by the formula (17) with a compound having a polymerizable functional group represented by the formula (18). Manufacturing method.

【化４１】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕[Chemical 41] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ]

【化４２】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基、Ｘ1、Ｙ1、Ｚ1のうちの残りはそれ
ぞれ独立に水素原子またはヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。〕[Chemical 42] [In the formula, at least one of X 1 , Y 1 and Z 1 has a substituent having a polymerizable functional group, and the rest of X 1 , Y 1 and Z 1 each independently have a hydrogen atom or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ]

【００３５】［２６］ 前記式（１８）におけるＸ1ま
たはＺ1が重合性官能基を有する置換基である［２５］
に記載の単核イリジウム錯体部分を含む重合性化合物の
製造方法。 ［２７］ 前記式（１８）におけるＹ1が重合性官能基
を有する置換基である［２５］に記載の単核イリジウム
錯体部分を含む重合性化合物の製造方法。[26] X 1 or Z 1 in the above formula (18) is a substituent having a polymerizable functional group [25]
The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to 1. [27] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [25], wherein Y 1 in the formula (18) is a substituent having a polymerizable functional group.

【００３６】［２８］ 式（１７）で示されるイリジウ
ム二核錯体と式（１９）で示される反応性置換基を有す
る化合物を反応させた後、得られた単核イリジウム錯体
の反応性置換基と重合性官能基を有する化合物を反応さ
せることを特徴とする単核イリジウム錯体部分を含む重
合性化合物の製造方法。[28] After reacting the iridium binuclear complex represented by the formula (17) with the compound having the reactive substituent represented by the formula (19), the reactive substituent of the obtained mononuclear iridium complex is reacted. And a compound having a polymerizable functional group are reacted with each other to provide a method for producing a polymerizable compound containing a mononuclear iridium complex portion.

【化４３】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕[Chemical 43] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ]

【化４４】 〔式中、Ｘ2、Ｙ2、Ｚ2の少なくとも１つは反応性置換
基、Ｘ2、Ｙ2、Ｚ2のうちの残りはそれぞれ独立に水素
原子またはヘテロ原子を有してもよい炭素数１〜２０の
有機基を表す。〕[Chemical 44] [In the formula, at least one of X 2 , Y 2 and Z 2 is a reactive substituent, and the rest of X 2 , Y 2 and Z 2 are each independently a carbon atom which may have a hydrogen atom or a hetero atom. Represents an organic group of the number 1 to 20. ]

【００３７】［２９］ 式（１９）におけるＸ2または
Ｙ2が水酸基を有する置換基である［２８］に記載の単
核イリジウム錯体部分を含む重合性化合物の製造方法。 ［３０］ 式（１９）におけるＹ2が水酸基を有する置
換基である請求項２８に記載の単核イリジウム錯体部分
を含む重合性化合物の製造方法。[29] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [28], wherein X 2 or Y 2 in the formula (19) is a substituent having a hydroxyl group. [30] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 28, wherein Y 2 in formula (19) is a substituent having a hydroxyl group.

【００３８】［３１］ 式（２０）で示される化合物。[31] A compound represented by the formula (20).

【化４５】 〔式中、Ｘ2、Ｙ2、Ｚ2の少なくとも１つは水酸基を有
する置換基を表し、Ｘ2、Ｙ2、Ｚ2のうちの残りはそれ
ぞれ独立に水素原子またはヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。Ｒ1〜Ｒ12はそれぞれ独
立に水素原子、ハロゲン原子、ニトロ基、アミノ基、ス
ルホン酸基、スルホン酸エステル基またはヘテロ原子を
有してもよい炭素数１〜２０の有機基を表す。〕 ［３２］ 式（２０）におけるＸ2またはＺ2が水酸基を
有する置換基である［３１］に記載の化合物。[Chemical formula 45] Wherein, X 2, Y 2, at least one of Z 2 represents a substituent having a hydroxyl group, with a X 2, Y 2, each remaining independently a hydrogen atom or a heteroatom of Z 2 Represents an organic group having 1 to 20 carbon atoms. R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. [32] The compound according to [31], wherein X 2 or Z 2 in the formula (20) is a substituent having a hydroxyl group.

【００３９】［３３］ 式（２１）で示される化合物。[33] A compound represented by the formula (21).

【化４６】 〔式中、ｎは０〜２０の整数を表し、Ｑ1およびＱ2はそ
れぞれ独立に水素原子またはヘテロ原子を有してもよい
炭素数１〜２０の有機基を表す。〕[Chemical formula 46] [In the formula, n represents an integer of 0 to 20, and Q 1 and Q 2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

【００４０】［３４］式（２２）で示される化合物。[34] A compound represented by the formula (22).

【化４７】 〔式中、ｎは０〜２０の整数を表し、Ｑ1およびＱ2はそ
れぞれ独立に水素原子またはヘテロ原子を有してもよい
炭素数１〜２０の有機基を表す。〕 ［３５］ 式（２０）におけるＹ2が水酸基を有する置
換基である［３１］に記載の化合物。[Chemical 47] [In the formula, n represents an integer of 0 to 20, and Q 1 and Q 2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. [35] The compound described in [31], wherein Y 2 in the formula (20) is a substituent having a hydroxyl group.

【００４１】［３６］ 式（２３）で示される化合物。[36] A compound represented by the formula (23).

【化４８】 〔式中、ｎは０〜２０の整数を表し、Ｑ2およびＱ3はそ
れぞれ独立に水素原子またはヘテロ原子を有してもよい
炭素数１〜２０の有機基を表す。〕[Chemical 48] [In the formula, n represents an integer of 0 to 20, and Q 2 and Q 3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

【００４２】［３７］ ［１］〜［２４］のいずれか一
つに記載の重合性化合物の重合体。 ［３８］ ［１］〜［２４］のいずれか一つに記載の重
合性化合物を１種以上含む組成物を重合してなる重合
体。 ［３９］ ［１］〜［２４］のいずれか一つに記載の重
合性化合物を含むことを特徴とする発光材料。 ［４０］ ［１］〜［２４］のいずれか一つに記載の重
合性化合物を重合してなる発光材料。 ［４１］ ［１］〜［２４］のいずれか一つに記載の重
合性化合物を１種以上含む組成物を重合してなる発光材
料。 ［４２］ ［１］〜［２４］のいずれか一つに記載の発
光材料を用いた有機発光素子。[37] A polymer of the polymerizable compound according to any one of [1] to [24]. [38] A polymer obtained by polymerizing a composition containing at least one polymerizable compound according to any one of [1] to [24]. [39] A luminescent material containing the polymerizable compound according to any one of [1] to [24]. [40] A luminescent material obtained by polymerizing the polymerizable compound according to any one of [1] to [24]. [41] A luminescent material obtained by polymerizing a composition containing at least one polymerizable compound according to any one of [1] to [24]. [42] An organic light emitting device using the light emitting material according to any one of [1] to [24].

【００４３】[0043]

【発明の実施の形態】以下、本発明を具体的に説明す
る。本発明により式（１）BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. According to the present invention, the formula (1)

【００４４】[0044]

【化４９】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基を表し、Ｘ1、Ｙ1、Ｚ1のうちの残り
はそれぞれ独立に水素原子またはヘテロ原子を有しても
よい炭素数１〜２０の有機基を表す。Ｒ1〜Ｒ12はそれ
ぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ
基、スルホン酸基、スルホン酸エステル基またはヘテロ
原子を有してもよい炭素数１〜２０の有機基を表す。〕
で表される重合性化合物が提供される。[Chemical 49] Wherein, X 1, Y 1, at least one of Z 1 represents a substituent having a polymerizable functional group, the X 1, Y 1, each remaining independently a hydrogen atom or a heteroatom of Z 1 It represents an organic group which may have 1 to 20 carbon atoms. R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
A polymerizable compound represented by:

【００４５】式（１）におけるＸ1、Ｙ1、Ｚ1のうちの
重合性官能基を有する置換基は、ラジカル重合性、カチ
オン重合性、アニオン重合性、付加重合性、縮合重合性
のいずれであってもよいが、ラジカル重合性の官能基が
好ましい。この重合性官能基としては、ビニル基、アリ
ル基、アルケニル基、アクリレート基、メタクリレート
基、メタクリロイルオキシエチルカルバメート基等のウ
レタン（メタ）アクリレート基、スチリル基及びその誘
導体、ビニルアシド基及びその誘導体などを有する置換
基を挙げることができる。これらの重合性官能基の中
で、その重合性という観点から、アクリレート基、メタ
アクリレート基、ウレタン（メタ）アクリレート基が好
ましい。The substituent having a polymerizable functional group of X 1 , Y 1 and Z 1 in the formula (1) is any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable and condensation polymerizable. , But a radically polymerizable functional group is preferred. Examples of the polymerizable functional group include a vinyl group, an allyl group, an alkenyl group, an acrylate group, a methacrylate group, a urethane (meth) acrylate group such as a methacryloyloxyethyl carbamate group, a styryl group and a derivative thereof, a vinyl acid group and a derivative thereof, and the like. The substituent which it has can be mentioned. Among these polymerizable functional groups, an acrylate group, a methacrylate group, and a urethane (meth) acrylate group are preferable from the viewpoint of the polymerizability.

【００４６】各式におけるＸ1、Ｙ1、Ｚ1のうちの重合
性官能基を有しない置換基、Ｑ1〜Ｑ 3としては水素原
子、メチル、エチル、プロピル、イソプロピル、ブチ
ル、イソブチル、ターシャリーブチル、アミル、ヘキシ
ル等のアルキル基、またメトキシ、エトキシ、プロポキ
シ、イソブトキシ、ターシャリーブトキシ等のアルコキ
シ基、アセトキシ基、プロポキシカルボニル基などのエ
ステル基、アリール基等の有機基を挙げることができ
る。X in each equation1, Y1, Z1Polymerization of
Group having no functional group, Q1~ Q 3As a hydrogen source
Child, methyl, ethyl, propyl, isopropyl, buty
Ru, isobutyl, tert-butyl, amyl, hex
Alkyl groups such as methoxy, ethoxy, propoxy
Alkoxy such as Si, isobutoxy, tertiary butoxy
Groups such as silane, acetoxy, and propoxycarbonyl.
Examples thereof include organic groups such as stell group and aryl group.
It

【００４７】各式におけるＲ1〜Ｒ12およびＲ13〜Ｒ24
としては水素原子、ハロゲン原子、ニトロ基、アミノ
基、スルホン酸基、スルホン酸メチル等のスルホン酸エ
ステル基、メチル、エチル、プロピル、イソプロピル、
ブチル、イソブチル、ターシャリーブチル、アミル、ヘ
キシル等のアルキル基、またメトキシ、エトキシ、プロ
ポキシ、イソブトキシ、ターシャリーブトキシ等のアル
コキシ基、アセトキシ基、プロポキシカルボニル基など
のエステル基、アリール基等の有機基を挙げることがで
きる。また、これらの有機基は、更にハロゲン原子、ニ
トロ基、アミノ基等の置換基を有していてもよい。R 1 to R 12 and R 13 to R 24 in each formula
Examples of the hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonate ester group such as methyl sulfonate, methyl, ethyl, propyl, isopropyl,
Alkyl groups such as butyl, isobutyl, tert-butyl, amyl and hexyl, alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, tert-butoxy, ester groups such as acetoxy group and propoxycarbonyl group, organic groups such as aryl group Can be mentioned. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group or an amino group.

【００４８】次に、本発明による重合性化合物の合成方
法の例を以下に挙げるが、本発明は何らこれらに限定さ
れるものではない。Next, examples of the method for synthesizing the polymerizable compound according to the present invention will be given below, but the present invention is not limited thereto.

【００４９】その第１の合成方法は、式（１７）で示さ
れるイリジウムの二核錯体と式（１８）で示される重合
性置換基を有する化合物を反応させることにより単核イ
リジウム錯体部分を含む重合性化合物を得る方法であ
る。The first synthetic method includes a mononuclear iridium complex portion by reacting a binuclear iridium complex represented by the formula (17) with a compound having a polymerizable substituent represented by the formula (18). It is a method of obtaining a polymerizable compound.

【化５０】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕[Chemical 50] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ]

【化５１】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基、Ｘ1、Ｙ1、Ｚ1のうちの残りはそれ
ぞれ独立に水素原子またはヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。〕[Chemical 51] [In the formula, at least one of X 1 , Y 1 and Z 1 has a substituent having a polymerizable functional group, and the rest of X 1 , Y 1 and Z 1 each independently have a hydrogen atom or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ]

【００５０】式（１７）のイリジウムの二核錯体は公知
の方法（S. Lamansky et al., Inorganic Chemistry, 4
0, 1704 (2001)）により合成することができる。式（１
７）のＲ1〜Ｒ24としては水素原子、ハロゲン原子、ニ
トロ基、アミノ基、スルホン酸基、スルホン酸メチル等
のスルホン酸エステル基、メチル、エチル、プロピル、
イソプロピル、ブチル、イソブチル、ターシャリーブチ
ル、アミル、ヘキシル等のアルキル基、またメトキシ、
エトキシ、プロポキシ、イソブトキシ、ターシャリーブ
トキシ等のアルコキシ基、更にはアセトキシ基、プロポ
キシカルボニル基などのエステル基等の有機基を挙げる
ことができる。また、これらの有機基は、更にハロゲン
原子、ニトロ基、アミノ基等の置換基を有していてもよ
い。The iridium binuclear complex of the formula (17) can be prepared by a known method (S. Lamansky et al., Inorganic Chemistry, 4).
0, 1704 (2001)). Expression (1
As R 1 to R 24 in 7), a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonate ester group such as methyl sulfonate, methyl, ethyl, propyl,
Alkyl groups such as isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, methoxy,
Examples thereof include alkoxy groups such as ethoxy, propoxy, isobutoxy and tert-butoxy, and organic groups such as acetoxy group and ester group such as propoxycarbonyl group. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group or an amino group.

【００５１】式（１８）で示される化合物の置換基
Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能基を有す
る置換基であり、式（１）の説明と同じものを意味す
る。また、式（１８）で示される化合物の置換基Ｘ1、
Ｙ1、Ｚ1のうちの重合性官能基を有しない置換基も式
（１）の場合と同様である。At least one of the substituents X 1 , Y 1 and Z 1 of the compound represented by the formula (18) is a substituent having a polymerizable functional group, and has the same meaning as described in the formula (1). . Further, the substituent X 1 of the compound represented by the formula (18),
The substituent having no polymerizable functional group in Y 1 and Z 1 is the same as in the case of the formula (1).

【００５２】本発明による重合性化合物の第２の合成方
法は、式（１７）で示されるイリジウムの二核錯体と式
（１９）で示される反応性置換基を有する化合物を反応
させることにより反応性置換基を有する単核のイリジウ
ム錯体を中間体として得、この中間体の反応性置換基と
重合性置換基を有する化合物を反応させることにより単
核イリジウム錯体部分を含む重合性化合物を得る方法で
ある。The second method for synthesizing the polymerizable compound according to the present invention is to react the dinuclear complex of iridium represented by the formula (17) with a compound having a reactive substituent represented by the formula (19). Method for obtaining a polymerizable compound containing a mononuclear iridium complex moiety by obtaining a mononuclear iridium complex having a polymerizable substituent as an intermediate and reacting the reactive substituent of the intermediate with a compound having a polymerizable substituent Is.

【化５２】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕[Chemical 52] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ]

【化５３】 〔式中、Ｘ2、Ｙ2、Ｚ2の少なくとも１つは反応性置換
基、Ｘ2、Ｙ2、Ｚ2のうちの残りはそれぞれ独立に水素
原子またはヘテロ原子を有してもよい炭素数１〜２０の
有機基を表す。〕[Chemical 53] [In the formula, at least one of X 2 , Y 2 and Z 2 is a reactive substituent, and the rest of X 2 , Y 2 and Z 2 are each independently a carbon atom which may have a hydrogen atom or a hetero atom. Represents an organic group of the number 1 to 20. ]

【００５３】式（１９）のＸ2、Ｙ2、Ｚ2の少なくとも
１つは反応性置換基であり、水酸基などの官能基を有す
る。官能基としては水酸基、アミノ基、カルボキシル基
などを例示することができるが、何らこれに限定される
ものではない。これら官能基を有する反応性置換基とし
ては水酸基、ヒドロキシアルキル基、ヒドロキシフェニ
ル基などが挙げられる。At least one of X 2 , Y 2 and Z 2 in the formula (19) is a reactive substituent and has a functional group such as a hydroxyl group. Examples of the functional group include, but are not limited to, a hydroxyl group, an amino group, a carboxyl group and the like. Examples of the reactive substituent having these functional groups include a hydroxyl group, a hydroxyalkyl group and a hydroxyphenyl group.

【００５４】また、この反応性置換基は保護基で保護さ
れていてもよい。尚、この場合は保護基により保護され
たまま反応を行って単核イリジウム錯体を得た後、脱保
護により反応性置換基を有する単核イリジウム錯体を中
間体として得る。その後、この中間体の反応性置換基と
重合性官能基を有する化合物と反応させることにより、
単核イリジウム錯体部分を含む重合性化合物を得る。な
お、これら反応性置換基の官能基としては前述の重合性
官能基は除かれる。Further, this reactive substituent may be protected by a protecting group. In this case, the mononuclear iridium complex is obtained by carrying out the reaction while being protected by the protecting group, and then deprotected to obtain the mononuclear iridium complex having a reactive substituent as an intermediate. Then, by reacting with a compound having a reactive functional group and a polymerizable functional group of this intermediate,
A polymerizable compound containing a mononuclear iridium complex portion is obtained. The functional groups of these reactive substituents exclude the above-mentioned polymerizable functional groups.

【００５５】式（１９）で示される化合物の置換基
Ｘ2、Ｙ2、Ｚ2のうちの反応性置換基でない置換基とし
ては水素原子、ハロゲン原子、メチル、エチル、プロピ
ル、イソプロピル、ブチル、イソブチル、ターシャリー
ブチル、アミル、ヘキシル等のアルキル基、またメトキ
シ、エトキシ、プロポキシ、イソブトキシ、ターシャリ
ーブトキシ等のアルコキシ基、アセトキシ基、プロポキ
シカルボニル基などのエステル基、アリール基等の有機
基を挙げることができる。また、これらの有機基は、更
にハロゲン原子等の置換基を有していてもよい。The substituent which is not a reactive substituent among the substituents X 2 , Y 2 and Z 2 of the compound represented by the formula (19) is a hydrogen atom, a halogen atom, methyl, ethyl, propyl, isopropyl, butyl, Examples include alkyl groups such as isobutyl, tert-butyl, amyl, and hexyl; alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, and tert-butoxy; ester groups such as acetoxy group and propoxycarbonyl group; and organic groups such as aryl group. be able to. Moreover, these organic groups may further have a substituent such as a halogen atom.

