2002 Fiscal Year Annual Research Report

刺激応答型金属錯体の創製とそれらの構造・物性・反応

Research Project

Project/Area Number	11304046
Research Institution	OCHANOMIZU UNIVERSITY
Principal Investigator	福田豊お茶の水女子大学, 理学部, 教授 (30021950)
Co-Investigator(Kenkyū-buntansha)	鈴木教之理化学研究所, 有機金属化学研究室, 研究員 (90241231) 山田眞二お茶の水女子大学, 大学院・人間文化研究科, 助教授 (30183122)
Keywords	混合配位子錯体 / クロモトロピズム / ソルバトクロミズム / サーモクロミズム / エレクトロクロミズム / 環状ジアミン / β-ジケトン / 光学活性配位子
Research Abstract	本年度の研究成果は以下の通りであります。(1)キラル配位子としてのジアミン(N-アルキル-1,2-ジアミノプロパン)およびジケトン(アセチルカンファー類)を含む銅およびニッケル混合配位子錯体の合成単離に成功し、その構造を決め、各種溶媒中でのソルバトクロミズムを検討した。本現象は、用いた溶媒のドナー性・アクセプター性に応じて、問題のニッケル錯体の4配位平面構造(赤色)と6配位八面体構造(緑色)間の平衡が、変化する事が主要な原因で有る。次ぎの大きな目的の一つであった不整選択の問題については、キラルーカンファーを含む系のみでは、他のキラル配位子の取込みに十分なものでない事が明かとなった。キラルジアミンでの取込みの方が強そうで有るが、それらの検討は現在進行中で有る。今後配位子等を大量合成して有用な効果を見い出したい。(2)環状ジアミンとジケトナート配位子によるクロモトロピック錯体の合成と溶液内挙動。N-alkylated 1,4-diazacycloheptane(環状ジアミン)と種々のβ-diketonateを組み合わせたニッケル混合錯体を合成し、そのソルバトクロミズム、サーモクロミズムを調べ、溶液内平衡定数を求め、対応する鎖状ジアミンとの違いを調べた。一般に、環状の系は、、立体的に配位平面の上下をシールドする傾向が強く、平面性の高い錯体を形成することが明らかとなった。(3)触媒機能を有すると知られているかさ高なジイミン配位子と、第一遷移金属イオンとの錯形成とその構造を明らかにした。今まで知られていた同配位子を含むパラジウム錯体はオレフィンの高分子化触媒として知られていたが、その構造は未知であった。このジイミンはかさ高い配位子で有るにも関わらず、5配位構造(銅錯体)を取るものもあった。ハロゲン架橋の複核構造のものも得られた。(4)マンガン(II, III)の変化による無色<=>赤色の可逆的な系をコンプレクソンタイプの配位子を用いて確立した。

Research Products

(20 results)

All Other

All Publications (20 results)

