1997 年度実績報告書

アルキン結合を利用した新しい有機金属錯体超分子の構築とその構造および機能

研究課題

研究課題/領域番号	09740501
研究機関	近畿大学
研究代表者	前川雅彦近畿大学, 理工学総合研究所, 助手 (70229293)
キーワード	Cu錯体 / Ag錯体 / Rh錯体 / 金属錯体ポリマー / 分子集合体 / X線構造 / interwoven構造 / 一次元無限鎖構造
研究概要	配位結合や水素結合、π-πスタッキングなどを用いて構築した金属錯体超分子はこれまでにない新しい分子構造や物性を発現することから興味が持たれている。本研究では金属イオンとπ系配位子により構築された新しいタイプの有機金属錯体超分子の合成を目指し、その系統的合成法の確立ならびに構造、物性研究を行った。本年度はπ系配位子として1,4-bis(4-pyridyl)butadiyne(bpb)ならびに1,4-bis(4′-pyridyl-ethynyl)benzene(bpeb)を合成し、これらを用いてCu(I),Ag(I)ならびにRh(I)錯体の合成を試み、有機金属錯体超分子{[Cu_2(bpb)_3(CH_3CN)_2](PF_6)_2}_∞(1)、{[Ag(bpb)]CF_3SO_3}_∞(2)、{[Rh(bpb)(cod)_2]BF_4}_∞(3)を単離し、その分子構造を決定した。錯体1は各々のCu原子に3つのbpbdのN原子とCH_3CNのN原子が配位し、またこれらのCu原子がbpbdの両端のピリジン環のN原子に橋かけされ、ジグザグ型の「はしっご型一次元無限鎖構造」を形成し、さらにこれらの一次元無限鎖がお互い絡み合い「interwoven二次元シート構造」を形成している。錯体2は各々のAg原子が2つのbpbdのN原子に配位され直線構造を取っており、これらAg原子がbpbdの両端のピリジン環のN原子により順次橋かけされることにより「直線型一次元無限鎖構造」を形成している。錯体3は各々のRh原子が2つのbdpdのN原子とcodの2つのC=C結合により配位されることにより四面体構造を取っており、またこれらのRh原子がbpbdの両端のピリジン環のN原子により橋かけされることにより「ジグザグ型一次元無限鎖構造」を形成していることが明らかとなった。次年度はこれら化合物の物性探索ならびに機能付与を行なう。

研究成果
(16件)

すべてその他

すべて文献書誌 (16件)

[文献書誌] M.Munakata and M.Maekawa, et al.: "Assembly of a mixed-valence Cu(I/II) system coupled by multiple hydrogen bonding through tetrahydrowybenzoquinone" Inorganica Chimica Acta. 268. 317-321 (1998)
[文献書誌] T.Kuroda-Sowa and M.Maekawa, et al.: "Structural control of copper(I) coordination polymers: Construction of one-,two- and three-dimensional frameworks of tetrahedral copper(I) ions bridged by dicyanobenzene derivatives" Inorganic Chemisty. 36. 6382-6389 (1997)
[文献書誌] M.Maekawa, et al.: "Synthesis and crystal structure of two ternary dicopper(I) complexes having the unsymmetrical coordination arrangement bridged by 1,8-naphthyridine (napy)" Inorganica Chimica Acta. (in press).
[文献書誌] M.Maekawa, et al: "Crystal structure of bis (diphenylphosphino)methane dipalladium (I) nitrate complex" Analytical Sciences. (in press).
[文献書誌] M.Maekawa, et al: "Crystal strudcture of tetranuclear palladium complexes bridged by bis (diphenylphosphino) methane" Analytical Sciences. (in press).
[文献書誌] J.Dai and M.Maekawa, et al.: "S…S contact-assembled silver(I) complexes of 4,5-ethylenedithio-1,3-dithiole-2-thione having unique supramolecular networks" J.Chem.Soc., Dalton Trans.2363-2368 (1997)
[文献書誌] M.Yamamoto and M.Maekawa, et al.: "Syntheses,structures and properties of linear copper(I) coordination polymers with tetrakis (ethylthio) tetrathiafulvalene and tetrakis-(prophylthio) tetrathafulvalne" Inorganica Chimica Acta. 261. 169-174 (1997)
[文献書誌] M.Munakata and M.Maekawa, et al.: "Construction and conductivity of W-type sandwich silver(I) polymers with phrene and perylene" Inorganic Chemistry. 36. 4903-4905 (1997)
[文献書誌] M.Munakata and M.Maekawa, et al.: "Two types of new polymeric copper(I) complexes of phrazinecarboxamide having channel and helical structures" Inorganic Chemistry. 36. 5416-5418 (1997)
[文献書誌] Y.Suenaga and M.Maekawa, et al.: "Comparative X-ray studies of a copper(I) coordination polymer with 1,2,4,5-tetramethylmercaptobenzene(tmmb)" Analytical Scienes. 13. 1047-1048 (1997)
[文献書誌] M.Munakata and M.Maekawa, et al.: "Solid and solution structures of ternary gold(I) complexes with triphenyl-phosphine and nitrogen-containing ligands" J.Chme.Soc, Dalton Trans.4257-4262 (1997)
[文献書誌] M.Munakata and M.Maekawa, et al.: "Assembly of a mixed-valence Cu(I/II)system coupled by multiple hydrogen bonding through tetrahydrowybenzoquinone" Inorganica Chimica Acta. 268. 317-321 (1998)
[文献書誌] T.Kuroda-Sowa and M.Maekawa, et al.: "Structural control of copper(I) coordination polymers: Construction of one-,two- and three-dimensional frameworks of tetrahedral copper(I) ions bridged by dicyanobenzene derivatives" Inorganic Chemisty. 36. 6382-6389 (1997)
[文献書誌] M.Maekawa, et al.: "Synthesis and crystal structure of two ternary dicopper(I) complexes having the unsymmetrical coordination arrangement bridged by 1,8-naphthyridine (napy)" Inorganica Chimica Acta. (in press).
[文献書誌] M.Maekawa, et al: "Crystal structure of bis (diphenylphosphino) methane dipalladium (I) nitrate complex" Analytical Sciences. (in press).
[文献書誌] M.Maekawa, et al: "Crystal strudcture of tetranuclear palladium complexes bridged by bis (diphenylphosphino) methane" Analytical Sciences. (in press).