【００５６】イリジウム二核錯体と反応性置換基を有す
る式（１９）で示される化合物との反応で得られる反応
性置換基を有する単核イリジウム錯体と反応させる重合
性官能基を有する化合物は重合性の基以外に式（１９）
の反応性置換基Ｘ2、Ｙ2、Ｙ 3と反応する基を有する官
能基を有して必要がある。本発明による重合性化合物の
第２の合成法による場合には式（１７）のＲ1〜Ｒ24は
上記の単核イリジウム錯体と反応させる重合性官能基を
有する化合物と反応しない基を選択しておく必要があ
る。Having iridium binuclear complex and reactive substituent
The reaction obtained by the reaction with a compound represented by the formula (19)
Polymerization by Reaction with Mononuclear Iridium Complex Having a Hydrophilic Substituent
The compound having a functional group is represented by the formula (19) in addition to the polymerizable group.
Reactive Substituent X of2, Y2, Y 3An officer having a group that reacts with
It is necessary to have a functional group. Of the polymerizable compound according to the present invention
In the case of the second synthesis method, R in the formula (17)1~ Rtwenty fourIs
The polymerizable functional group to react with the mononuclear iridium complex
It is necessary to select a group that does not react with the compound
It

【００５７】上記単核イリジウム錯体と反応させる重合
性官能基を有する化合物としては重合性酸塩化物や重合
性イソシアネートを例示することができるが、何らこれ
らに限定されるものではない。これらの化合物における
重合性官能基は、ラジカル重合性、カチオン重合性、ア
ニオン重合性、付加重合性、縮合重合性のいずれであっ
てもよいが、ラジカル重合性の官能基が好ましい。この
重合性官能基としてはビニル基、アリル基、アルケニル
基、アクリレート基、メタクリレート基、メタクリロイ
ルオキシエチルカルバメート基等のウレタン（メタ）ア
クリレート基、スチリル基及びその誘導体、ビニルアシ
ド基及びその誘導体など有するものを挙げることができ
る。これらの重合性官能基の中で、その重合性という観
点から、アクリレート基、メタアクリレート基、ウレタ
ン（メタ）アクリレート基が好ましい。具体的には、重
合性酸塩化物としてはアクリル酸クロライド、メタクリ
ル酸クロライド等が挙げられ、重合性イソシアネートと
してはメタクリロイルイソシアネート、メタクリロイル
オキシエチルイソシアネート等が挙げられる。なお、本
発明の化合物を示す式（１）などの化学式は金属錯体構
造を表し、Ｏ−Ｃ−Ｃ−Ｏは共鳴構造を表すが、化学的
に許容される構造を含むことは言うまでもない。Examples of the compound having a polymerizable functional group that reacts with the mononuclear iridium complex include a polymerizable acid chloride and a polymerizable isocyanate, but the compound is not limited thereto. The polymerizable functional group in these compounds may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable, but a radical polymerizable functional group is preferable. This polymerizable functional group has a vinyl group, an allyl group, an alkenyl group, an acrylate group, a methacrylate group, a urethane (meth) acrylate group such as a methacryloyloxyethyl carbamate group, a styryl group and its derivative, a vinyl acid group and its derivative, etc. Can be mentioned. Among these polymerizable functional groups, an acrylate group, a methacrylate group, and a urethane (meth) acrylate group are preferable from the viewpoint of the polymerizability. Specifically, examples of the polymerizable acid chloride include acrylic acid chloride and methacrylic acid chloride, and examples of the polymerizable isocyanate include methacryloyl isocyanate and methacryloyloxyethyl isocyanate. Chemical formulas such as formula (1) representing the compound of the present invention represent a metal complex structure, and O—C—C—O represents a resonance structure, but needless to say, it includes a chemically acceptable structure.

【００５８】[0058]

【実施例】以下に本発明について代表的な例を示し、更
に具体的に説明する。尚、これらは説明のための単なる
例示であって、本発明は何らこれらに限定されるもので
はない。The present invention will be described in more detail below by showing typical examples. Note that these are merely examples for description, and the present invention is not limited to these.

【００５９】＜測定装置等＞ １）1Ｈ−ＮＭＲ 日本電子（株）製 ＪＮＭ ＥＸ２７０ ２７０Ｍｚ 溶媒：重クロロホルムまたは重ジメチルス
ルホシキド ２）元素分析装置 ＲＥＣ０社製 ＣＨＮＳ−９３２型<Measurement device, etc.> 1) 1H-NMR JNM EX270 270Mz manufactured by JEOL Ltd. Solvent: deuterated chloroform or deuterated dimethylsulfoxide 2) Elemental analysis device REC0 CHNS-932 type

【００６０】＜試薬類＞特に断らない限り、市販品（特
級）を精製することなく使用した。<Reagents> Unless otherwise specified, commercially available products (special grade) were used without purification.

【００６１】（実施例１）重合性化合物：（８−ノネン
−２，４−ジオナート）ビス（２−フェニルピリジン）
イリジウム（ＩＩＩ）（以下Ｉｒ（ｐｐｙ）2（１−Ｂ
ｕ−ａｃａｃ）と略す）の合成 スキーム（１Ａ）に示すように、常法に従い合成したビ
ス（μ−クロロ）テトラキス（２−フェニルピリジン）
ジイリジウム（ＩＩＩ）（以下［Ｉｒ（ｐｐｙ）2Ｃ
ｌ］2と略す）と、公知の方法（H. Gerlach et al., He
lv. Chim. Acta, 60, 638 (1977)）により合成した８−
ノネン−２，４−ジオンを反応させてＩｒ（ｐｐｙ）2
（１−Ｂｕ−ａｃａｃ）を合成した。即ち、［Ｉｒ（ｐ
ｐｙ）2Ｃｌ］2 ２６１ｍｇ（０．２４ｍｍｏｌ）を３
０ｍｌの窒素ガスで脱気したメタノール中に懸濁させ、
８−ノネン−２，４−ジオン８７ｍｇ（０．５６ｍｍｏ
ｌ）とトリエチルアミン７６ｍｇ（０．７５ｍｍｏｌ）
を加えて油浴上で3時間加熱還流させた。得られた薄黄
色の反応液を室温にまで冷却し、ロータリーエバポレー
タで濃縮した。次に希塩酸水溶液２００ｍｌとクロロホ
ルム５０ｍｌを加えて激しく攪拌し、クロロホルム層を
分取して硫酸マグネシウムで乾燥後、減圧して溶媒を留
去した。得られた黄色の残渣をジクロロメタンに溶解
し、ジクロロメタンを溶出液とするシリカゲルカラムク
ロマトグラフィーで薄黄色の主生成物を分取した。この
溶液を減圧して濃縮後、少量のヘキサンを加えて−２０
℃に冷却し、目的とするＩｒ（ｐｐｙ）2（１−Ｂｕ−
ａｃａｃ）２７０ｍｇ（０．４１ｍｍｏｌ）を薄黄色結
晶として得た（収率８５％）。同定はＣＨＮ元素分析、
1Ｈ−ＮＭＲで行った。(Example 1) Polymerizable compound: (8-nonene-2,4-dionate) bis (2-phenylpyridine)
Iridium (III) (hereinafter Ir (ppy) 2 (1-B
abbreviated as u-acac)), and bis (μ-chloro) tetrakis (2-phenylpyridine) synthesized by a conventional method, as shown in the synthetic scheme (1A).
Diiridium (III) (hereinafter [Ir (ppy) 2 C
l] 2 ) and known methods (H. Gerlach et al., He
lv. Chim. Acta, 60, 638 (1977))
Nonene-2,4-dione is reacted to produce Ir (ppy) 2
(1-Bu-acac) was synthesized. That is, [Ir (p
py) 2 Cl] 2 261 mg (0.24 mmol) 3
Suspend in methanol degassed with 0 ml of nitrogen gas,
87 mg of 8-nonene-2,4-dione (0.56 mmo
l) and 76 mg (0.75 mmol) of triethylamine
Was added and the mixture was heated to reflux on an oil bath for 3 hours. The resulting pale yellow reaction solution was cooled to room temperature and concentrated on a rotary evaporator. Next, 200 ml of dilute hydrochloric acid aqueous solution and 50 ml of chloroform were added and vigorously stirred, the chloroform layer was separated and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained yellow residue was dissolved in dichloromethane, and the pale yellow main product was separated by silica gel column chromatography using dichloromethane as an eluent. After this solution was depressurized and concentrated, a small amount of hexane was added to it and
The target Ir (ppy) 2 (1-Bu-
270 mg (0.41 mmol) of acac) was obtained as pale yellow crystals (yield 85%). Identification is CHN elemental analysis,
It was performed by 1 H-NMR.

【００６２】1H NMR (CDCl3): d 8.49 (d, J = 5.7 Hz,
2 H, ppy), 7.83 (t, J = 7.8 Hz, 2H, ppy), 7.70
(m, 2 H, ppy), 7.54 (t, J = 6.8 Hz, 2 H, ppy), 7.1
0 (m, 2H, ppy), 6.80 (t, J = 7.3 Hz, 2 H, ppy), 6.
68 (m, 2 H, ppy), 6.35 (d, J= 6.2 Hz, 1 H, ppy),
6.25 (d, J = 6.2 Hz, 1 H, ppy), 5.61 (m, 1 H, -CH=
CH2), 5.19 (s, 1 H, diketonate-methine), 4.86 (m,
2 H, -CH=CH2), 1.99 (t, J = 7.3 Hz, 2 H, methylen
e), 1.79 (s, 3 H, CH3), 1.72 (m, 2 H, methylene),
1.38 (m, 2 H, methylene). E.A.: Calcd for C31H29I
rN2O2: C, 56.95;H, 4.47; N, 4.28. Found: C, 55.8
4; H, 4.32; N, 3.97. 1 H NMR (CDCl 3 ): d 8.49 (d, J = 5.7 Hz,
2 H, ppy), 7.83 (t, J = 7.8 Hz, 2H, ppy), 7.70
(m, 2 H, ppy), 7.54 (t, J = 6.8 Hz, 2 H, ppy), 7.1
0 (m, 2H, ppy), 6.80 (t, J = 7.3 Hz, 2 H, ppy), 6.
68 (m, 2 H, ppy), 6.35 (d, J = 6.2 Hz, 1 H, ppy),
6.25 (d, J = 6.2 Hz, 1 H, ppy), 5.61 (m, 1 H, -CH =
CH 2 ), 5.19 (s, 1 H, diketonate-methine), 4.86 (m,
2 H, -CH = CH 2 ), 1.99 (t, J = 7.3 Hz, 2 H, methylen
e), 1.79 (s, 3 H, CH 3 ), 1.72 (m, 2 H, methylene),
1.38 (m, 2 H, methylene) .EA: Calcd for C 31 H 29 I
rN 2 O 2 : C, 56.95; H, 4.47; N, 4.28. Found: C, 55.8
4; H, 4.32; N, 3.97.

【００６３】[0063]

【化５４】 [Chemical 54]

【００６４】（実施例２）重合性化合物：［６−（４−
ビニルフェニル）−２，４−ヘキサンジオナート］ビス
（２−フェニルピリジン）イリジウム（ＩＩＩ）（以下
Ｉｒ（ｐｐｙ）2［１−（Ｓｔ−Ｍｅ）−ａｃａｃ］と
略す）の合成 スキーム（２Ａ）に示すように、アセチルアセトンと４
−ビニルベンジルクロライドを反応させて６−（４−ビ
ニルフェニル）−２，４−ヘキサジオンを合成した。即
ち、水素化ナトリウム１．２３ｇ（６０％ ｉｎ ｏｉ
ｌ）（３１ｍｍｏｌ）を窒素雰囲気下で秤量し、これに
乾燥テトラヒドロフラン（以下ＴＨＦと略す）６０ｍｌ
を加えて氷浴で０℃に冷却した。この懸濁液にアセチル
アセトン２．５ｇ（２４ｍｍｏｌ）とヘキサメチルホス
ホリックトリアミド１ｍｌの混合溶液を滴下すると無色
の沈殿が生成した。０℃で１０分間攪拌した後、ｎ−ブ
チルリチウムのヘキサン溶液（１．６Ｍ）１７．５ｍｌ
（２８ｍｍｏｌ）を滴下すると沈殿が溶解し、更に０℃
で２０分間攪拌した。得られた薄黄色の溶液に４−ビニ
ルベンジルクロライド４．０ｇ（２６ｍｍｏｌ）を滴下
し、反応液を室温に戻して２０分間攪拌後、希塩酸を加
えて水層を酸性にした。有機層を飽和塩化ナトリウム水
溶液で洗浄し、硫酸マグネシウムで乾燥した後、ロータ
リーエバポレータで溶媒を留去した。得られた反応混合
物をシリカゲルカラムに加えてヘキサン／ジクロロメタ
ンの１：１（体積比）混合溶媒で展開し、主生成物を分
取した。得られた溶液から減圧で溶媒を留去することに
より、目的とする６−（４−ビニルフェニル）−２，４
−ヘキサジオン３．０ｇ（１４ｍｍｏｌ）を褐色の液体
として得た。収率５６％。同定はＣＨＮ元素分析、1Ｈ
−ＮＭＲで行った。(Example 2) Polymerizable compound: [6- (4-
Vinylphenyl) -2,4-hexanedionate] bis (2-phenylpyridine) iridium (III) (hereinafter abbreviated as Ir (ppy) 2 [1- (St-Me) -acac]) (2A) As shown in,
-Vinylbenzyl chloride was reacted to synthesize 6- (4-vinylphenyl) -2,4-hexadione. That is, 1.23 g of sodium hydride (60% in oi
1) (31 mmol) was weighed under a nitrogen atmosphere, and 60 ml of dry tetrahydrofuran (hereinafter abbreviated as THF) was added thereto.
Was added and the mixture was cooled to 0 ° C. in an ice bath. When a mixed solution of 2.5 g (24 mmol) of acetylacetone and 1 ml of hexamethylphosphoric triamide was added dropwise to this suspension, a colorless precipitate was produced. After stirring at 0 ° C for 10 minutes, 17.5 ml of a hexane solution of n-butyllithium (1.6M).
The precipitate dissolves when (28 mmol) is added dropwise, and at 0 ° C.
And stirred for 20 minutes. To the resulting pale yellow solution, 4.0 g (26 mmol) of 4-vinylbenzyl chloride was added dropwise, the reaction solution was returned to room temperature and stirred for 20 minutes, and then diluted hydrochloric acid was added to acidify the aqueous layer. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and then the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was added to a silica gel column and developed with a 1: 1 (volume ratio) mixed solvent of hexane / dichloromethane to separate the main product. By distilling off the solvent from the obtained solution under reduced pressure, the target 6- (4-vinylphenyl) -2,4 was obtained.
-3.0 g (14 mmol) hexadione was obtained as a brown liquid. Yield 56%. Identification is by CHN elemental analysis, 1 H
-Performed by NMR.

【００６５】1H NMR (CDCl3): enol; d 7.33 (d, J =
8.1 Hz, 2 H, aromatic), 7.14 (d, J= 8.4 Hz, 2 H, a
romatic), 6.68 (dd, J = 8.1 Hz, 1 H, vinylic), 5.7
0 (d,J = 17.0 Hz, 1 H, vinylic), 5.46 (s, 1 H, dik
etonate-methine), 5.20 (d,J = 11.1 Hz, 1 H, vinyli
c), 2.91 (t, J = 5.7 Hz, 2 H, methylene), 2.58 (t,
J = 7.3 Hz, 2 H, methylene), 2.03 (s, 3 H, methy
l). keto; d 7.33 (d,J = 8.1 Hz, 2 H, aromatic),
7.14 (d, J = 8.4 Hz, 2 H, aromatic), 6.68 (dd, J =
8.1 Hz, 1 H, vinylic), 5.70 (d, J = 17.0 Hz, 1 H,
vinylic), 5.20(d, J = 11.1 Hz, 1 H, vinylic), 3.5
3 (s, 2 H, C(=O)CH2C(=O)), 2.89 (m,4 H, ethylene),
2.19 (s, 3 H, methyl). enol : keto = 6 : 1. E.
A.: Calcdfor C14H9O2: C, 77.75; H, 7.46. Found:
C, 77.49; H, 7.52. 1 H NMR (CDCl 3 ): enol; d 7.33 (d, J =
8.1 Hz, 2 H, aromatic), 7.14 (d, J = 8.4 Hz, 2 H, a
romatic), 6.68 (dd, J = 8.1 Hz, 1 H, vinylic), 5.7
0 (d, J = 17.0 Hz, 1 H, vinylic), 5.46 (s, 1 H, dik
etonate-methine), 5.20 (d, J = 11.1 Hz, 1 H, vinyli
c), 2.91 (t, J = 5.7 Hz, 2 H, methylene), 2.58 (t,
J = 7.3 Hz, 2 H, methylene), 2.03 (s, 3 H, methy
l). keto; d 7.33 (d, J = 8.1 Hz, 2 H, aromatic),
7.14 (d, J = 8.4 Hz, 2 H, aromatic), 6.68 (dd, J =
8.1 Hz, 1 H, vinylic), 5.70 (d, J = 17.0 Hz, 1 H,
vinylic), 5.20 (d, J = 11.1 Hz, 1 H, vinylic), 3.5
3 (s, 2 H, C (= O) CH 2 C (= O)), 2.89 (m, 4 H, ethylene),
2.19 (s, 3 H, methyl) .enol: keto = 6: 1.E.
A .: Calcdfor C 14 H 9 O 2 : C, 77.75; H, 7.46. Found:
C, 77.49; H, 7.52.