[Publications] T.M.Yoshida, et al.: "Phase relation and molecular motions of mixed ligand complex [Zn(hfac)_2(tmen)]as studied by calorimetry and 'H-NMR measarement"J. Phys. Chem. Solids. 60. 1787-1796 (1999)
[Publications] F.Renz et al.: "Anisotropic effect after streching of the spin crossover compound [Fe(II)(2,6-bis(benzimidazol-2'-yl)pynidine)_2](ce04)_2 in polyvinyl-alcohol…"Mol. Cryst, Lig. Cryst.. 335. 531-540 (1999)
[Publications] F.Renz et al.: "Spin-transition in [Fe^<11>(2,6-bis(benzimidazol-2'-yl)pyridine)_2](ce04)_2 : Hysteresis effect dependent on the matrix"Mol. Cryst, Lig. Cryst.. 335. 521-530 (1999)
[Publications] S.Gou et al.: "Cyano-bridged dinuclear iron complexes in different oxidation states"Inorg. chim. Acta. 287. 95-100 (1999)
[Publications] K.Manseki et al.: "Template syntheses and properties of Cu(II)-La(III)complexes of phenol-based symmetric and unsymmetric dinuclear macrocycles"J. Coord. Chem.. 48. 1-13 (1999)
[Publications] A.Paulovicova et al.: "Synthesis, characterization and X-ray crystal structures of two 5-coordinate ternary Cu(II)complexes containing acetylacetonate with …"Inorg. Chim. Acta. 321. 56-62 (2001)
[Publications] U.I.El-Ayaan et al.: "Thermochromism and Solvatochromism in Solution"Monatsh. Chem.. 132. 1279-1294 (2001)
[Publications] M.Hasegawa et al.: "Higher excited state fluorescence of mixed ligand lanchanide(III)complexes with acetylacetonate, ritrate and ecrpyriline"Chem. Phys.. 269. 323-337 (2001)
[Publications] W.Linert et al.: "Chromotropism of coordination Compounds in Solution"Coord. Chem. Rev.. 218. 113-152 (2001)
[Publications] A.Pauloricova et al.: "Mixed ligand Cu(II)Complexes with the rigid bidentate bis(N-aryliminolacenaphtene Ligand : Synelesis, Spectroscopic …"Europ. J. Inorg. Chem.. 2001. 2641-2646 (2001)
[Publications] M.Hasegawa et al.: "Fluorescence spectra of Fe(II)spin crossover complexes with 2,6-bis(benzimidazole-2'-yl) pyridine"Chem. Phys. 227. 21-30 (2002)
[Publications] Kh.S.Abou-El Sherbini et al.: "Study on the complex formation between N-propylsalicylidene based on silica as ion exchanger and some trantion metalions"J. Sci. Islamic Rep. Iran. 13. 217-223 (2002)
[Publications] Y.Fukuda et al.: "Syntheses and specific structures of higher order mixed chelate lanthanide complexes containing terpyridine, acetylacetonate, and …"J. Chem. Soc. Dalton Fans.. 2002. 527-533 (2002)
[Publications] M.Enamulla et al.: "Synthesis, characterization and spin-crossover behaviors of [Co (hydroxycarboxylate)(triphos)]complexes"Bull. Chem. Soc. Jpn.. 75. 2449-2453 (2002)
[Publications] A.Paulovicora et al.: "Synthesis and structural studies of diamagnetic first-row transition metal complexes with the rigid nitrogen ligand : bis(…"Inorg. Chim. Acta. 339. 209-214 (2002)
[Publications] Y.Fukuda et al.: "New chromotropic behavior of Manganese complexes with 1,4,7-triazacyclononane-N, N', N"-tricarboxylates"Inorg. Chim. Acta. 339. 322-326 (2002)
[Publications] S.Yamada, A.Homma: "N-Substituent effect on the cis-trans geometry of nine-membered lactams"J. Chem. Soc. Chem. Commun.. 2002. 2656-2657 (2002)
[Publications] Y.Fukuda et al.: "X-ray crystal shructure of bis(N-(2,6-diiso propylphenyl)-imino]aceraphthene ligand and some studier including …"J. Coord. Chem.. (in press). (2003)
[Publications] U.I.El-Ayaan et al.: "Structural studies of mixed ligand Cu(II) and Cu(I) complexes with the rigid nitrogen ligand : Bis(N-(2,6-diiso …"J. Mol. Struc.. (in press). (2003)
[Publications] R.Boca, et al.: "Spin crossover in mononuclear and dinuclear Fe(III) complexes with pentadentate Schiff-base ligands"Coordination chemistry at the turn of the Century, Ed. by G.Ondrejiavic and A.Shirota, Slovakia Tech.Univ.Press. 6 (1999)

2002 Fiscal Year Annual Research Report

刺激応答型金属錯体の創製とそれらの構造・物性・反応

Principal Investigator

福田 豊 お茶の水女子大学, 理学部, 教授 (30021950)

Research Products

[Publications] T.M.Yoshida, et al.: "Phase relation and molecular motions of mixed ligand complex [Zn(hfac)_2(tmen)]as studied by calorimetry and 'H-NMR measarement"J. Phys. Chem. Solids. 60. 1787-1796 (1999)

[Publications] F.Renz et al.: "Anisotropic effect after streching of the spin crossover compound [Fe(II)(2,6-bis(benzimidazol-2'-yl)pynidine)_2](ce04)_2 in polyvinyl-alcohol…"Mol. Cryst, Lig. Cryst.. 335. 531-540 (1999)