1997 年度 実績報告書

アルキン結合を利用した新しい有機金属錯体超分子の構築とその構造および機能

研究代表者

前川 雅彦 近畿大学, 理工学総合研究所, 助手 (70229293)

研究成果

[文献書誌] M.Munakata and M.Maekawa, et al.: "Assembly of a mixed-valence Cu(I/II) system coupled by multiple hydrogen bonding through tetrahydrowybenzoquinone" Inorganica Chimica Acta. 268. 317-321 (1998)

[文献書誌] T.Kuroda-Sowa and M.Maekawa, et al.: "Structural control of copper(I) coordination polymers: Construction of one-,two- and three-dimensional frameworks of tetrahedral copper(I) ions bridged by dicyanobenzene derivatives" Inorganic Chemisty. 36. 6382-6389 (1997)

[文献書誌] M.Maekawa, et al.: "Synthesis and crystal structure of two ternary dicopper(I) complexes having the unsymmetrical coordination arrangement bridged by 1,8-naphthyridine (napy)" Inorganica Chimica Acta. (in press).

[文献書誌] M.Maekawa, et al: "Crystal structure of bis (diphenylphosphino)methane dipalladium (I) nitrate complex" Analytical Sciences. (in press).

[文献書誌] M.Maekawa, et al: "Crystal strudcture of tetranuclear palladium complexes bridged by bis (diphenylphosphino) methane" Analytical Sciences. (in press).

[文献書誌] J.Dai and M.Maekawa, et al.: "S…S contact-assembled silver(I) complexes of 4,5-ethylenedithio-1,3-dithiole-2-thione having unique supramolecular networks" J.Chem.Soc., Dalton Trans.2363-2368 (1997)

[文献書誌] M.Yamamoto and M.Maekawa, et al.: "Syntheses,structures and properties of linear copper(I) coordination polymers with tetrakis (ethylthio) tetrathiafulvalene and tetrakis-(prophylthio) tetrathafulvalne" Inorganica Chimica Acta. 261. 169-174 (1997)

[文献書誌] M.Munakata and M.Maekawa, et al.: "Construction and conductivity of W-type sandwich silver(I) polymers with phrene and perylene" Inorganic Chemistry. 36. 4903-4905 (1997)

[文献書誌] M.Munakata and M.Maekawa, et al.: "Two types of new polymeric copper(I) complexes of phrazinecarboxamide having channel and helical structures" Inorganic Chemistry. 36. 5416-5418 (1997)

[文献書誌] Y.Suenaga and M.Maekawa, et al.: "Comparative X-ray studies of a copper(I) coordination polymer with 1,2,4,5-tetramethylmercaptobenzene(tmmb)" Analytical Scienes. 13. 1047-1048 (1997)

[文献書誌] M.Munakata and M.Maekawa, et al.: "Solid and solution structures of ternary gold(I) complexes with triphenyl-phosphine and nitrogen-containing ligands" J.Chme.Soc, Dalton Trans.4257-4262 (1997)

[文献書誌] M.Munakata and M.Maekawa, et al.: "Assembly of a mixed-valence Cu(I/II)system coupled by multiple hydrogen bonding through tetrahydrowybenzoquinone" Inorganica Chimica Acta. 268. 317-321 (1998)

[文献書誌] T.Kuroda-Sowa and M.Maekawa, et al.: "Structural control of copper(I) coordination polymers: Construction of one-,two- and three-dimensional frameworks of tetrahedral copper(I) ions bridged by dicyanobenzene derivatives" Inorganic Chemisty. 36. 6382-6389 (1997)

[文献書誌] M.Maekawa, et al.: "Synthesis and crystal structure of two ternary dicopper(I) complexes having the unsymmetrical coordination arrangement bridged by 1,8-naphthyridine (napy)" Inorganica Chimica Acta. (in press).

[文献書誌] M.Maekawa, et al: "Crystal structure of bis (diphenylphosphino) methane dipalladium (I) nitrate complex" Analytical Sciences. (in press).

[文献書誌] M.Maekawa, et al: "Crystal strudcture of tetranuclear palladium complexes bridged by bis (diphenylphosphino) methane" Analytical Sciences. (in press).

1997 年度実績報告書

前川雅彦近畿大学, 理工学総合研究所, 助手 (70229293)