【００６６】[0066]

【化５５】 [Chemical 55]

【００６７】次いで、スキーム（２Ｂ）に示すように、
この６−（４−ビニルフェニル）−２，４−ヘキサンジ
オンと常法に従い合成した［Ｉｒ（ｐｐｙ）2Ｃｌ］2を
反応させてＩｒ（ｐｐｙ）2［１−（Ｓｔ−Ｍｅ）−ａ
ｃａｃ］を合成した。即ち、［Ｉｒ（ｐｐｙ）2Ｃｌ］2
３４２ｍｇ（０．３２ｍｍｏｌ）、炭酸ナトリウム１５
８ｍｇ（１．５ｍｍｏｌ）および２，６−ジ−ｔｅｒｔ
−ブチル−４−メチルフェノール５ｍｇ（０．０２３ｍ
ｍｏｌ）を5 mlのＮ，Ｎ−ジメチルホルムアミド（以下
ＤＭＦと略す）に溶解し、これに６−（４−ビニルフェ
ニル）−２，４−ヘキサンジオン２１０ｍｇ（０．９７
ｍｍｏｌ）を加えて６５℃で1時間加熱攪拌した。次に
室温まで冷却した反応溶液に希塩酸水溶液を加えた後、
薄黄色の成分をクロロホルムで抽出した。ロータリーエ
バポレータを用いて溶媒を留去後、残渣を少量のジクロ
ロメタンに溶解し、シリカゲルカラムクロマトグラフィ
ー(展開液：ジクロロメタン)で黄色の主生成物を分取し
た。この溶液を減圧乾固し、ジクロロメタン−ヘキサン
混合溶液を加えて−２０℃で再結晶を行い、目的とする
Ｉｒ（ｐｐｙ）2［１−（Ｓｔ−Ｍｅ）−ａｃａｃ］３
５４ｍｇ（０．４９ｍｍｏｌ）を薄黄色結晶として得
た。収率７８％。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲ
で行った。Then, as shown in Scheme (2B),
This 6- (4-vinylphenyl) -2,4-hexanedione was reacted with [Ir (ppy) 2 Cl] 2 synthesized according to a conventional method to produce Ir (ppy) 2 [1- (St-Me) -a.
cac] was synthesized. That is, [Ir (ppy) 2 Cl] 2
342 mg (0.32 mmol), sodium carbonate 15
8 mg (1.5 mmol) and 2,6-di-tert
-Butyl-4-methylphenol 5 mg (0.023 m
mol) was dissolved in 5 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), and 210 mg (0.97 of 6- (4-vinylphenyl) -2,4-hexanedione) was dissolved therein.
mmol) was added and the mixture was heated with stirring at 65 ° C. for 1 hour. Next, after adding a dilute hydrochloric acid aqueous solution to the reaction solution cooled to room temperature,
The pale yellow component was extracted with chloroform. After the solvent was distilled off using a rotary evaporator, the residue was dissolved in a small amount of dichloromethane and the yellow main product was separated by silica gel column chromatography (developing solution: dichloromethane). This solution was dried under reduced pressure, a dichloromethane-hexane mixed solution was added, and recrystallization was performed at -20 ° C to obtain the desired Ir (ppy) 2 [1- (St-Me) -acac] 3
54 mg (0.49 mmol) was obtained as pale yellow crystals. Yield 78%. Identification is by CHN elemental analysis, 1 H-NMR
I went there.

【００６８】1H NMR (CDCl3): d 8.47 (d, J = 5.7 Hz,
1 H, ppy), 8.21 (d, J = 5.7 Hz, 1H, ppy), 7.9 7.
5 (m, 6 H, ppy), 7.18 (d, J = 8.1 Hz, 2 H, stylyl-
aromatic), 7.00 (m, 2 H, ppy), 6.89 (d, J = 8.1 H
z, 2 H, stylyl-aromatic), 6.75 (m, 5 H, ppy and vi
nylic), 6.28 (t, J = 7.3 Hz, 2 H, ppy), 7.67 (d, J
= 17.6 Hz, 1 H, vinylic), 5.19 (d, J = 9.5 Hz, 1
H, vinylic), 5.17 (s,1 H, diketonate-methine), 2.6
0 (t, J = 7.3 Hz, 2 H, ethylene), 2.36 (m,2 H, eth
ylene), 1.75 (s, 3 H, methyl). E.A.: Calcd for C36
H31IrN2O2: C,60.40; H, 4.36; N, 3.91. Found: C, 6
1.35; H, 4.34; N, 3.83. 1 H NMR (CDCl 3 ): d 8.47 (d, J = 5.7 Hz,
1 H, ppy), 8.21 (d, J = 5.7 Hz, 1H, ppy), 7.9 7.
5 (m, 6 H, ppy), 7.18 (d, J = 8.1 Hz, 2 H, stylyl-
aromatic), 7.00 (m, 2 H, ppy), 6.89 (d, J = 8.1 H
z, 2 H, stylyl-aromatic), 6.75 (m, 5 H, ppy and vi
nylic), 6.28 (t, J = 7.3 Hz, 2 H, ppy), 7.67 (d, J
= 17.6 Hz, 1 H, vinylic), 5.19 (d, J = 9.5 Hz, 1
H, vinylic), 5.17 (s, 1 H, diketonate-methine), 2.6
0 (t, J = 7.3 Hz, 2 H, ethylene), 2.36 (m, 2 H, eth
ylene), 1.75 (s, 3 H, methyl). EA: Calcd for C 36
H 31 IrN 2 O 2 : C, 60.40; H, 4.36; N, 3.91.Found: C, 6
1.35; H, 4.34; N, 3.83.

【００６９】[0069]

【化５６】 [Chemical 56]

【００７０】（実施例３）重合性化合物：（９−アクリ
ロイルオキシ−２，４−ノナンジオナート）ビス（２−
フェニルピリジン）イリジウム（ＩＩＩ）（以下Ｉｒ
（ｐｐｙ）2［１−（Ａ−Ｂｕ）−ａｃａｃ］と略す）
の合成 スキーム（３Ａ）に示すように、常法に従い、（９−ヒ
ドロキシ−２，４−ノナンジオナート）ビス（２−フェ
ニルピリジン）イリジウム（以下Ｉｒ（ｐｐｙ）2［１
−（ＯＨ−Ｂｕ）−ａｃａｃ］と略す）を合成した。即
ち、実施例１と同様にして合成したＩｒ（ｐｐｙ）
2（１−Ｂｕ−ａｃａｃ）１６７ｍｇ（０．２６ｍｍｏ
ｌ）をＴＨＦ１０ｍｌに溶解し、これに９−ボラビシク
ロ［３．３．１］ノナン（以下９−ＢＢＮと略す）の
０．５Ｍ ＴＨＦ溶液１．０ｍｌ（０．５ｍｍｏｌ）を
滴下した。この溶液を２５分間加熱還流した後、得られ
た反応混合物に３Ｍ ＮａＯＨ水溶液０．２ｍｌ（０．
６０ｍｍｏｌ）と３５％Ｈ2Ｏ2溶液０．０６０ｍｌ
（０．６２ｍｍｏｌ）を順に加えて室温で１２時間攪拌
した。次に２０ｍｌの水を加えてロータリーエバポレー
タで濃縮し、クロロホルムを加えてよく振盪した後、有
機層を減圧乾固した。得られた黄色固体を少量のジクロ
ロメタンに溶解してシリカゲルカラムに加え、まずジク
ロロメタンを流して溶出した不純物を除いた。引き続き
ジクロロメタン／酢酸エチルの１：１（体積比）混合溶
媒を流すと薄黄色の錯体が溶出した。これを回収して減
圧乾燥し、ジクロロメタン／ヘキサン混合溶液から−２
０℃で再結晶することによりＩｒ（ｐｐｙ）2［１−
（ＯＨ−Ｂｕ）−ａｃａｃ］ ２３ｍｇ（０．０３４ｍ
ｍｏｌ）を薄黄色の固体として得た。収率１３％。同定
はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。Example 3 Polymerizable compound: (9-acryloyloxy-2,4-nonanedionate) bis (2-
Phenylpyridine) iridium (III) (hereinafter Ir
(Ppy) 2 [1- (A-Bu) -acac] abbreviated)
As shown in Synthesis Scheme (3A) of (9-hydroxy-2,4-nonanedionate) bis (2-phenylpyridine) iridium (hereinafter Ir (ppy) 2 [1
-(OH-Bu) -acac] was synthesized. That is, Ir (ppy) synthesized in the same manner as in Example 1.
2 (1-Bu-acac) 167 mg (0.26 mmo
l) was dissolved in 10 ml of THF, and 1.0 ml (0.5 mmol) of a 0.5 M THF solution of 9-borabicyclo [3.3.1] nonane (hereinafter abbreviated as 9-BBN) was added dropwise thereto. This solution was heated under reflux for 25 minutes, and then the resulting reaction mixture was added with 0.2 ml of a 3M aqueous NaOH solution (0.
60 mmol) and 35% H 2 O 2 solution 0.060 ml
(0.62 mmol) were added in that order and the mixture was stirred at room temperature for 12 hours. Next, 20 ml of water was added, the mixture was concentrated with a rotary evaporator, chloroform was added, and the mixture was shaken well, and then the organic layer was dried under reduced pressure. The obtained yellow solid was dissolved in a small amount of dichloromethane and added to a silica gel column, and dichloromethane was first run to remove the eluted impurities. Subsequently, when a 1: 1 (volume ratio) mixed solvent of dichloromethane / ethyl acetate was flown, the pale yellow complex was eluted. This was collected, dried under reduced pressure, and mixed with a dichloromethane / hexane mixed solution to give -2.
By recrystallizing at 0 ° C., Ir (ppy) 2 [1-
(OH-Bu) -acac] 23 mg (0.034 m
mol) was obtained as a pale yellow solid. Yield 13%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００７１】1H NMR (CDCl3): d 8.50 (d, J = 5.9 Hz,
2 H, ppy), 7.82 (t, J = 7.0 Hz, 2H, ppy), 7.72
(t, J = 7.3 Hz, 2 H, ppy), 7.55 (t, J = 7.0 Hz, 2
H, ppy), 7.12 (t, J = 5.9 Hz, 2 H, ppy), 6.81 (t,
J = 7.6 Hz, 2 H, ppy), 6.69 (t, J = 7.3 Hz, 2 H, p
py), 6.31 (d, J = 5.9 Hz, 1 H, ppy), 6.26 (d, J =
5.9 Hz, 1 H, ppy), 5.19 (s, 1 H, diketonate-methin
e), 3.44 (t, J = 7.0 Hz, 2 H, CH2OH), 1.98 (t, J =
7.0 Hz, 2 H, methylene), 1.79 (s, 3 H, methyl),
1.34 (m, 4 H, methylene), 1.05 (m, 2 H, methylen
e). E.A.: Calcd forC31H31IrN2O3: C, 55.42; H, 4.6
5; N, 4.17. Found: C, 55.76; H, 4.71; N,4.19. 1 H NMR (CDCl 3 ): d 8.50 (d, J = 5.9 Hz,
2 H, ppy), 7.82 (t, J = 7.0 Hz, 2H, ppy), 7.72
(t, J = 7.3 Hz, 2 H, ppy), 7.55 (t, J = 7.0 Hz, 2
H, ppy), 7.12 (t, J = 5.9 Hz, 2 H, ppy), 6.81 (t,
J = 7.6 Hz, 2 H, ppy), 6.69 (t, J = 7.3 Hz, 2 H, p
py), 6.31 (d, J = 5.9 Hz, 1 H, ppy), 6.26 (d, J =
5.9 Hz, 1 H, ppy), 5.19 (s, 1 H, diketonate-methin
e), 3.44 (t, J = 7.0 Hz, 2 H, CH 2 OH), 1.98 (t, J =
7.0 Hz, 2 H, methylene), 1.79 (s, 3 H, methyl),
1.34 (m, 4 H, methylene), 1.05 (m, 2 H, methylen
e). EA: Calcd for C 31 H 31 IrN 2 O 3 : C, 55.42; H, 4.6
5; N, 4.17. Found: C, 55.76; H, 4.71; N, 4.19.

【００７２】[0072]

【化５７】 [Chemical 57]

【００７３】次いで、スキーム（３Ｂ）に示すように、
このＩｒ（ｐｐｙ）2［１−（ＯＨ−Ｂｕ）−ａｃａ
ｃ］とアクリル酸クロライドを反応させることによりＩ
ｒ（ｐｐｙ）2［１−（Ａ−Ｂｕ）−ａｃａｃ］を合成
した。即ち、Ｉｒ（ｐｐｙ）2［１−（ＯＨ−Ｂｕ）−
ａｃａｃ］ ９５ｍｇ（０．１４ｍｍｏｌ）をジクロロ
メタン１０ｍｌに溶解し、これにトリエチルアミン０．
１０ｍｌ（０．７２ｍｍｏｌ）を加えた。この溶液にア
クリル酸クロライド０．０６０ｍｌ（０．７４ｍｍｏ
ｌ）を加えて室温で30分間攪拌した。次にメタノール１
ｍｌを加えた後、減圧下、溶媒を留去した。残渣をシリ
カゲルカラムに通して（展開液：ジクロロメタン）最初
に溶出した黄色の溶液を分取して減圧乾固し、ジクロロ
メタン−ヘキサン混合溶液から−２０℃で再結晶するこ
とにより目的とするＩｒ（ｐｐｙ）2［１−（Ａ−Ｂ
ｕ）−ａｃａｃ］ ９９ｍｇ（０．１４ｍｍｏｌ）を 薄
黄色の固体として得た。収率９６％。同定はＣＨＮ元素
分析、1Ｈ−ＮＭＲで行った。Then, as shown in Scheme (3B),
This Ir (ppy) 2 [1- (OH-Bu) -aca
c] by reacting acrylic acid chloride with I
r (ppy) 2 [1- (A-Bu) -acac] was synthesized. That is, Ir (ppy) 2 [1- (OH-Bu)-
acac] 95 mg (0.14 mmol) was dissolved in 10 ml of dichloromethane, and triethylamine (0.1.
10 ml (0.72 mmol) was added. 0.060 ml of acrylic acid chloride (0.74 mmo)
1) was added and the mixture was stirred at room temperature for 30 minutes. Then methanol 1
After adding ml, the solvent was distilled off under reduced pressure. The residue is passed through a silica gel column (developing solution: dichloromethane), and the yellow solution that is first eluted is collected, dried under reduced pressure, and recrystallized from a dichloromethane-hexane mixed solution at -20 ° C to obtain the desired Ir ( ppy) 2 [1- (AB
u) -acac] 99 mg (0.14 mmol) was obtained as a pale yellow solid. Yield 96%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００７４】1H NMR (CDCl3): d 8.50 (d, J = 5.9 Hz,
2 H, ppy), 7.80 (m, 4 H, ppy), 7.51 (t, J = 7.3 H
z, 2 H, ppy), 7.18 (t, J = 5.9 Hz, 2 H, ppy), 6.84
(t, J= 7.3 Hz, 2 H, ppy), 6.70 (t, J = 7.6 Hz, 2
H, ppy), 6.25 (m, 3 H, ppy+ vinylic), 6.12 (dd, J
= 15.6, 9.3 Hz, 1 H, vinylic), 5.75 (d, J = 9.3Hz,
1 H, vinylic), 5.17 (s, 1 H, diketonate-methine),
4.05 (t, J = 7.0 Hz, 2 H, -COOCH2-), 1.84 (t, J =
7.0 Hz, 2 H, methylene), 1.80 (s, 3 H, methyl),
1.34 (m, 4 H, methylene), 1.06 (m, 2 H, methylen
e). E.A.: Calcdfor C34H33IrN2O4: C, 56.26; H, 4.5
8; N, 3.86. Found: C, 56.55; H, 4.53; N, 3.60. 1 H NMR (CDCl 3 ): d 8.50 (d, J = 5.9 Hz,
2 H, ppy), 7.80 (m, 4 H, ppy), 7.51 (t, J = 7.3 H
z, 2 H, ppy), 7.18 (t, J = 5.9 Hz, 2 H, ppy), 6.84
(t, J = 7.3 Hz, 2 H, ppy), 6.70 (t, J = 7.6 Hz, 2
H, ppy), 6.25 (m, 3 H, ppy + vinylic), 6.12 (dd, J
= 15.6, 9.3 Hz, 1 H, vinylic), 5.75 (d, J = 9.3Hz,
1 H, vinylic), 5.17 (s, 1 H, diketonate-methine),
4.05 (t, J = 7.0 Hz, 2 H, -COOCH 2- ), 1.84 (t, J =
7.0 Hz, 2 H, methylene), 1.80 (s, 3 H, methyl),
1.34 (m, 4 H, methylene), 1.06 (m, 2 H, methylen
e). EA: Calcdfor C 34 H 33 IrN 2 O 4 : C, 56.26; H, 4.5
8; N, 3.86. Found: C, 56.55; H, 4.53; N, 3.60.

【００７５】[0075]

【化５８】 [Chemical 58]

【００７６】（実施例４）重合性化合物：｛１−［４−
（２−メタクリロイルオキシ）カルバモイルオキシフェ
ニル］−３−フェニル−１，３−プロパンジオナート｝
ビス（２−フェニルピリジン）イリジウム（ＩＩＩ）
（以下Ｉｒ（ｐｐｙ）2（ＭＯＩ−Ｐｈ−ａｃａｃ）と
略す）の合成 スキーム（４Ａ）に示すように、常法に従い合成したビ
ス（μ−クロロ）テトラキス（２−フェニルピリジン）
ジイリジウム（ＩＩＩ）（［Ｉｒ（ｐｐｙ）2Ｃｌ］2）
と、公知の方法（M. Cushman et al., Tetrahedron Let
t., 31, 6497(1990)）を参考に合成したｐ−ヒドロキシ
−ジベンゾイルメタンを反応させて［１−（４−ヒドロ
キシフェニル）−３−フェニル−１，３−プロパンジオ
ナート］ビス（２−フェニルピリジン）イリジウム（Ｉ
ＩＩ）（以下Ｉｒ（ｐｐｙ）2（ＯＨ−Ｐｈ−ａｃａ
ｃ）と略す）を合成した。即ち、［Ｉｒ（ｐｐｙ）2Ｃ
ｌ］2 １１２ｍｇ（０．１０ｍｍｏｌ）と炭酸ナトリ
ウム６４ｍｇ（０．６０ｍｍｏｌ）およびｐ−ヒドロキ
シ−ジベンゾイルメタン７６ｍｇ（０．３２ｍｍｏｌ）
をＤＭＦ１０ｍｌに溶解し、６０℃で０．５時間加熱攪
拌した。得られた反応溶液を１００ｍｌの希塩酸水溶液
中に注ぎ、クロロホルムでイリジウム錯体を抽出した。
ロータリーエバポレータを用いてクロロホルムを留去
し、残渣を少量のジクロロメタンに溶解してシリカゲル
カラムに加えた。ジクロロメタン／アセトンの３０：１
０（体積比）混合溶媒で展開するとオレンジ色の成分が
溶出してくるため、これを回収して減圧乾固した。得ら
れた固体を少量のジエチルエーテルに溶解し、ヘキサン
を加えて析出した錯体沈殿物を濾取して減圧乾燥するこ
とにより、目的とするＩｒ（ｐｐｙ）2（ＯＨ−Ｐｈ−
ａｃａｃ）１１１ｍｇ（０．１５ｍｍｏｌ）をオレンジ
色の固体として得た。収率７２％。同定はＣＨＮ元素分
析、1Ｈ−ＮＭＲで行った。Example 4 Polymerizable compound: {1- [4-
(2-methacryloyloxy) carbamoyloxyphenyl] -3-phenyl-1,3-propanedionate}
Bis (2-phenylpyridine) iridium (III)
(Hereinafter, abbreviated as Ir (ppy) 2 (MOI-Ph-acac)) As shown in the synthetic scheme (4A), bis (μ-chloro) tetrakis (2-phenylpyridine) synthesized by a conventional method.
Diiridium (III) ([Ir (ppy) 2 Cl] 2 )
And known methods (M. Cushman et al., Tetrahedron Let
t., 31, 6497 (1990)) and reacted with p-hydroxy-dibenzoylmethane to synthesize [1- (4-hydroxyphenyl) -3-phenyl-1,3-propanedionate] bis ( 2-phenylpyridine) iridium (I
II) (hereinafter Ir (ppy) 2 (OH-Ph-aca
abbreviated as c)) was synthesized. That is, [Ir (ppy) 2 C
l] 2 112 mg (0.10 mmol) and sodium carbonate 64 mg (0.60 mmol) and p-hydroxy-dibenzoylmethane 76 mg (0.32 mmol).
Was dissolved in 10 ml of DMF, and the mixture was heated with stirring at 60 ° C. for 0.5 hours. The obtained reaction solution was poured into 100 ml of a dilute hydrochloric acid aqueous solution, and the iridium complex was extracted with chloroform.
Chloroform was distilled off using a rotary evaporator, the residue was dissolved in a small amount of dichloromethane and added to a silica gel column. 30: 1 dichloromethane / acetone
When developed with a 0 (volume ratio) mixed solvent, an orange component was eluted, so this was collected and dried under reduced pressure. The obtained solid was dissolved in a small amount of diethyl ether, hexane was added, and the precipitated complex precipitate was collected by filtration and dried under reduced pressure to obtain the desired Ir (ppy) 2 (OH-Ph-
Acac) 111 mg (0.15 mmol) was obtained as an orange solid. Yield 72%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００７７】1H NMR (CDCl3): d 8.58 (d, 2 H, ppy),
7.9 6.7 (m, 21 H, ppy + phenyl),6.52 (s, 1 H, dik
etonate-methine), 6.37 (d, 2 H, ppy), 4.91 (s, 1
H, OH). E.A.: Calcd for C37H27IrN2O3: C, 60.07; H,
3.68; N, 3.79. Found: C,60.77; H, 3.75; N, 3.62. 1 H NMR (CDCl 3 ): d 8.58 (d, 2 H, ppy),
7.9 6.7 (m, 21 H, ppy + phenyl), 6.52 (s, 1 H, dik
etonate-methine), 6.37 (d, 2 H, ppy), 4.91 (s, 1
H, OH). EA: Calcd for C 37 H 27 IrN 2 O 3 : C, 60.07; H,
3.68; N, 3.79. Found: C, 60.77; H, 3.75; N, 3.62.