[Publications] F.Renz et al.: "Spin-transition in [Fe^<11>(2,6-bis(benzimidazol-2'-yl)pyridine)_2](ce04)_2 : Hysteresis effect dependent on the matrix"Mol. Cryst, Lig. Cryst.. 335. 521-530 (1999)

[Publications] S.Gou et al.: "Cyano-bridged dinuclear iron complexes in different oxidation states"Inorg. chim. Acta. 287. 95-100 (1999)

[Publications] K.Manseki et al.: "Template syntheses and properties of Cu(II)-La(III)complexes of phenol-based symmetric and unsymmetric dinuclear macrocycles"J. Coord. Chem.. 48. 1-13 (1999)

[Publications] A.Paulovicova et al.: "Synthesis, characterization and X-ray crystal structures of two 5-coordinate ternary Cu(II)complexes containing acetylacetonate with …"Inorg. Chim. Acta. 321. 56-62 (2001)

[Publications] U.I.El-Ayaan et al.: "Thermochromism and Solvatochromism in Solution"Monatsh. Chem.. 132. 1279-1294 (2001)

[Publications] M.Hasegawa et al.: "Higher excited state fluorescence of mixed ligand lanchanide(III)complexes with acetylacetonate, ritrate and ecrpyriline"Chem. Phys.. 269. 323-337 (2001)

[Publications] W.Linert et al.: "Chromotropism of coordination Compounds in Solution"Coord. Chem. Rev.. 218. 113-152 (2001)

[Publications] A.Pauloricova et al.: "Mixed ligand Cu(II)Complexes with the rigid bidentate bis(N-aryliminolacenaphtene Ligand : Synelesis, Spectroscopic …"Europ. J. Inorg. Chem.. 2001. 2641-2646 (2001)

[Publications] M.Hasegawa et al.: "Fluorescence spectra of Fe(II)spin crossover complexes with 2,6-bis(benzimidazole-2'-yl) pyridine"Chem. Phys. 227. 21-30 (2002)

[Publications] Kh.S.Abou-El Sherbini et al.: "Study on the complex formation between N-propylsalicylidene based on silica as ion exchanger and some trantion metalions"J. Sci. Islamic Rep. Iran. 13. 217-223 (2002)

[Publications] Y.Fukuda et al.: "Syntheses and specific structures of higher order mixed chelate lanthanide complexes containing terpyridine, acetylacetonate, and …"J. Chem. Soc. Dalton Fans.. 2002. 527-533 (2002)

[Publications] M.Enamulla et al.: "Synthesis, characterization and spin-crossover behaviors of [Co (hydroxycarboxylate)(triphos)]complexes"Bull. Chem. Soc. Jpn.. 75. 2449-2453 (2002)

[Publications] A.Paulovicora et al.: "Synthesis and structural studies of diamagnetic first-row transition metal complexes with the rigid nitrogen ligand : bis(…"Inorg. Chim. Acta. 339. 209-214 (2002)

[Publications] Y.Fukuda et al.: "New chromotropic behavior of Manganese complexes with 1,4,7-triazacyclononane-N, N', N"-tricarboxylates"Inorg. Chim. Acta. 339. 322-326 (2002)

[Publications] S.Yamada, A.Homma: "N-Substituent effect on the cis-trans geometry of nine-membered lactams"J. Chem. Soc. Chem. Commun.. 2002. 2656-2657 (2002)

[Publications] Y.Fukuda et al.: "X-ray crystal shructure of bis(N-(2,6-diiso propylphenyl)-imino]aceraphthene ligand and some studier including …"J. Coord. Chem.. (in press). (2003)

[Publications] U.I.El-Ayaan et al.: "Structural studies of mixed ligand Cu(II) and Cu(I) complexes with the rigid nitrogen ligand : Bis(N-(2,6-diiso …"J. Mol. Struc.. (in press). (2003)

[Publications] R.Boca, et al.: "Spin crossover in mononuclear and dinuclear Fe(III) complexes with pentadentate Schiff-base ligands"Coordination chemistry at the turn of the Century, Ed. by G.Ondrejiavic and A.Shirota, Slovakia Tech.Univ.Press. 6 (1999)

福田豊お茶の水女子大学, 理学部, 教授 (30021950)