【００７８】[0078]

【化５９】 [Chemical 59]

【００７９】次いで、スキーム（４Ｂ）に示すように、
このＩｒ（ｐｐｙ）2（ＯＨ−Ｐｈ−ａｃａｃ）とメタ
クリロイルオキシエチルイソシアネート（商品名：ＭＯ
Ｉ、昭和電工製）を反応させることによりＩｒ（ｐｐ
ｙ）2（ＭＯＩ−Ｐｈ−ａｃａｃ）を合成した。即ち、
Ｉｒ（ｐｐｙ）2（ＯＨ−Ｐｈ−ａｃａｃ）１１０ｍｇ
（０．１５ｍｍｏｌ）をトルエン５０ｍｌに溶解し、こ
れに２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノ
ール（以下ＢＨＴと略す）５ｍｇ（０．０２３ｍｍｏ
ｌ）、ジブチル錫（ＩＶ）ジラウレート（以下ＤＢＴＬ
と略す）３２ｍｇ（０．０５１ｍｍｏｌ）及びＭＯＩ
１２１ｍｇ（０．７８ｍｍｏｌ）を加えて７０℃で6時
間加熱攪拌した。得られた反応混合物を室温にまで空冷
してシリカゲルカラムに加え、ジクロロメタン／アセト
ンの２０：１（体積比）混合溶媒で展開すると橙色の化
合物が溶出した。この溶液をロータリーエバポレータで
減圧乾固し、得られた固体を少量のジクロロメタンに溶
解してヘキサンを少しずつ加えると橙色の沈殿が析出し
た。これを濾取して減圧乾燥することにより、目的とす
るＩｒ（ｐｐｙ）2（ＭＯＩ−Ｐｈ−ａｃａｃ）１００
ｍｇ（０．１１ｍｍｏｌ）を橙色の固体として得た。収
率７５％。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行っ
た。Then, as shown in Scheme (4B),
This Ir (ppy) 2 (OH-Ph-acac) and methacryloyloxyethyl isocyanate (trade name: MO
Ir (pp, Showa Denko)
y) 2 (MOI-Ph-acac) was synthesized. That is,
Ir (ppy) 2 (OH-Ph-acac) 110 mg
(0.15 mmol) was dissolved in 50 ml of toluene, and 2,6-di-tert-butyl-4-methylphenol (hereinafter abbreviated as BHT) 5 mg (0.023 mmo).
l), dibutyltin (IV) dilaurate (hereinafter DBTL
32 mg (0.051 mmol) and MOI
121 mg (0.78 mmol) was added, and the mixture was heated with stirring at 70 ° C. for 6 hours. The obtained reaction mixture was air-cooled to room temperature, added to a silica gel column, and developed with a dichloromethane / acetone 20: 1 (volume ratio) mixed solvent to elute an orange compound. This solution was dried under reduced pressure with a rotary evaporator, the obtained solid was dissolved in a small amount of dichloromethane, and hexane was added little by little, whereby an orange precipitate was deposited. This is filtered and dried under reduced pressure to obtain the desired Ir (ppy) 2 (MOI-Ph-acac) 100.
mg (0.11 mmol) was obtained as an orange solid. Yield 75%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００８０】1H NMR (CDCl3): d 8.60 (d, 2 H, ppy),
7.9 6.7 (m, 21 H, ppy and phenyl), 6.56 (s, 1 H,
diketonate-methine), 6.39 (d, 2 H, ppy), 6.18 (s,
1 H, olefinic), 5.65 (s, 1 H, olefinic), 5.29 (s,
1 H, NH), 4.31 (t, 2 H, ethylene), 3.59 (t, 2 H, e
thylene), 2.00 (s, 3 H, methyl). E.A.: Calcd for C
44H36IrN3O6: C, 59.05; H, 4.05; N, 4.70. Found:
C, 59.79; H, 4.05; N, 4.64.[0080]1H NMR (CDCl3): d 8.60 (d, 2 H, ppy),
7.9 6.7 (m, 21 H, ppy and phenyl), 6.56 (s, 1 H,
diketonate-methine), 6.39 (d, 2 H, ppy), 6.18 (s,
1 H, olefinic), 5.65 (s, 1 H, olefinic), 5.29 (s,
1 H, NH), 4.31 (t, 2 H, ethylene), 3.59 (t, 2 H, e
thylene), 2.00 (s, 3 H, methyl). E.A .: Calcd for C
44H36IrN3O6: C, 59.05; H, 4.05; N, 4.70. Found:
C, 59.79; H, 4.05; N, 4.64.

【００８１】[0081]

【化６０】 [Chemical 60]

【００８２】（実施例５）重合性化合物：［６−（４−
メタクリロイルオキシフェニル）−２，４−ヘキサンジ
オナート］ビス（２−フェニルピリジン）イリジウム
（ＩＩＩ）（以下Ｉｒ（ｐｐｙ）2［１−（ＭＡ−Ｐｈ
−Ｍｅ）−ａｃａｃ］と略す）の合成 スキーム（５Ａ）に示すように、アセチルアセトンと、
公知の方法（C. Cativiela, et al., J. Org. Chem., 6
0, 3074 (1995)）により合成した４−ベンジルオキシベ
ンジルイオダイドを反応させて６−（ベンジルオキシフ
ェニル）−２，４−ヘキサンジオンを合成した。即ち、
水素化ナトリウム（６０％ ｉｎ ｏｉｌ）０．３０ｇ
（７．５ｍｍｏｌ）を窒素雰囲気下で秤量し、これにＴ
ＨＦ２０ｍｌを加えて水浴で０℃に冷却した。この懸濁
液にアセチルアセトン０．７５ｇ（７．５ｍｍｏｌ）と
ヘキサメチルホスホリックトリアミド０．５ｍｌの混合
溶液を滴下すると無色の沈殿が生成した。０℃で１０分
間攪拌後、ｎ−ブチルリチウムのヘキサン溶液（１．６
Ｍ）４．６ｍｌ（７．５ｍｍｏｌ）を滴下し、更に０℃
で２０分間攪拌した。得られた薄黄色の透明な溶液に、
４−ベンジルオキシベンジルイオダイド２．２８ｇ
（７．０ｍｍｏｌ）をＴＨＦ１０ｍｌに溶かした溶液を
滴下した。反応溶液を室温で1時間攪拌し、再び０℃に
冷却した後、希塩酸を加えて中和した。有機層を飽和塩
化ナトリウム水溶液で洗浄後、ロータリーエバポレータ
で溶媒を留去した。残渣をシリカゲルカラムに通し（展
開液：ジクロロメタン／ヘキサンの１：１（体積比）混
合溶媒）、主生成物を分取して減圧乾固することによ
り、目的とする６−（ベンジルオキシフェニル）−２，
４−ヘキサンジオン１．３１ｇ（４．４ｍｍｏｌ）を薄
黄色の固体として得た。収率６３％。同定はＣＨＮ元素
分析、1Ｈ−ＮＭＲで行った。Example 5 Polymerizable compound: [6- (4-
Methacryloyloxyphenyl) -2,4-hexanedionate] bis (2-phenylpyridine) iridium (III) (hereinafter Ir (ppy) 2 [1- (MA-Ph
-Me) -acac]), as shown in the synthetic scheme (5A).
Known method (C. Cativiela, et al., J. Org. Chem., 6
0, 3074 (1995)) was reacted with 4-benzyloxybenzyl iodide to synthesize 6- (benzyloxyphenyl) -2,4-hexanedione. That is,
Sodium hydride (60% in oil) 0.30g
(7.5 mmol) was weighed under a nitrogen atmosphere, and T
20 ml of HF was added and the mixture was cooled to 0 ° C. in a water bath. When a mixed solution of 0.75 g (7.5 mmol) of acetylacetone and 0.5 ml of hexamethylphosphoric triamide was added dropwise to this suspension, a colorless precipitate was produced. After stirring at 0 ° C. for 10 minutes, a hexane solution of n-butyllithium (1.6
M) 4.6 ml (7.5 mmol) was added dropwise, and further 0 ° C.
And stirred for 20 minutes. In the obtained light yellow transparent solution,
4-benzyloxybenzyl iodide 2.28 g
A solution of (7.0 mmol) in 10 ml of THF was added dropwise. The reaction solution was stirred at room temperature for 1 hour, cooled to 0 ° C. again, and diluted hydrochloric acid was added to neutralize the solution. The organic layer was washed with saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The residue is passed through a silica gel column (developing solution: dichloromethane / hexane 1: 1 (volume ratio) mixed solvent), the main product is collected and dried under reduced pressure to give the desired 6- (benzyloxyphenyl). -2
1.31 g (4.4 mmol) of 4-hexanedione was obtained as a pale yellow solid. Yield 63%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００８３】1H NMR (CDCl3): enol; d 7.5 6.8 (m, 9
H, aromatic), 5.46 (s, 1 H, enol-methine), 5.04
(s, 2 H, -O-CH2-), 2.88 (t, J = 7.6 Hz, 2 H, ethyl
ene), 2.55 (t, J = 8.4 Hz, 2 H, ethylene), 2.04
(s, 3 H, methyl). keto; d 7.56.8 (m, 9 H, aromati
c), 5.04 (s, 2 H, -O-CH2-), 3.53 (s, 2 H, C(=O)CH2
C(=O)), 2.84 (m, 4 H, ethylene), 2.19 (s, 3 H, met
hyl). enol : keto = 5: 1. E.A.: Calcd for C19H20
O3: C, 77.00; H, 6.86. Found: C, 77.46; H,6.77. 1 H NMR (CDCl 3 ): enol; d 7.5 6.8 (m, 9
H, aromatic), 5.46 (s, 1 H, enol-methine), 5.04
(s, 2 H, -O-CH 2- ), 2.88 (t, J = 7.6 Hz, 2 H, ethyl
ene), 2.55 (t, J = 8.4 Hz, 2 H, ethylene), 2.04
(s, 3 H, methyl) .keto; d 7.56.8 (m, 9 H, aromati
c), 5.04 (s, 2 H, -O-CH 2- ), 3.53 (s, 2 H, C (= O) CH 2
C (= O)), 2.84 (m, 4 H, ethylene), 2.19 (s, 3 H, met
hyl). enol: keto = 5: 1. EA: Calcd for C 19 H 20
O 3 : C, 77.00; H, 6.86.Found: C, 77.46; H, 6.77.

【００８４】[0084]

【化６１】 [Chemical formula 61]

【００８５】次いで、スキーム（５Ｂ）に示すように、
この６−（ベンジルオキシフェニル）−２，４−ヘキサ
ンジオンを水素化することにより６−（ヒドロキシフェ
ニル）−２，４−ヘキサンジオンを生成した。即ち、窒
素雰囲気下でＰｄ−活性炭（１０％）１．５ｇを秤量
し、ジクロロメタン２０ｍｌと６−（ベンジルオキシフ
ェニル）−２，４−ヘキサンジオン１．３１ｇ（４．４
ｍｍｏｌ）を加えた。反応系内を1気圧の水素で置換
し、室温で１１時間攪拌した。得られた反応溶液を濾過
して不溶物を除き、減圧で溶媒を留去した。残渣をシリ
カゲルカラムに加えてまずジクロロメタンで展開し、副
生成物を除いた。続いてアセトン／ヘキサンの１：１
（体積比）混合溶媒で溶出した化合物を含む溶液を減圧
乾燥することにより目的とする６−（ヒドロキシフェニ
ル）−２，４−ヘキサンジオン０．７０ｇ（３．４ｍｍ
ｏｌ）を薄黄色の固体として得た。収率７７％。同定は
ＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。Then, as shown in Scheme (5B),
This 6- (benzyloxyphenyl) -2,4-hexanedione was hydrogenated to produce 6- (hydroxyphenyl) -2,4-hexanedione. That is, 1.5 g of Pd-activated carbon (10%) was weighed under a nitrogen atmosphere, and 20 ml of dichloromethane and 1.31 g (4.4% of 4- (benzyloxyphenyl) -2,4-hexanedione).
mmol) was added. The atmosphere in the reaction system was replaced with hydrogen at 1 atm, and the mixture was stirred at room temperature for 11 hours. The resulting reaction solution was filtered to remove insoluble matter, and the solvent was distilled off under reduced pressure. The residue was added to a silica gel column and developed with dichloromethane first to remove by-products. Then acetone / hexane 1: 1
(Volume ratio) 0.70 g (3.4 mm) of the target 6- (hydroxyphenyl) -2,4-hexanedione was obtained by drying the solution containing the compound eluted with the mixed solvent under reduced pressure.
ol) was obtained as a pale yellow solid. Yield 77%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００８６】1H NMR (CDCl3): enol; d 7.04 (d, J =
8.4 Hz, 2 H, aromatic), 6.65 (d, J= 8.4 Hz, 2 H, a
romatic), 5.55 (br, 1 H, OH), 5.47 (s, 1 H, enol-m
ethine), 2.86 (t, J = 7.3 Hz, 2 H, ethylene), 2.55
(t, J = 7.3 Hz, 2 H, ethylene), 2.04 (s, 3 H, met
hyl). keto; d 7.04 (d, J = 8.4 Hz, 2 H, aromati
c), 6.65 (d, J = 8.4 Hz, 2 H, aromatic), 5.55 (br,
1 H, OH), 3.55 (s, 2 H,C(=O)CH2C(=O)), 2.83 (m, 4
H, ethylene), 2.19 (s, 3 H, methyl). enol :keto
= 5 : 1. E.A.: Calcd for C12H14O3: C, 69.88; H,
6.84. Found: C,69.67; H, 6.79. 1 H NMR (CDCl 3 ): enol; d 7.04 (d, J =
8.4 Hz, 2 H, aromatic), 6.65 (d, J = 8.4 Hz, 2 H, a
romatic), 5.55 (br, 1 H, OH), 5.47 (s, 1 H, enol-m
ethine), 2.86 (t, J = 7.3 Hz, 2 H, ethylene), 2.55
(t, J = 7.3 Hz, 2 H, ethylene), 2.04 (s, 3 H, met
hyl). keto; d 7.04 (d, J = 8.4 Hz, 2 H, aromati
c), 6.65 (d, J = 8.4 Hz, 2 H, aromatic), 5.55 (br,
1 H, OH), 3.55 (s, 2 H, C (= O) CH 2 C (= O)), 2.83 (m, 4
H, ethylene), 2.19 (s, 3 H, methyl). Enol: keto
= 5: 1.EA: Calcd for C 12 H 14 O 3 : C, 69.88; H,
6.84. Found: C, 69.67; H, 6.79.

【００８７】[0087]

【化６２】 [Chemical formula 62]

【００８８】スキーム（５Ｃ）に示すように、この６−
（４−ヒドロキシフェニル）−２，４−ヘキサンジオン
と、常法に従い合成したビス（μ−クロロ）テトラキス
（２−フェニルピリジン）ジイリジウム（ＩＩＩ）
（［Ｉｒ（ｐｐｙ）2Ｃｌ］2）を反応させて［６−（４
−ヒドロキシフェニル）−２，４−ヘキサンジオナー
ト］ビス（２−フェニルピリジン）イリジウム（ＩＩ
Ｉ）（以下Ｉｒ（ｐｐｙ）2［１−（ＯＨ−Ｐｈ−Ｍ
ｅ）−ａｃａｃ］と略す）を合成した。即ち、［Ｉｒ
（ｐｐｙ）2Ｃｌ］2）７１ｍｇ（０．０６６ｍｍｏｌ）
と炭酸ナトリウム４７ｍｇ（０．４４ｍｍｏｌ）の混合
物に、６−（４−ヒドロキシフェニル）−２，４−ヘキ
サンジオン４１ｍｇ（０．２０ｍｍｏｌ）をＤＭＦ５ｍ
ｌに溶かした溶液を加えて６５℃で1時間加熱攪拌し
た。得られた反応溶液に希塩酸とクロロホルムを加えて
よく振盪し、分離した有機層を硫酸マグネシウムで乾燥
して減圧下溶媒留去した。残渣をシリカゲルカラムに通
し(展開液：ヘキサン／酢酸エチルの１：１（体積比）
混合溶媒)、少量の薄黄色の副生成物の次に溶出した薄
黄色の溶液を回収して減圧乾固した。得られた固体を少
量のジクロロメタンに溶解し、ヘキサンを加えて−２０
℃に冷却することにより、目的とするＩｒ（ｐｐｙ）2
［１−（ＯＨ−Ｐｈ−Ｍｅ）−ａｃａｃ］８６ｍｇ
（０．１２ｍｍｏｌ）を薄黄色の固体として得た。収率
９２％。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行っ
た。As shown in scheme (5C), this 6-
(4-Hydroxyphenyl) -2,4-hexanedione and bis (μ-chloro) tetrakis (2-phenylpyridine) diiridium (III) synthesized by a conventional method.
([Ir (ppy) 2 Cl] 2 ) is reacted to [6- (4
-Hydroxyphenyl) -2,4-hexanedionate] bis (2-phenylpyridine) iridium (II
I) (hereinafter Ir (ppy) 2 [1- (OH-Ph-M
e) -acac]) was synthesized. That is, [Ir
(Ppy) 2 Cl] 2 ) 71 mg (0.066 mmol)
DMF 5m was obtained by adding 41-mg (0.20 mmol) of 6- (4-hydroxyphenyl) -2,4-hexanedione to a mixture of 5 mg of sodium carbonate and 47 mg (0.44 mmol) of sodium carbonate.
The solution dissolved in 1 was added, and the mixture was heated with stirring at 65 ° C. for 1 hour. Dilute hydrochloric acid and chloroform were added to the obtained reaction solution and shaken well, the separated organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Pass the residue through a silica gel column (developing solution: hexane / ethyl acetate 1: 1 (volume ratio)).
A mixed solvent), and a small amount of a pale yellow by-product, which was eluted next, was collected and dried under reduced pressure. The obtained solid was dissolved in a small amount of dichloromethane, and hexane was added to the resulting solution.
By cooling to ℃, the desired Ir (ppy) 2
[1- (OH-Ph-Me) -acac] 86 mg
(0.12 mmol) was obtained as a pale yellow solid. Yield 92%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００８９】1H NMR (CDCl3): d 8.48 (d, J = 6.2 Hz,
1 H, ppy), 8.23 (d, J = 5.9 Hz, 1H, ppy), 7.9 7.
6 (m, 4 H, ppy), 7.53 (t, J = 7.3 Hz, 2 H, ppy),
7.11 (t, J = 7.0 Hz, 1 H, ppy), 6.99 (t, J = 7.0 H
z, 1 H, ppy), 6.8 6.4 (m, 8H, ppy + C6H4OH), 6.27
(t, J = 8.1 Hz, 2 H, ppy), 5.18 (s, 1 H, diketona
te-methine), 5.10 (br, 1 H, OH), 2.54 (t, J = 7.0
Hz, 2 H, methylene),2.31 (m, 2 H, methylene), 1.75
(s, 3 H, methyl). E.A.: Calcd for C34H29IrN2O3:
C, 57.86; H, 4.14; N, 3.97. Found: C, 58.03; H,
4.11; N, 3.86. 1 H NMR (CDCl 3 ): d 8.48 (d, J = 6.2 Hz,
1 H, ppy), 8.23 (d, J = 5.9 Hz, 1H, ppy), 7.9 7.
6 (m, 4 H, ppy), 7.53 (t, J = 7.3 Hz, 2 H, ppy),
7.11 (t, J = 7.0 Hz, 1 H, ppy), 6.99 (t, J = 7.0 H
z, 1 H, ppy), 6.8 6.4 (m, 8H, ppy + C 6 H 4 OH), 6.27
(t, J = 8.1 Hz, 2 H, ppy), 5.18 (s, 1 H, diketona
te-methine), 5.10 (br, 1 H, OH), 2.54 (t, J = 7.0
Hz, 2 H, methylene), 2.31 (m, 2 H, methylene), 1.75
(s, 3 H, methyl). EA: Calcd for C 34 H 29 IrN 2 O 3 :
C, 57.86; H, 4.14; N, 3.97. Found: C, 58.03; H,
4.11; N, 3.86.

【００９０】[0090]

【化６３】 [Chemical formula 63]

【００９１】次いで、スキーム（５Ｄ）に示すように、
このＩｒ（ｐｐｙ）2［１−（ＯＨ−Ｐｈ−Ｍｅ）−ａ
ｃａｃ］とメタクリル酸クロライドを反応させることに
よりＩｒ（ｐｐｙ）2［１−（ＭＡ−Ｐｈ−Ｍｅ）−ａ
ｃａｃ］を合成した。即ち、窒素雰囲気下でＩｒ（ｐｐ
ｙ）2［１−（ＯＨ−Ｐｈ−Ｍｅ）−ａｃａｃ］１６９
ｍｇ（０．２４ｍｍｏｌ）をジクロロメタン１０ｍｌに
溶解し、トリエチルアミン０．３０ｍｌ（２．２ｍｍｏ
ｌ）を加えた。この溶液にメタクリル酸クロライド０．
０６０ｍｌ（０．６１ｍｍｏｌ）を加えると速やかに生
成物を生じた。更に少量のメタノールを加えた後、減圧
で溶媒を留去した。残渣をヘキサン／ジクロロメタン／
アセトンの混合溶媒（１０：１０：１（体積比））を用
いてシリカゲルカラムに通し、黄色の主生成物を分取し
た。減圧で溶媒留去後、ジクロロメタン−ヘキサン混合
溶液から再結晶することにより目的とするＩｒ（ｐｐ
ｙ） 2［１−（ＭＡ−Ｐｈ−Ｍｅ）−ａｃａｃ］１４１
ｍｇ（０．１８ｍｍｏｌ）を黄色の固体として得た。収
率７６％。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行っ
た。Then, as shown in Scheme (5D),
This Ir (ppy)2[1- (OH-Ph-Me) -a
cac] and methacrylic acid chloride
From Ir (ppy)2[1- (MA-Ph-Me) -a
cac] was synthesized. That is, Ir (pp
y)2[1- (OH-Ph-Me) -acac] 169
mg (0.24 mmol) in 10 ml of dichloromethane
Dissolve, 0.30 ml of triethylamine (2.2 mmo
l) was added. Methacrylic acid chloride was added to this solution.
Add 060 ml (0.61 mmol) of the product
Produced a product. After adding a small amount of methanol, depressurize
The solvent was distilled off. The residue is hexane / dichloromethane /
Use a mixed solvent of acetone (10: 10: 1 (volume ratio))
And pass it through a silica gel column to collect the yellow main product.
It was After distilling off the solvent under reduced pressure, mix dichloromethane-hexane.
By recrystallizing from solution, the desired Ir (pp
y) 2[1- (MA-Ph-Me) -acac] 141
Obtained mg (0.18 mmol) as a yellow solid. Income
Rate 76%. Identification is CHN elemental analysis,1Performed by 1 H-NMR
It was

【００９２】1H NMR (CDCl3): d 8.48 (d, J = 5.1 Hz,
1 H, ppy), 8.27 (d, J = 5.9 Hz, 1H, ppy), 7.9 7.
5 (m, 6 H, ppy), 7.12 (t, J = 7.0 Hz, 1 H, ppy),
7.04 (t, J = 7.0 Hz, 1 H, ppy), 6.9 6.6 (m, 8 H,
aromatic), 6.33 (s, 1 H, olefinic), 6.27 (d, J =
7.6 Hz, 2 H, ppy), 5.74 (s, 1 H, olefinic), 5.17
(s, 1 H, diketonate-methine), 2.61 (t, J = 7.0 Hz,
2 H, ethylene), 2.34 (m, 2 H, ethylene), 2.07 (s,
3 H, methacryl-methyl), 1.76 (s, 3 H, diketonate-
methyl). E.A.: Calcd for C38H33IrN2O4: C, 58.98;
H, 4.30; N, 3.62.Found: C, 58.69; H, 4.17; N, 3.8
1. 1 H NMR (CDCl 3 ): d 8.48 (d, J = 5.1 Hz,
1 H, ppy), 8.27 (d, J = 5.9 Hz, 1H, ppy), 7.9 7.
5 (m, 6 H, ppy), 7.12 (t, J = 7.0 Hz, 1 H, ppy),
7.04 (t, J = 7.0 Hz, 1 H, ppy), 6.9 6.6 (m, 8 H,
aromatic), 6.33 (s, 1 H, olefinic), 6.27 (d, J =
7.6 Hz, 2 H, ppy), 5.74 (s, 1 H, olefinic), 5.17
(s, 1 H, diketonate-methine), 2.61 (t, J = 7.0 Hz,
2 H, ethylene), 2.34 (m, 2 H, ethylene), 2.07 (s,
3 H, methacryl-methyl), 1.76 (s, 3 H, diketonate-
methyl). EA: Calcd for C 38 H 33 IrN 2 O 4 : C, 58.98;
H, 4.30; N, 3.62.Found: C, 58.69; H, 4.17; N, 3.8
1.

【００９３】[0093]

【化６４】 [Chemical 64]

【００９４】（実施例６）重合性化合物：（１−メタク
リロイルオキシ−２，４−ペンタンジオナート）ビス
（２−フェニルピリジン）イリジウム（ＩＩＩ）（以下
Ｉｒ（ｐｐｙ）2（１−ＭＡ−ａｃａｃ）と略す）の合
成 スキーム（６Ａ）に示すように、常法に従い合成したビ
ス（μ−クロロ）テトラキス（２−フェニルピリジン）
ジイリジウム（ＩＩＩ）（［Ｉｒ（ｐｐｙ）2Ｃｌ］2）
と、公知の方法（欧州特許ＥＰ０５１４２１７）を参考
に合成した１−（ｔｅｒｔ−ブチルジメチルシリルオキ
シ）−２，４−ペンタジオンを反応させて（１−ヒドロ
キシ−２，４−ペンタンジオナート）ビス（２−フェニ
ルピリジン）イリジウム（ＩＩＩ）（以下Ｉｒ（ｐｐ
ｙ）2（１−ＯＨ−ａｃａｃ）と略す）を合成した。即
ち、［Ｉｒ（ｐｐｙ）2Ｃｌ］2４９２ｍｇ（０．４６ｍ
ｍｏｌ）と炭酸ナトリウム１３９ｍｇ（１．３１ｍｍｏ
ｌ）をＤＭＦ１０ｍｌ中に溶解し、１−（ｔｅｒｔ−ブ
チルジメチルシリルオキシ）−２，４−ペンタジオン
（１−ＴＢＤＭＳＯ−２，４−ペンタジオン）３２１ｍ
ｇ（１．３９ｍｍｏｌ）を加えて７０℃で1時間加熱撹
拌した。得られた反応混合物を室温にまで冷却した後、
１００ｍｌの飽和塩化アンモニウム水溶液および５０ｍ
ｌのクロロホルムを加えてよく振盪した。有機層を硫酸
マグネシウムで乾燥して減圧で溶媒留去し、残渣をジク
ロロメタンを溶出液とするシリカゲルカラムに通し黄色
の溶液を得た。これを減圧乾燥した後に得られた黄色の
固体をＴＨＦ２０ｍｌ中に溶解し、テトラ−ｎ−ブチル
アンモニウムフルオライド（以下Ｂｕn 4ＮＦと略す）の
１．０Ｍ ＴＨＦ溶液０．４６ｍｌ（０．４６ｍｍｏ
ｌ）を激しく撹拌しながら滴下した。この反応溶液を室
温で０．５時間撹拌後、減圧で溶媒留去した。残渣をシ
リカゲルカラムに通し（溶出液：ヘキサン／ジクロロメ
タン／アセトンの１：３：１（体積比）の混合溶媒）、
溶出した黄色の主生成物を回収して減圧乾燥した。得ら
れた粗生成物をジクロロメタン／ヘキサン混合溶液から
再結晶することにより、目的とするＩｒ（ｐｐｙ）
2（１−ＯＨ−ａｃａｃ）３８９ｍｇ（０．６３ｍｍｏ
ｌ）を黄色の固体として得た。収率６９％。同定はＣＨ
Ｎ元素分析、 1Ｈ−ＮＭＲで行った。(Example 6) Polymerizable compound: (1-methac)
Liloyloxy-2,4-pentanedionate) bis
(2-phenylpyridine) iridium (III) (hereinafter
Ir (ppy)2(1-MA-acac))
Success As shown in scheme (6A),
Su (μ-chloro) tetrakis (2-phenylpyridine)
Diiridium (III) ([Ir (ppy)2Cl]2)
And refer to a known method (European Patent EP0514217)
Synthesized in 1- (tert-butyldimethylsilyloxy)
Si) -2,4-pentadione is reacted to give (1-hydro
Xy-2,4-pentanedionato) bis (2-phenyl
Rupyridine) iridium (III) (hereinafter Ir (pp
y)2(1-OH-acac) was synthesized. Immediately
Then, [Ir (ppy)2Cl]2492 mg (0.46 m
mol) and sodium carbonate 139 mg (1.31 mmo
1) was dissolved in 10 ml of DMF, and 1- (tert-but
Cyldimethylsilyloxy) -2,4-pentadione
(1-TBDMSO-2,4-pentadione) 321 m
g (1.39 mmol), and heat with stirring at 70 ° C for 1 hour.
I stirred. After cooling the resulting reaction mixture to room temperature,
100 ml saturated aqueous ammonium chloride solution and 50 m
l of chloroform was added and shaken well. Sulfate the organic layer
Dry over magnesium, evaporate the solvent under reduced pressure and dilute the residue.
Pass through a silica gel column with rolomethane as the eluent
A solution of The yellow color obtained after drying this under reduced pressure
Dissolve the solid in 20 ml of THF and add tetra-n-butyl.
Ammonium fluoride (hereinafter Bun FourAbbreviated as NF)
1.0M THF solution 0.46 ml (0.46 mmo
l) was added dropwise with vigorous stirring. Room the reaction solution
After stirring at temperature for 0.5 hours, the solvent was distilled off under reduced pressure. Remove the residue
Pass through a silica gel column (eluent: hexane / dichloromethane
Mixed solvent of tan / acetone 1: 3: 1 (volume ratio),
The eluted yellow main product was collected and dried under reduced pressure. Got
The crude product obtained from the dichloromethane / hexane mixed solution
By recrystallizing, the desired Ir (ppy)
2(1-OH-acac) 389 mg (0.63 mmo
l) was obtained as a yellow solid. Yield 69%. Identification is CH
N element analysis, 1It was conducted by 1 H-NMR.

【００９５】1H NMR (CDCl3): d 8.48 (d, J = 5.7 Hz,
1 H, ppy), 8.42 (d, J = 5.7 Hz, 1H, ppy), 7.86
(m, 2 H, ppy), 7.74 (t, J = 7.6 Hz, 2 H, ppy), 7.5
4 (t, J= 5.9 Hz, 2 H, ppy), 7.14 (t, J = 5.9 Hz, 2
H, ppy), 6.82 (t, J = 7.3 Hz, 2 H, ppy), 6.69 (m,
2 H, ppy), 6.28 (d, J = 6.8 Hz, 1 H, ppy), 6.23
(d, J = 6.5 Hz, 1 H, ppy), 5.17 (s, 1 H, diketonat
e-methine), 3.88 (dd, J= 8.1, 5.4 Hz, 1 H, -CHH'-O
-), 3.78 (dd, J = 8.1, 4.3 Hz, 1 H, -CHH'-O-), 3.1
0 (t, J = 4.6 Hz, 1 H, OH), 1.82 (s, 3 H, methyl).
E.A.: Calcd for C27H23IrN2O3: C, 52.67; H, 3.77;
N, 4.55. Found: C, 52.45; H, 3.68; N, 4.79. 1 H NMR (CDCl 3 ): d 8.48 (d, J = 5.7 Hz,
1 H, ppy), 8.42 (d, J = 5.7 Hz, 1H, ppy), 7.86
(m, 2 H, ppy), 7.74 (t, J = 7.6 Hz, 2 H, ppy), 7.5
4 (t, J = 5.9 Hz, 2 H, ppy), 7.14 (t, J = 5.9 Hz, 2
H, ppy), 6.82 (t, J = 7.3 Hz, 2 H, ppy), 6.69 (m,
2 H, ppy), 6.28 (d, J = 6.8 Hz, 1 H, ppy), 6.23
(d, J = 6.5 Hz, 1 H, ppy), 5.17 (s, 1 H, diketonat
e-methine), 3.88 (dd, J = 8.1, 5.4 Hz, 1 H, -CHH'-O
-), 3.78 (dd, J = 8.1, 4.3 Hz, 1 H, -CHH'-O-), 3.1
0 (t, J = 4.6 Hz, 1 H, OH), 1.82 (s, 3 H, methyl).
EA: Calcd for C 27 H 23 IrN 2 O 3 : C, 52.67; H, 3.77;
N, 4.55. Found: C, 52.45; H, 3.68; N, 4.79.

【００９６】[0096]

【化６５】 [Chemical 65]

【００９７】次いで、スキーム（６Ｂ）に示すように、
このＩｒ（ｐｐｙ）2（１−ＯＨ−ａｃａｃ）とメタク
リル酸クロライドを反応させることによりＩｒ（ｐｐ
ｙ）2（１−ＭＡ−ａｃａｃ）を合成した。即ち、Ｉｒ
（ｐｐｙ）2（１−ＯＨ−ａｃａｃ）２００ｍｇ（０．
３２ｍｍｏｌ）を乾燥ジクロロメタン１５ｍｌに溶解
し、トリエチルアミン０．２５ｍｌ（１．８ｍｍｏｌ）
と０．２０ｍｌのメタクリル酸クロライド０．２０ｍｌ
（２．０ｍｍｏｌ）を加えて室温で1時間撹拌した。次
に反応溶液を炭酸ナトリウム水溶液２０ｍｌで洗浄し、
減圧で溶媒を留去した。残渣を再びジクロロメタンに溶
解してシリカゲルカラム上部に加え、ヘキサン／ジクロ
ロメタン／アセトンの２：４：１（体積比）の混合溶媒
で展開した。最初に得られる黄色溶液を回収して減圧で
乾燥することにより、目的とするＩｒ（ｐｐｙ）2（１
−ＭＡ−ａｃａｃ）１６５ｍｇ（０．２４ｍｍｏｌ）を
黄色の固体として得た。収率７４％。同定はＣＨＮ元素
分析、1Ｈ−ＮＭＲで行った。Then, as shown in Scheme (6B),
By reacting this Ir (ppy) 2 (1-OH-acac) with methacrylic acid chloride, Ir (pp
y) 2 (1-MA-acac) was synthesized. That is, Ir
(Ppy) 2 (1-OH-acac) 200 mg (0.
32 mmol) is dissolved in 15 ml of dry dichloromethane, and 0.25 ml (1.8 mmol) of triethylamine is dissolved.
And 0.20 ml methacrylic acid chloride 0.20 ml
(2.0 mmol) was added and the mixture was stirred at room temperature for 1 hour. Then the reaction solution is washed with 20 ml of an aqueous solution of sodium carbonate,
The solvent was distilled off under reduced pressure. The residue was again dissolved in dichloromethane, added to the top of the silica gel column, and developed with a mixed solvent of hexane / dichloromethane / acetone 2: 4: 1 (volume ratio). The yellow solution obtained first is recovered and dried under reduced pressure to obtain the desired Ir (ppy) 2 (1
165 mg (0.24 mmol) of -MA-acac) was obtained as a yellow solid. Yield 74%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【００９８】1H NMR (CDCl3): d 8.53 (d, J = 5.7 Hz,
1 H, ppy), 8.48 (d, J = 5.4 Hz, 1H, ppy), 7.84
(d, J = 7.8 Hz, 2 H, ppy), 7.73 (t, J = 7.0 Hz, 2
H, ppy), 7.53 (t, J = 6.8 Hz, 2 H, ppy), 5.14 (m,
2 H, ppy), 6.79 (m, 2 H, ppy), 6.69 (m, 2 H, ppy),
6.29 (d, J = 7.6 Hz, 1 H, ppy), 6.23 (d, J = 7.6
Hz, 1 H, ppy), 6.04 (s, 1 H, olefinic), 5.51 (s, 1
H, olefinic), 5.31 (s,1 H, diketonate-methine),
4.38 (d, J = 15.4 Hz, 1 H, -CHH-OC(=O)-), 4.27 (d,
J = 14.9 Hz, 1 H, -CHH-OC(=O)-), 1.87 (s, 3 H, me
thacryl-methyl),1.82 (s, 3 H, diketonate-methyl).
E.A.: Calcd for C31H27IrN2O4: C, 54.45; H, 3.98;
N, 4.10. Found: C, 54.18; H, 3.96; N, 4.33. 1 H NMR (CDCl 3 ): d 8.53 (d, J = 5.7 Hz,
1 H, ppy), 8.48 (d, J = 5.4 Hz, 1H, ppy), 7.84
(d, J = 7.8 Hz, 2 H, ppy), 7.73 (t, J = 7.0 Hz, 2
H, ppy), 7.53 (t, J = 6.8 Hz, 2 H, ppy), 5.14 (m,
2 H, ppy), 6.79 (m, 2 H, ppy), 6.69 (m, 2 H, ppy),
6.29 (d, J = 7.6 Hz, 1 H, ppy), 6.23 (d, J = 7.6
Hz, 1 H, ppy), 6.04 (s, 1 H, olefinic), 5.51 (s, 1
H, olefinic), 5.31 (s, 1 H, diketonate-methine),
4.38 (d, J = 15.4 Hz, 1 H, -CHH-OC (= O)-), 4.27 (d,
J = 14.9 Hz, 1 H, -CHH-OC (= O)-), 1.87 (s, 3 H, me
thacryl-methyl), 1.82 (s, 3 H, diketonate-methyl).
EA: Calcd for C 31 H 27 IrN 2 O 4 : C, 54.45; H, 3.98;
N, 4.10. Found: C, 54.18; H, 3.96; N, 4.33.

【００９９】[0099]

【化６６】 [Chemical formula 66]

【０１００】（実施例７）重合性化合物：［６−（４−
ビニルフェニル）−２，４−ヘキサンジオナート］ビス
［２−（２，４−ジフルオロフェニル）ピリジン］イリ
ジウム（ＩＩＩ）（以下Ｉｒ（２，４−Ｆ−ｐｐｙ）2
［１−（Ｓｔ−Ｍｅ）ａｃａｃ］と略す）の合成 スキーム（７Ａ）に示すように、常法に従い２−（２，
４−ジフルオロフェニル）ピリジンを合成した。即ち、
アルゴン気流下において２−ブロモピリジン８．６９ｇ
（５５．０ｍｍｏｌ）を脱水テトラヒドロフラン２００
ｍｌに溶解して−７８℃まで冷却し、１．６Ｍ ｎ−ブ
チルリチウムのヘキサン溶液３８．７ｍｌ（６１．９ｍ
ｍｏｌ）を３０分かけて滴下した。滴下後、さらに塩化
亜鉛７．５ｇ（５５．０ｍｍｏｌ）を脱水テトラヒドロ
フラン５０ｍｌに溶解した溶液を３０分かけて滴下し
た。滴下後、０℃までゆっくりと昇温し、１−ブロモ−
２，４−ジフルオロベンゼン９．６５ｇ（５５．０ｍｍ
ｏｌ）とテトラキス（トリフェニルホスフィン）パラジ
ウム（０） ２．３１ｇ（２．０ｍｍｏｌ）を加え、還
流下に６時間攪拌した後、反応液に飽和食塩水２００ｍ
ｌを加えジエチルエーテルで抽出した。抽出液を乾燥
後、濃縮し、カラムクロマトグラフィー（シリカゲル；
クロロホルム／ヘキサン（１／１：体積比））で精製す
ることにより、２−（２，４−ジフルオロフェニル）ピ
リジン６．００ｇ（３１．４ｍｍｏｌ）を無色透明のオ
イルとして得た。収率６３％。同定は1Ｈ ＮＭＲとＣ
ＨＮ元素分析で行った。Example 7 Polymerizable compound: [6- (4-
Vinylphenyl) -2,4-hexanedionate] bis [2- (2,4-difluorophenyl) pyridine] iridium (III) (hereinafter Ir (2,4-F-ppy) 2
As shown in the synthetic scheme (7A) of [1- (St-Me) acac], 2- (2,2
4-difluorophenyl) pyridine was synthesized. That is,
8.69 g of 2-bromopyridine under an argon stream
(55.0 mmol) of dehydrated tetrahydrofuran 200
It was dissolved in ml and cooled to −78 ° C., and 38.7 ml (61.9 m) of hexane solution of 1.6 M n-butyllithium.
(mol) was added dropwise over 30 minutes. After the dropping, a solution of 7.5 g (55.0 mmol) of zinc chloride dissolved in 50 ml of dehydrated tetrahydrofuran was added dropwise over 30 minutes. After the dropping, the temperature was slowly raised to 0 ° C. and 1-bromo-
2,4-Difluorobenzene 9.65g (55.0mm
Ol) and tetrakis (triphenylphosphine) palladium (0) (2.31 g, 2.0 mmol) were added, and the mixture was stirred under reflux for 6 hours, and then the reaction solution was saturated with brine (200 m).
1 was added and extracted with diethyl ether. The extract was dried, concentrated, and subjected to column chromatography (silica gel;
By refining with chloroform / hexane (1/1: volume ratio), 6.00 g (31.4 mmol) of 2- (2,4-difluorophenyl) pyridine was obtained as a colorless transparent oil. Yield 63%. Identification is by 1 H NMR and C
HN elemental analysis was performed.

【０１０１】1H NMR(270 MHz, CDCl3), ppm: 8.71(d, 1
H, J 4.6 Hz), 8.00(td, 1H, J 8.9, 6.5 Hz), 7.8 -
7.7(m, 2H), 7.3 - 7.2(over wrapped with CHCl3, 1
H), 7.1- 6.8(m, 2H). E. A. : Found: C 68.98, H 3.
80, N 7.31. Calcd: C 69.11,H 3.69, N 7.33. 1 H NMR (270 MHz, CDCl 3 ), ppm: 8.71 (d, 1
H, J 4.6 Hz), 8.00 (td, 1H, J 8.9, 6.5 Hz), 7.8-
7.7 (m, 2H), 7.3-7.2 (over wrapped with CHCl 3 , 1
H), 7.1- 6.8 (m, 2H). EA: Found: C 68.98, H 3.
80, N 7.31.Calcd: C 69.11, H 3.69, N 7.33.

【０１０２】[0102]

【化６７】 [Chemical formula 67]

【０１０３】次いで、スキーム（７Ｂ）に示すように、
この２−（２，４−ジフルオロフェニル）ピリジンとヘ
キサクロロイリジウム（ＩＩＩ）酸ナトリウムｎ水和物
を反応させることによりビス（μ−クロロ）テトラキス
［２−（２，４−ジフルオロフェニル）ピリジン］ジイ
リジウム（ＩＩＩ）（以下［Ｉｒ（２，４−Ｆ−ｐｐ
ｙ）2Ｃｌ］2と略す）を合成した。即ち、２−（２，４
−ジフルオロフェニル）ピリジン０．９６ｇ（５．０ｍ
ｍｏｌ）とヘキサクロロイリジウム（ＩＩＩ）酸ナトリ
ウムｎ水和物１．００ｇを２−エトキシエタノール：水
＝３：１（体積比）の混合溶媒４０ｍｌに溶解し、３０
分間アルゴンガスを吹き込んだ後、還流下に５時間攪拌
した。生じた沈殿を濾取し、エタノールと少量のアセト
ンで洗浄し、真空下で５時間乾燥することにより、目的
とする［Ｉｒ（２，４−Ｆ−ｐｐｙ）2Ｃｌ］2０．７９
ｇ（０．６５ｍｍｏｌ）を黄色粉末として得た。収率８
６％。同定は1Ｈ ＮＭＲとＣＨＮ元素分析で行った。Then, as shown in Scheme (7B),
By reacting this 2- (2,4-difluorophenyl) pyridine with sodium hexachloroiridium (III) nhydrate, bis (μ-chloro) tetrakis [2- (2,4-difluorophenyl) pyridine] di Iridium (III) (hereinafter [Ir (2,4-F-pp
y) 2 Cl] 2 ) was synthesized. That is, 2- (2,4
-Difluorophenyl) pyridine 0.96 g (5.0 m
mol) and sodium hexachloroiridium (III) nhydrate 1.00 g are dissolved in 40 ml of a mixed solvent of 2-ethoxyethanol: water = 3: 1 (volume ratio),
After bubbling argon gas for a minute, the mixture was stirred under reflux for 5 hours. The resulting precipitate was collected by filtration, washed with ethanol and a small amount of acetone, and dried under vacuum for 5 hours to give the desired [Ir (2,4-F-ppy) 2 Cl] 2 0.79.
g (0.65 mmol) was obtained as a yellow powder. Yield 8
6%. Identification was performed by 1 H NMR and CHN elemental analysis.

【０１０４】1H NMR(270 MHz, CDCl3), ppm: 9.12(d, 4
H, J = 5.7 Hz), 8.31(d, 4H, J = 8.6 Hz), 7.83(dd,
4H, J = 7.6, 7.6 Hz), 6.82(dd, 4H, J = 7.3, 7.3 H
z), 6.34(ddd, 4H, J = 11.6, 10.0, 2.4 Hz), 5.29(d
d, 4H, J = 9.5, 2.4 Hz). Anal. Found: C 43.39, H
2.03, N 4.55. Calcd: C 43.46, H 1.99, N 4.61. 1 H NMR (270 MHz, CDCl 3 ), ppm: 9.12 (d, 4
H, J = 5.7 Hz), 8.31 (d, 4H, J = 8.6 Hz), 7.83 (dd,
4H, J = 7.6, 7.6 Hz), 6.82 (dd, 4H, J = 7.3, 7.3 H
z), 6.34 (ddd, 4H, J = 11.6, 10.0, 2.4 Hz), 5.29 (d
d, 4H, J = 9.5, 2.4 Hz). Anal. Found: C 43.39, H
2.03, N 4.55. Calcd: C 43.46, H 1.99, N 4.61.

【０１０５】[0105]

【化６８】 [Chemical 68]

【０１０６】次いで、スキーム（７Ｃ）に示すように、
この［Ｉｒ（２，４−Ｆ−ｐｐｙ） 2Ｃｌ］2と６−（４
−ビニルフェニル）−２，４−ヘキサジオンを反応させ
ることによりＩｒ（２，４−Ｆ−ＰＰｙ）2［１−（Ｓ
Ｔ−Ｍｅ）ａｃａｃ］を合成した。即ち、［Ｉｒ（２，
４−Ｆ−ｐｐｙ）2Ｃｌ］2 ２４３ｍｇ（０．２０ｍｍ
ｏｌ）、炭酸ナトリウム２１２ｍｇ（２．００ｍｍｏ
ｌ）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェ
ノール１．３ｍｇ、実施例２と同様に合成した６−（４
−ビニルフェニル）−２，４−ヘキサジオン１３０ｍｇ
（０．６０ｍｍｏｌ）をアルゴン気流下にＤＭＦ２０ｍ
ｌに溶解し、８０℃で２時間攪拌した後、反応液に水を
加え、クロロホルムで抽出した。抽出液を乾燥後、濃縮
し、カラムクロマトグラフィー（シリカゲル；クロロホ
ルム）で精製し、さらにクロロホルム／ヘキサン溶液か
ら再結晶することにより、Ｉｒ（２，４−Ｆ−ＰＰｙ）
2［１−（ＳＴ−Ｍｅ）ａｃａｃ］２６１ｍｇ（０．３
３ｍｍｏｌ）を黄色結晶として得た。収率８３％。同定
はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。Then, as shown in Scheme (7C),
This [Ir (2,4-F-ppy) 2Cl]2And 6- (4
-Vinylphenyl) -2,4-hexadione is reacted
Ir (2,4-F-PPy)2[1- (S
T-Me) acac] was synthesized. That is, [Ir (2,
4-F-ppy)2Cl]2  243 mg (0.20 mm
ol), sodium carbonate 212 mg (2.00 mmo
l), 2,6-di-tert-butyl-4-methylphene
1.3 mg of nor, 6- (4 synthesized in the same manner as in Example 2)
-Vinylphenyl) -2,4-hexadione 130 mg
(0.60 mmol) of DMF 20m under argon stream
l, and stirred at 80 ° C for 2 hours, water was added to the reaction solution.
In addition, it was extracted with chloroform. Concentrate after drying the extract
Column chromatography (silica gel; chloropho
Or chloroform / hexane solution.
By recrystallization from Ir (2,4-F-PPy)
2[1- (ST-Me) acac] 261 mg (0.3
3 mmol) was obtained as yellow crystals. Yield 83%. Identification
Is CHN elemental analysis,1It was conducted by 1 H-NMR.

【０１０７】1H NMR(270 MHz, CDCl3), ppm: 8.39(d, 1
H, J = 5.7 Hz), 8.3 - 8.2(m, 2H),8.04(d, 1H, J =
5.7 Hz), 7.8 - 7.7(m, 2H), 7.19(d, 2H, J = 7.8 H
z), 7.15(dd, 1H, J = 6.6, 6.6 Hz), 6.97(dd, 1H, J
= 6.6, 6.6 Hz), 6.89(d, 2H, J= 7.8 Hz), 6.67(dd, 1
H, J = 17.6, 10.8 Hz), .6.4 - 6.2(m, 2H), 5.7 - 5.
6(m, 3H), 5.22(s, 1H), 5.21(d, 1H, J = 11.1 Hz),
2.62(t, 2H, J = 7.0 Hz),2.39(m, 2H), 1.78(s, 3H).
Anal. Found: C 54.82, H 3.50, N 3.49. Calcd: C 5
4.88, H 3.45, N 3.56. 1 H NMR (270 MHz, CDCl 3 ), ppm: 8.39 (d, 1
H, J = 5.7 Hz), 8.3-8.2 (m, 2H), 8.04 (d, 1H, J =
5.7 Hz), 7.8-7.7 (m, 2H), 7.19 (d, 2H, J = 7.8 H
z), 7.15 (dd, 1H, J = 6.6, 6.6 Hz), 6.97 (dd, 1H, J
= 6.6, 6.6 Hz), 6.89 (d, 2H, J = 7.8 Hz), 6.67 (dd, 1
H, J = 17.6, 10.8 Hz), .6.4-6.2 (m, 2H), 5.7-5.
6 (m, 3H), 5.22 (s, 1H), 5.21 (d, 1H, J = 11.1 Hz),
2.62 (t, 2H, J = 7.0 Hz), 2.39 (m, 2H), 1.78 (s, 3H).
Anal. Found: C 54.82, H 3.50, N 3.49. Calcd: C 5
4.88, H 3.45, N 3.56.

【０１０８】[0108]

【化６９】 [Chemical 69]

【０１０９】（実施例８）重合性化合物：｛３−［４−
（２−メタクリロイルオキシエチル）カルバモイルオキ
シフェニルメチル］−２，４−ペンタンジオナート｝ビ
ス（２−フェニルピリジン）イリジウム（ＩＩＩ）（以
下Ｉｒ（ｐｐｙ）2［３−（ＭＯＩ−Ｐｈ−Ｍｅ）−ａ
ｃａｃ］と略す）の合成 スキーム（８Ａ）に示すように、常法に従い合成したビ
ス（μ−クロロ）テトラキス（２−フェニルピリジン）
ジイリジウム（ＩＩＩ）（［Ｉｒ（ｐｐｙ）2Ｃｌ］2）
と３−（４−ヒドロキシフェニルメチル）−２，４−ペ
ンタンジオンを反応させて［３−（４−ヒドロキシフェ
ニルメチル）−２，４−ペンタンジオナート］ビス（２
−フェニルピリジン）イリジウム（ＩＩＩ）（以下Ｉｒ
（ｐｐｙ）2［１−（ＯＨ−Ｐｈ−Ｍｅ）−ａｃａｃ］
と略す）を合成した。即ち、［Ｉｒ（ｐｐｙ）2Ｃ
ｌ］2）５６ｍｇ（０．０５２ｍｍｏｌ）および炭酸ナ
トリウム４４ｍｇ（０．４２ｍｍｏｌ）をＤＭＦ５ｍｌ
に溶解した。この溶液に、公知の方法（C. Cativiela e
t al., J. Org. Chem., 60, 3074 (1995)）により合成
した３−（４−ヒドロキシフェニルメチル）−２，４−
ペンタンジオン３０ｍｇ（０．１５ｍｍｏｌ）をＤＭＦ
５ｍｌに溶解した溶液を加えて８０℃で１．５時間加熱
攪拌した。次に、室温にまで冷却した反応溶液に希塩酸
とクロロホルムを加えてよく振とうし、有機層を分取し
てロータリーエバポレータで溶媒を留去した。残渣をヘ
キサン／酢酸エチルの１：１（体積比）混合溶媒を展開
液とするシリカゲルカラムに通し、主生成物のバンドを
分取した。得られた薄黄色の溶液から減圧で溶媒を留去
し、ジクロロメタン／ヘキサンの混合溶液から再結晶す
ることによりＩｒ（ｐｐｙ）2［１−（ＯＨ−Ｐｈ−Ｍ
ｅ）−ａｃａｃ］３４ｍｇ（０．０４８ｍｍｏｌ）を薄
黄色の固体として得た。収率４６％。同定はＣＨＮ元素
分析、1Ｈ−ＮＭＲで行った。Example 8 Polymerizable compound: {3- [4-
(2-methacryloyloxyethyl) carbamoyloxyphenylmethyl] -2,4-pentanedionate} bis (2-phenylpyridine) iridium (III) (hereinafter Ir (ppy) 2 [3- (MOI-Ph-Me)- a
abbreviated as “cac”), and bis (μ-chloro) tetrakis (2-phenylpyridine) synthesized by a conventional method
Diiridium (III) ([Ir (ppy) 2 Cl] 2 )
And 3- (4-hydroxyphenylmethyl) -2,4-pentanedione are reacted to give [3- (4-hydroxyphenylmethyl) -2,4-pentanedionate] bis (2
-Phenylpyridine) iridium (III) (hereinafter Ir
(Ppy) 2 [1- (OH-Ph-Me) -acac]
Abbreviated) was synthesized. That is, [Ir (ppy) 2 C
l] 2 ) 56 mg (0.052 mmol) and sodium carbonate 44 mg (0.42 mmol) were added to DMF 5 ml.
Dissolved in. A known method (C. Cativiela e
al., J. Org. Chem., 60, 3074 (1995)), 3- (4-hydroxyphenylmethyl) -2,4-
30 mg (0.15 mmol) of pentanedione was added to DMF.
The solution dissolved in 5 ml was added, and the mixture was heated with stirring at 80 ° C. for 1.5 hours. Next, diluted hydrochloric acid and chloroform were added to the reaction solution cooled to room temperature, and the mixture was shaken well, the organic layer was separated, and the solvent was distilled off with a rotary evaporator. The residue was passed through a silica gel column using a 1: 1 (volume ratio) mixed solvent of hexane / ethyl acetate as a developing solution to separate a band of a main product. The solvent was distilled off from the obtained pale yellow solution under reduced pressure, and recrystallization from a mixed solution of dichloromethane / hexane was carried out to obtain Ir (ppy) 2 [1- (OH-Ph-M
e) -acac] 34 mg (0.048 mmol) was obtained as a pale yellow solid. Yield 46%. Identification was performed by CHN elemental analysis and 1 H-NMR.

【０１１０】1H NMR (CDCl3): d 8.58 (d, J = 5.9 Hz,
2 H, ppy), 7.84 (d, J = 7.8 Hz, 2H, ppy), 7.73
(t, J = 6.5 Hz, 2 H, ppy), 7.55 (d, J = 7.6 Hz, 2
H, ppy), 7.1 6.6 (m, 10 H, aromatic), 6.27 (d, J
= 7.6 Hz, 2 H, ppy), 4.86 (br-s, 1 H, OH), 3.62
(s, 2 H, benzyl), 1.80 (s, 6 H, methyl). E.A.: Cal
cdfor C34H29IrN2O3: C, 57.86; H, 4.14; N, 3.97. F
ound: C, 57.97; H, 4.22;N, 4.15. 1 H NMR (CDCl 3 ): d 8.58 (d, J = 5.9 Hz,
2 H, ppy), 7.84 (d, J = 7.8 Hz, 2H, ppy), 7.73
(t, J = 6.5 Hz, 2 H, ppy), 7.55 (d, J = 7.6 Hz, 2
H, ppy), 7.1 6.6 (m, 10 H, aromatic), 6.27 (d, J
= 7.6 Hz, 2 H, ppy), 4.86 (br-s, 1 H, OH), 3.62
(s, 2 H, benzyl), 1.80 (s, 6 H, methyl). EA: Cal
cdfor C 34 H 29 IrN 2 O 3 : C, 57.86; H, 4.14; N, 3.97. F
ound: C, 57.97; H, 4.22; N, 4.15.

【０１１１】[0111]

【化７０】 [Chemical 70]

【０１１２】次いで、スキーム（８Ｂ）に示すように、
このＩｒ（ｐｐｙ）2［１−（ＯＨ−Ｐｈ−Ｍｅ）−ａ
ｃａｃ］とメタクリロイルオキシエチルイソシアネート
（ＭＯＩ：商品名、昭和電工製）を反応させることによ
りＩｒ（ｐｐｙ）2［１−（ＭＯＩ−Ｐｈ−Ｍｅ）−ａ
ｃａｃ］を合成した。即ち、Ｉｒ（ｐｐｙ）2［１−
（ＯＨ−Ｐｈ−Ｍｅ）−ａｃａｃ］７１ｍｇ（０．１０
ｍｍｏｌ）と２，６−ジ−ｔｅｒｔ−ブチル−４−メチ
ルフェノール３ｍｇ（０．０１４ｍｍｏｌ）、ジブチル
錫（ＩＶ）ジラウレート２７ｍｇ（０．１２ｍｍｏｌ）
及びＭＯＩ ５５ｍｇ（０．３５ｍｍｏｌ）をＴＨＦ１
０ｍｌに溶解し、７０℃で2時間加熱攪拌した。得られ
た反応混合物をロータリーエバポレータで減圧乾固し、
残渣をヘキサン／酢酸エチルの１：１（体積比）混合溶
媒を展開液とするシリカゲルカラムに通した。最初に溶
出する薄黄色の副生成物の次に溶出する薄黄色の溶液を
回収して減圧乾固した。得られた固体を少量のジクロロ
メタンに溶解し、ヘキサンを加えて生成した沈殿を濾取
して減圧で乾燥することにより目的とするＩｒ（ｐｐ
ｙ）2［３−（ＭＯＩ−Ｐｈ−Ｍｅ）−ａｃａｃ］５９
ｍｇ（０．０６９ｍｍｏｌ）を薄黄色の固体として得
た。収率６８％。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲ
で行った。1H NMR (CDCl3): d 8.58 (d, J = 5.9 Hz, 2
H, ppy), 7.88 (d,J = 7.8 Hz, 2 H, ppy), 7.76 (t,
J = 6.5 Hz, 2 H, ppy), 7.57 (d, J = 7.6Hz, 2 H, pp
y), 7.2 6.6 (m, 10 H, aromatic), 6.27 (d, J = 7.6
Hz, 2 H,ppy), 6.16 (s, 1 H, olefinic), 5.63 (s, 1
H, olefinic), 5.31 (br-s, 1 H,NH), 4.31 (m, 2 H,
ethylene), 3.69 (s, 2 H, benzyl), 3.59 (m, 2 H, et
hylene), 1.98 (s, 3 H, methacryl-methyl), 1.80 (s,
6 H, diketonate-methyl). E.A.: Calcd for C41H38Ir
N3O6: C, 57.20; H, 4.45; N, 4.88. Found: C, 57.3
6; H, 4.43; N, 4.91.Then, as shown in Scheme (8B),
This Ir (ppy) 2 [1- (OH-Ph-Me) -a
cac] and methacryloyloxyethyl isocyanate (MOI: trade name, manufactured by Showa Denko) to produce Ir (ppy) 2 [1- (MOI-Ph-Me) -a
cac] was synthesized. That is, Ir (ppy) 2 [1-
(OH-Ph-Me) -acac] 71 mg (0.10
mmol) and 3,6-di-tert-butyl-4-methylphenol 3 mg (0.014 mmol), dibutyltin (IV) dilaurate 27 mg (0.12 mmol).
And MOI 55 mg (0.35 mmol) in THF1
It was dissolved in 0 ml and heated with stirring at 70 ° C. for 2 hours. The reaction mixture obtained was dried under reduced pressure on a rotary evaporator,
The residue was passed through a silica gel column using a 1: 1 (volume ratio) mixed solvent of hexane / ethyl acetate as a developing solution. The light yellow solution, which elutes first and then the light yellow by-product, was collected and evaporated to dryness under reduced pressure. The obtained solid is dissolved in a small amount of dichloromethane, hexane is added, and the formed precipitate is collected by filtration and dried under reduced pressure to obtain the desired Ir (pp
y) 2 [3- (MOI-Ph-Me) -acac] 59
Obtained mg (0.069 mmol) as a pale yellow solid. Yield 68%. Identification is by CHN elemental analysis, 1 H-NMR
I went there. 1 H NMR (CDCl 3 ): d 8.58 (d, J = 5.9 Hz, 2
H, ppy), 7.88 (d, J = 7.8 Hz, 2 H, ppy), 7.76 (t,
J = 6.5 Hz, 2 H, ppy), 7.57 (d, J = 7.6 Hz, 2 H, pp
y), 7.2 6.6 (m, 10 H, aromatic), 6.27 (d, J = 7.6
Hz, 2 H, ppy), 6.16 (s, 1 H, olefinic), 5.63 (s, 1
H, olefinic), 5.31 (br-s, 1 H, NH), 4.31 (m, 2 H,
ethylene), 3.69 (s, 2 H, benzyl), 3.59 (m, 2 H, et
hylene), 1.98 (s, 3 H, methacryl-methyl), 1.80 (s,
6 H, diketonate-methyl). EA: Calcd for C 41 H 38 Ir
N 3 O 6 : C, 57.20; H, 4.45; N, 4.88.Found: C, 57.3
6; H, 4.43; N, 4.91.

【０１１３】[0113]

【化７１】 [Chemical 71]

【０１１４】[0114]

【発明の効果】本発明の新規な重合性化合物はイリジウ
ム錯体部分を含む新規な重合体を与え、これを有機発光
素子の発光材料として使用することにより励起三重項状
態から高効率で発光し、かつ大面積化が可能で量産に適
した有機発光素子を提供することができる。INDUSTRIAL APPLICABILITY The novel polymerizable compound of the present invention provides a novel polymer containing an iridium complex moiety, and by using it as a light emitting material for an organic light emitting device, it emits light with high efficiency from an excited triplet state, In addition, it is possible to provide an organic light emitting device that can be made large in area and suitable for mass production.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 11/06 ６６０ Ｃ０９Ｋ 11/06 ６６０ ６８０ ６８０ Ｈ０５Ｂ 33/14 Ｈ０５Ｂ 33/14 Ｂ // Ｃ０７Ｆ 15/00 Ｃ０７Ｆ 15/00 Ｅ (72)発明者 蒲池 元昭 千葉県千葉市緑区大野台一丁目１番１号 昭和電工株式会社総合研究所内 (72)発明者 伊藤 直子 千葉県千葉市緑区大野台一丁目１番１号 昭和電工株式会社総合研究所内 Ｆターム(参考） 3K007 AB02 AB03 AB11 AB18 DB03 4H006 AA01 AA03 AB46 AB92 4H050 AA01 AA03 AB46 AB92 WB11 WB13 WB14 4J031 BA19 BB03 BB09 BD21 4J100 AB07P AQ31P BA38P BB07P BC43P BC52P BC58P BC69P BD04P BD15P CA01 JA32─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09K 11/06 660 C09K 11/06 660 680 680 H05B 33/14 H05B 33/14 B // C07F 15/00 C07F 15/00 E (72) Inventor Motoaki Kamike 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Showa Denko K.K. Research Institute (72) Inventor Naoko Ito 1-1, Onodai, Midori-ku, Chiba-shi No. 1 Showa Denko Co., Ltd. Research Center F-term (reference) 3K007 AB02 AB03 AB11 AB18 DB03 4H006 AA01 AA03 AB46 AB92 4H050 AA01 AA03 AB46 AB92 WB11 WB13 WB14 4J031 BA19 BB03 BB09 BD21 BD58PBCP BD58P BC58P BC38P BC58P BC38P CA01 JA32

Claims (42)

【特許請求の範囲】[Claims] 【請求項１】式（１）で示される重合性化合物。 【化１】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基を表し、Ｘ1、Ｙ1、Ｚ1のうちの残り
はそれぞれ独立に水素原子またはヘテロ原子を有しても
よい炭素数１〜２０の有機基を表す。Ｒ1〜Ｒ12はそれ
ぞれ独立に水素原子、ハロゲン原子、ニトロ基、アミノ
基、スルホン酸基、スルホン酸エステル基またはヘテロ
原子を有してもよい炭素数１〜２０の有機基を表す。〕1. A polymerizable compound represented by formula (1). [Chemical 1] Wherein, X 1, Y 1, at least one of Z 1 represents a substituent having a polymerizable functional group, the X 1, Y 1, each remaining independently a hydrogen atom or a heteroatom of Z 1 It represents an organic group which may have 1 to 20 carbon atoms. R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項２】前記式（１）におけるＸ1またはＺ1のいず
れか一方が重合性官能基を有する置換基である請求項１
に記載の重合性化合物。2. One of X 1 and Z 1 in the formula (1) is a substituent having a polymerizable functional group.
The polymerizable compound according to. 【請求項３】式（２）で示される重合性化合物。 【化２】 〔式中、Ｘ1は重合性官能基を有する置換基を表し、Ｑ1
およびＱ2はそれぞれ独立に水素原子またはヘテロ原子
を有してもよい炭素数１〜２０の有機基を表す。〕3. A polymerizable compound represented by formula (2). [Chemical 2] [In the formula, X 1 represents a substituent having a polymerizable functional group, and Q 1
And Q 2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項４】重合性官能基が炭素−炭素二重結合である
請求項１〜３のいずれか一つに記載の重合性化合物。4. The polymerizable compound according to claim 1, wherein the polymerizable functional group is a carbon-carbon double bond. 【請求項５】式（３）で示される重合性化合物。 【化３】 5. A polymerizable compound represented by formula (3). [Chemical 3] 【請求項６】重合性官能基がスチリル基である請求項１
〜３のいずれか一つに記載の重合性化合物。6. The polymerizable functional group is a styryl group.
The polymerizable compound according to any one of to 3. 【請求項７】式（４）で示される重合性化合物。 【化４】 7. A polymerizable compound represented by formula (4). [Chemical 4] 【請求項８】重合性官能基がアクリレート基またはメタ
クリレート基である請求項１〜３のいずれか一つに記載
の重合性化合物。8. The polymerizable compound according to claim 1, wherein the polymerizable functional group is an acrylate group or a methacrylate group. 【請求項９】式（５）で示される重合性化合物。 【化５】 〔式中、Ｒは水素原子またはメチル基を表す。〕9. A polymerizable compound represented by formula (5). [Chemical 5] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１０】式（６）で示される重合性化合物。 【化６】 〔式中、Ｒは水素原子またはメチル基を表す。〕10. A polymerizable compound represented by formula (6). [Chemical 6] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１１】式（７）で示される重合性化合物。 【化７】 〔式中、Ｒは水素原子またはメチル基を表す。〕11. A polymerizable compound represented by formula (7). [Chemical 7] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１２】式（８）で示される重合性化合物。 【化８】 〔式中、Ｒは水素原子またはメチル基を表す。〕12. A polymerizable compound represented by formula (8). [Chemical 8] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１３】式（９）で示される重合性化合物。 【化９】 〔式中、Ｒは水素原子またはメチル基を表す。〕13. A polymerizable compound represented by formula (9). [Chemical 9] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１４】式（１０）で示される重合性化合物。 【化１０】 〔式中、Ｒは水素原子またはメチル基を表す。〕14. A polymerizable compound represented by formula (10). [Chemical 10] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１５】式（１１）で示される重合性化合物。 【化１１】 〔式中、Ｒは水素原子またはメチル基を表す。〕15. A polymerizable compound represented by the formula (11). [Chemical 11] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１６】式（１２）で示される重合性化合物。 【化１２】 〔式中、Ｒは水素原子またはメチル基を表す。〕16. A polymerizable compound represented by formula (12). [Chemical 12] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項１７】式（１３）で示される重合性化合物。 【化１３】 17. A polymerizable compound represented by the formula (13). [Chemical 13] 【請求項１８】前記式（１）におけるＹ1が重合性官能
基を有する置換基である請求項１に記載の重合性化合
物。18. The polymerizable compound according to claim 1, wherein Y 1 in the formula (1) is a substituent having a polymerizable functional group. 【請求項１９】式（１４）で示される重合性化合物。 【化１４】 〔式中、Ｙ1は重合性官能基を有する置換基を表し、Ｑ2
およびＱ3はそれぞれ独立に水素原子またはヘテロ原子
を有してもよい炭素数１〜２０の有機基を表す。〕19. A polymerizable compound represented by formula (14). [Chemical 14] [In the formula, Y 1 represents a substituent having a polymerizable functional group, and Q 2
And Q 3 each independently represent an organic group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. ] 【請求項２０】重合性官能基が炭素−炭素二重結合であ
る請求項１８または１９に記載の重合性化合物。20. The polymerizable compound according to claim 18, wherein the polymerizable functional group is a carbon-carbon double bond. 【請求項２１】重合性官能基がスチリル基である請求項
１８または１９に記載の重合性化合物。21. The polymerizable compound according to claim 18, wherein the polymerizable functional group is a styryl group. 【請求項２２】重合性官能基がアクリレート基またはメ
タクリレート基である請求項１８または１９に記載の重
合性化合物。22. The polymerizable compound according to claim 18, wherein the polymerizable functional group is an acrylate group or a methacrylate group. 【請求項２３】式（１５）で示される重合性化合物。 【化１５】 〔式中、Ｒは水素原子またはメチル基を表す。〕23. A polymerizable compound represented by formula (15). [Chemical 15] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項２４】式（１６）で示される重合性化合物。 【化１６】 〔式中、Ｒは水素原子またはメチル基を表す。〕24. A polymerizable compound represented by formula (16). [Chemical 16] [In the formula, R represents a hydrogen atom or a methyl group. ] 【請求項２５】式（１７）で示されるイリジウム二核錯
体と式（１８）で示される重合性官能基を有する化合物
を反応させることを特徴とする単核イリジウム錯体部分
を含む重合性化合物の製造方法。 【化１７】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕 【化１８】 〔式中、Ｘ1、Ｙ1、Ｚ1の少なくとも１つは重合性官能
基を有する置換基、Ｘ1、Ｙ1、Ｚ1のうちの残りはそれ
ぞれ独立に水素原子またはヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。〕25. A polymerizable compound containing a mononuclear iridium complex moiety characterized by reacting a iridium binuclear complex represented by formula (17) with a compound having a polymerizable functional group represented by formula (18). Production method. [Chemical 17] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ] [Chemical 18] [In the formula, at least one of X 1 , Y 1 and Z 1 has a substituent having a polymerizable functional group, and the rest of X 1 , Y 1 and Z 1 each independently have a hydrogen atom or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ] 【請求項２６】前記式（１８）におけるＸ1またはＺ1が
重合性官能基を有する置換基である請求項２５に記載の
単核イリジウム錯体部分を含む重合性化合物の製造方
法。26. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 25, wherein X 1 or Z 1 in the formula (18) is a substituent having a polymerizable functional group. 【請求項２７】前記式（１８）におけるＹ1が重合性官
能基を有する置換基である請求項２５に記載の単核イリ
ジウム錯体部分を含む重合性化合物の製造方法。27. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 25, wherein Y 1 in the formula (18) is a substituent having a polymerizable functional group. 【請求項２８】式（１７）で示されるイリジウム二核錯
体と式（１９）で示される反応性置換基を有する化合物
を反応させた後、得られた単核イリジウム錯体の反応性
置換基と重合性官能基を有する化合物を反応させること
を特徴とする単核イリジウム錯体部分を含む重合性化合
物の製造方法。 【化１９】 〔式中、Ｒ1〜Ｒ24はそれぞれ独立に水素原子、ハロゲ
ン原子、ニトロ基、アミノ基、スルホン酸基、スルホン
酸エステル基またはヘテロ原子を有してもよい炭素数１
〜２０の有機基を表す。〕 【化２０】 〔式中、Ｘ2、Ｙ2、Ｚ2の少なくとも１つは反応性置換
基、Ｘ2、Ｙ2、Ｚ2のうちの残りはそれぞれ独立に水素
原子またはヘテロ原子を有してもよい炭素数１〜２０の
有機基を表す。〕28. After reacting the iridium binuclear complex represented by the formula (17) with a compound having a reactive substituent represented by the formula (19), the resulting mononuclear iridium complex is reacted with the reactive substituent. A method for producing a polymerizable compound containing a mononuclear iridium complex portion, which comprises reacting a compound having a polymerizable functional group. [Chemical 19] [In the formula, R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a carbon atom which may have a hetero atom.
Represents an organic group of 20. ] [Chemical 20] [In the formula, at least one of X 2 , Y 2 and Z 2 is a reactive substituent, and the rest of X 2 , Y 2 and Z 2 are each independently a carbon atom which may have a hydrogen atom or a hetero atom. Represents an organic group of the number 1 to 20. ] 【請求項２９】式（１９）におけるＸ2またはＹ2が水酸
基を有する置換基である請求項２８に記載の単核イリジ
ウム錯体部分を含む重合性化合物の製造方法。29. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 28, wherein X 2 or Y 2 in formula (19) is a substituent having a hydroxyl group. 【請求項３０】式（１９）におけるＹ2が水酸基を有す
る置換基である請求項２８に記載の単核イリジウム錯体
部分を含む重合性化合物の製造方法。30. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 28, wherein Y 2 in formula (19) is a substituent having a hydroxyl group. 【請求項３１】式（２０）で示される化合物。 【化２１】 〔式中、Ｘ2、Ｙ2、Ｚ2の少なくとも１つは水酸基を有
する置換基を表し、Ｘ2、Ｙ2、Ｚ2のうちの残りはそれ
ぞれ独立に水素原子またはヘテロ原子を有してもよい炭
素数１〜２０の有機基を表す。Ｒ1〜Ｒ12はそれぞれ独
立に水素原子、ハロゲン原子、ニトロ基、アミノ基、ス
ルホン酸基、スルホン酸エステル基またはヘテロ原子を
有してもよい炭素数１〜２０の有機基を表す。〕31. A compound represented by the formula (20): [Chemical 21] Wherein, X 2, Y 2, at least one of Z 2 represents a substituent having a hydroxyl group, with a X 2, Y 2, each remaining independently a hydrogen atom or a heteroatom of Z 2 Represents an organic group having 1 to 20 carbon atoms. R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group, or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項３２】式（２０）におけるＸ2またはＺ2が水酸
基を有する置換基である請求項３１に記載の化合物。32. The compound according to claim 31, wherein X 2 or Z 2 in the formula (20) is a substituent having a hydroxyl group. 【請求項３３】式（２１）で示される化合物。 【化２２】 〔式中、ｎは０〜２０の整数を表し、Ｑ1およびＱ2はそ
れぞれ独立に水素原子またはヘテロ原子を有してもよい
炭素数１〜２０の有機基を表す。〕(33) A compound represented by the formula (21): [Chemical formula 22] [In the formula, n represents an integer of 0 to 20, and Q 1 and Q 2 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項３４】式（２２）で示される化合物。 【化２３】 〔式中、ｎは０〜２０の整数を表し、Ｑ1およびＱ2はそ
れぞれ独立に基またはヘテロ原子を有してもよい炭素数
１〜２０の有機基を表す。〕34. A compound represented by the formula (22): [Chemical formula 23] [In the formula, n represents an integer of 0 to 20, and Q 1 and Q 2 each independently represent a group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項３５】式（２０）におけるＹ2が水酸基を有す
る置換基である請求項３１に記載の化合物。35. The compound according to claim 31, wherein Y 2 in formula (20) is a substituent having a hydroxyl group. 【請求項３６】式（２３）で示される化合物。 【化２４】 〔式中、ｎは０〜２０の整数を表し、Ｑ2およびＱ3はそ
れぞれ独立に水素原子またはヘテロ原子を有してもよい
炭素数１〜２０の有機基を表す。〕36. A compound represented by the formula (23): [Chemical formula 24] [In the formula, n represents an integer of 0 to 20, and Q 2 and Q 3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 【請求項３７】請求項１〜２4のいずれか一つに記載の
重合性化合物の重合体。37. A polymer of the polymerizable compound according to any one of claims 1 to 24. 【請求項３８】請求項１〜２4のいずれか一つに記載の
重合性化合物を１種以上含む組成物を重合してなる重合
体。38. A polymer obtained by polymerizing a composition containing at least one polymerizable compound according to any one of claims 1 to 24. 【請求項３９】請求項１〜２4のいずれか一つに記載の
重合性化合物を含むことを特徴とする発光材料。39. A luminescent material comprising the polymerizable compound according to any one of claims 1 to 24. 【請求項４０】請求項１〜２4のいずれか一つに記載の
重合性化合物を重合してなる発光材料。40. A luminescent material obtained by polymerizing the polymerizable compound according to any one of claims 1 to 24. 【請求項４１】請求項１〜２4のいずれか一つに記載の
重合性化合物を１種以上含む組成物を重合してなる発光
材料。41. A luminescent material obtained by polymerizing a composition containing at least one polymerizable compound according to any one of claims 1 to 24. 【請求項４２】請求項３９〜４１のいずれか一つに記載
の発光材料を用いた有機発光素子。42. An organic light emitting device using the light emitting material according to any one of claims 39 to 41.
JP2001306282A 2001-06-20 2001-10-02 Polymerizable compound and method for producing the same Expired - Lifetime JP4035976B2 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
JP2001306282A JP4035976B2 (en) 2001-10-02 2001-10-02 Polymerizable compound and method for producing the same
TW91113391A TW584661B (en) 2001-06-20 2002-06-19 Light emitting material and organic light-emitting device
AU2002345362A AU2002345362A1 (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
AT02743651T ATE431970T1 (en) 2001-06-20 2002-06-20 LIGHT EMITTING MATERIAL AND ORGANIC LIGHT EMITTING DIODE
EP02743651A EP1407501B1 (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
US10/481,442 US7396598B2 (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
CNB028123123A CN100440568C (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
KR1020037016625A KR100925409B1 (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
PCT/JP2002/006139 WO2003001616A2 (en) 2001-06-20 2002-06-20 Light emitting material and organic light-emitting device
DE60232415T DE60232415D1 (en) 2001-06-20 2002-06-20 LIGHT-EMITTING MATERIAL AND ORGANIC LUMINAIRE DIODE
US12/026,877 US7736757B2 (en) 2001-06-20 2008-02-06 Light emitting material and organic light-emitting device
US12/026,798 US7763365B2 (en) 2001-06-20 2008-02-06 Light emitting material and organic light-emitting device
US12/026,854 US7635527B2 (en) 2001-06-20 2008-02-06 Light emitting material and organic light-emitting device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001306282A JP4035976B2 (en) 2001-10-02 2001-10-02 Polymerizable compound and method for producing the same

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP2007027557A Division JP4902381B2 (en) 2007-02-07 2007-02-07 Polymer of polymerizable compound

Publications (2)

Publication Number Publication Date
JP2003113246A true JP2003113246A (en) 2003-04-18
JP4035976B2 JP4035976B2 (en) 2008-01-23

Family

ID=19125943

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001306282A Expired - Lifetime JP4035976B2 (en) 2001-06-20 2001-10-02 Polymerizable compound and method for producing the same

Country Status (1)

Country Link
JP (1) JP4035976B2 (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003080687A1 (en) * 2002-03-26 2003-10-02 Canon Kabushiki Kaisha Polymeric compound and electroluminescent element
JP2003342325A (en) * 2001-08-31 2003-12-03 Nippon Hoso Kyokai <Nhk> Phosphorescent compound, phosphorescent composition and organic light-emitting element
JP2004182738A (en) * 2002-12-03 2004-07-02 Lg Electron Inc Phenylpyridine-iridium metal complex compound for organic electroluminescent element, method for producing the same and organic electroluminescent element using the same
JP2005097589A (en) * 2003-08-29 2005-04-14 Showa Denko Kk Phosphorescent polymer compound and organic light emitting device using this
WO2005061562A1 (en) * 2003-12-19 2005-07-07 Showa Denko K.K. Boron-containing polymer compound and organic light emitting device using the same
JP2005220351A (en) * 2004-01-27 2005-08-18 Samsung Sdi Co Ltd Polysilsesquioxane compound and organic electroluminescence element using this
JP2006503126A (en) * 2002-07-30 2006-01-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Metal complexes covalently bonded to conjugated polymers and electronic devices comprising such compositions
JP2007031679A (en) * 2005-07-29 2007-02-08 Showa Denko Kk Light emitting polymer material, organic electroluminescent element and display device
JP2007059939A (en) * 2001-08-31 2007-03-08 Nippon Hoso Kyokai <Nhk> Organic light emitting device and display unit
JP2007131815A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element, and display device
JP2007131813A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element, and display device
JP2007131814A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescence element, and display device
JP2007153917A (en) * 2005-11-30 2007-06-21 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2007153918A (en) * 2005-11-30 2007-06-21 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2007161933A (en) * 2005-12-15 2007-06-28 Showa Denko Kk Polymeric light-emitting material, organic electroluminescent element, and display device
JP2007161934A (en) * 2005-12-15 2007-06-28 Showa Denko Kk Polymer luminescent material, organoelectroluminescent element and display device
JP2007169475A (en) * 2005-12-22 2007-07-05 Showa Denko Kk Polymer light-emitting material, organic electroluminescent element and display
JP2007169334A (en) * 2005-12-19 2007-07-05 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element and display device
US7250226B2 (en) 2001-08-31 2007-07-31 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
JP2007197575A (en) * 2006-01-26 2007-08-09 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2008010653A (en) * 2006-06-29 2008-01-17 Showa Denko Kk Organic electroluminescence element, and display
JP2008505925A (en) * 2004-07-07 2008-02-28 ユニバーサル ディスプレイ コーポレイション Stable and efficient electroluminescent material
WO2008053935A1 (en) 2006-11-01 2008-05-08 Showa Denko K.K. Cyclic siloxane compound, organic electroluminescent element, and use thereof
US7445857B2 (en) 2004-12-22 2008-11-04 Industrial Technology Research Institute Organometallic complex and organic electroluminescent devices utilizing the same
WO2009101983A1 (en) 2008-02-15 2009-08-20 Showa Denko K.K. Method for treating surface of electrode, electrode, and process for producing organic electroluminescent element
WO2009131165A1 (en) 2008-04-24 2009-10-29 昭和電工株式会社 Charge-transporting polymer compound and organic electroluminescent device using the same
US7638071B2 (en) 2004-03-24 2009-12-29 Showa Denko K.K. Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device
JP2010013662A (en) * 2002-06-04 2010-01-21 Hc Starck Gmbh Phosphorescent and luminescent conjugated polymer, and method for its application to electroluminescent assembly
WO2010134518A1 (en) 2009-05-19 2010-11-25 昭和電工株式会社 Surface treatment method for electrodes and method for producing electrodes and organic luminescence elements
JP2011001553A (en) * 2001-08-31 2011-01-06 Nippon Hoso Kyokai <Nhk> Phosphorescent compound, phosphorescent composition, organic light-emitting element and display
WO2011010503A1 (en) 2009-07-21 2011-01-27 昭和電工株式会社 Light emitting element, method for manufacturing light emitting element, image display device, and illuminating device
WO2012029156A1 (en) 2010-09-02 2012-03-08 昭和電工株式会社 Electroluminescent element, electroluminescent element manufacturing method, display device, and illumination device
US9644048B2 (en) 2009-10-27 2017-05-09 Samsung Electronics Co., Ltd Composition for anode buffer layer, high-molecular weight compound for anode buffer layer, organic electroluminescence element, and production process and uses of the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2830790C2 (en) 1978-07-13 1982-09-30 Jurij Petrovi&ccaron; Leningrad Ivanov Method of building hulls

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003342325A (en) * 2001-08-31 2003-12-03 Nippon Hoso Kyokai <Nhk> Phosphorescent compound, phosphorescent composition and organic light-emitting element
US7250226B2 (en) 2001-08-31 2007-07-31 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
JP2011001553A (en) * 2001-08-31 2011-01-06 Nippon Hoso Kyokai <Nhk> Phosphorescent compound, phosphorescent composition, organic light-emitting element and display
JP4629643B2 (en) * 2001-08-31 2011-02-09 日本放送協会 Organic light emitting device and display device
JP2007059939A (en) * 2001-08-31 2007-03-08 Nippon Hoso Kyokai <Nhk> Organic light emitting device and display unit
US7108924B2 (en) 2002-03-26 2006-09-19 Canon Kabushiki Kaisha Polymer compound and electroluminescent element
WO2003080687A1 (en) * 2002-03-26 2003-10-02 Canon Kabushiki Kaisha Polymeric compound and electroluminescent element
JP2010013662A (en) * 2002-06-04 2010-01-21 Hc Starck Gmbh Phosphorescent and luminescent conjugated polymer, and method for its application to electroluminescent assembly
JP2006503126A (en) * 2002-07-30 2006-01-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Metal complexes covalently bonded to conjugated polymers and electronic devices comprising such compositions
JP2004182738A (en) * 2002-12-03 2004-07-02 Lg Electron Inc Phenylpyridine-iridium metal complex compound for organic electroluminescent element, method for producing the same and organic electroluminescent element using the same
JP2005097589A (en) * 2003-08-29 2005-04-14 Showa Denko Kk Phosphorescent polymer compound and organic light emitting device using this
WO2005061562A1 (en) * 2003-12-19 2005-07-07 Showa Denko K.K. Boron-containing polymer compound and organic light emitting device using the same
US7510782B2 (en) 2003-12-19 2009-03-31 Showa Denko K.K. Boron-containing polymer compound and organic light emitting device using the same
JP2005220351A (en) * 2004-01-27 2005-08-18 Samsung Sdi Co Ltd Polysilsesquioxane compound and organic electroluminescence element using this
US7857999B2 (en) 2004-03-24 2010-12-28 Showa Denko K.K. Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device
EP2207185A1 (en) 2004-03-24 2010-07-14 Showa Denko Kabushiki Kaisha Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device
US7638071B2 (en) 2004-03-24 2009-12-29 Showa Denko K.K. Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device
JP2008505925A (en) * 2004-07-07 2008-02-28 ユニバーサル ディスプレイ コーポレイション Stable and efficient electroluminescent material
US7445857B2 (en) 2004-12-22 2008-11-04 Industrial Technology Research Institute Organometallic complex and organic electroluminescent devices utilizing the same
JP2007031679A (en) * 2005-07-29 2007-02-08 Showa Denko Kk Light emitting polymer material, organic electroluminescent element and display device
JP2007131815A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element, and display device
JP2007131813A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element, and display device
JP2007131814A (en) * 2005-11-14 2007-05-31 Showa Denko Kk Polymeric luminescent material, organic electroluminescence element, and display device
JP2007153918A (en) * 2005-11-30 2007-06-21 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2007153917A (en) * 2005-11-30 2007-06-21 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2007161933A (en) * 2005-12-15 2007-06-28 Showa Denko Kk Polymeric light-emitting material, organic electroluminescent element, and display device
JP2007161934A (en) * 2005-12-15 2007-06-28 Showa Denko Kk Polymer luminescent material, organoelectroluminescent element and display device
JP2007169334A (en) * 2005-12-19 2007-07-05 Showa Denko Kk Polymeric luminescent material, organic electroluminescent element and display device
JP2007169475A (en) * 2005-12-22 2007-07-05 Showa Denko Kk Polymer light-emitting material, organic electroluminescent element and display
JP4717629B2 (en) * 2005-12-22 2011-07-06 昭和電工株式会社 Polymer light-emitting material, organic electroluminescence element, and display device
JP2007197575A (en) * 2006-01-26 2007-08-09 Showa Denko Kk Polymer luminescent material, organic electroluminescent element and display
JP2008010653A (en) * 2006-06-29 2008-01-17 Showa Denko Kk Organic electroluminescence element, and display
WO2008053935A1 (en) 2006-11-01 2008-05-08 Showa Denko K.K. Cyclic siloxane compound, organic electroluminescent element, and use thereof
WO2009101983A1 (en) 2008-02-15 2009-08-20 Showa Denko K.K. Method for treating surface of electrode, electrode, and process for producing organic electroluminescent element
WO2009131165A1 (en) 2008-04-24 2009-10-29 昭和電工株式会社 Charge-transporting polymer compound and organic electroluminescent device using the same
WO2010134518A1 (en) 2009-05-19 2010-11-25 昭和電工株式会社 Surface treatment method for electrodes and method for producing electrodes and organic luminescence elements
WO2011010503A1 (en) 2009-07-21 2011-01-27 昭和電工株式会社 Light emitting element, method for manufacturing light emitting element, image display device, and illuminating device
US8735875B2 (en) 2009-07-21 2014-05-27 Showa Denko K.K. Light emitting element, method for manufacturing light emitting element, image display device, and illuminating device
US9644048B2 (en) 2009-10-27 2017-05-09 Samsung Electronics Co., Ltd Composition for anode buffer layer, high-molecular weight compound for anode buffer layer, organic electroluminescence element, and production process and uses of the same
WO2012029156A1 (en) 2010-09-02 2012-03-08 昭和電工株式会社 Electroluminescent element, electroluminescent element manufacturing method, display device, and illumination device

Also Published As

Publication number Publication date
JP4035976B2 (en) 2008-01-23

Similar Documents

Publication Publication Date Title
JP4902381B2 (en) Polymer of polymerizable compound
JP4035976B2 (en) Polymerizable compound and method for producing the same
JP4986004B2 (en) Polymerizable iridium complex, polymer thereof and production method thereof
JP5198856B2 (en) Metal complex
KR100676965B1 (en) Novel iridium complex and organic electroluminescence device using the same
JP2003147021A (en) Polymerizable compound and method for producing the same
JP5281270B2 (en) Iridium complex compound, organic electroluminescence device using the same, and use thereof
WO2005033090A1 (en) Aromatic compound
JP2007045742A (en) Manufacturing method of transition metal complex and transition metal complex
EP2019108A2 (en) Novel red electroluminescent compounds and organic electronluminescent device using same
JP5294242B2 (en) Metal coordination compound and light emitting material using the same
US8293898B2 (en) Luminophores
EP1700860B1 (en) Polycyclic fused ring type pi-conjugated organic materials, intermediate therefor, process for producing polycyclic fused ring type pi-conjugated organic materials, and process for producing intermediate for polycyclic fused ring type pi-conjugated organic materials
CN111788212A (en) Spiro-containing platinum (II) emitters with tunable emission energy and synthesis thereof
JP2001261796A (en) Alkoxypolythiophene and alkoxythiophene
JP5034157B2 (en) Aromatic compounds
CN102325781A (en) Organic metal complexes for use in optoelectronic devices
JP4296995B2 (en) Fluorene compound and method for producing the same
US5990335A (en) Di-p-tolydialkylsilane derivative and photoluminescene polymer formed therefrom and methods for preparing these compounds
KR100688030B1 (en) Novel luminescent Ir(Ⅲ)-chelated dendritic complexes containing aryl ether-typed dendrons and their synthetic methods
JPH08113582A (en) Bifunctional alkylphosphine oxide and its production
KR100521662B1 (en) 9,10-Bis(styryl)anthracene derivatives and manufacturing method thereof
JP3385353B2 (en) Cyclic silicon compound having a functional group
JPH11171812A (en) Benzyl ether-based dendrimer compound
KR100497023B1 (en) Novel Preparing Method of 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (DPVA) for Blue Luminescence Material Using Phosphonium Halide Compound

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20040916

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20060829

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20061016

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20061212

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20070207

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20071009

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20071022

R150 Certificate of patent or registration of utility model

Ref document number: 4035976

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101109

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20101109

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131109

Year of fee payment: 6

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250