1992 Fiscal Year Annual Research Report

錯体の電子状態と電子移動過程のダイナミックス

Research Project

Project/Area Number	03303005
Research Institution	TOHOKU UNIVERSITY
Principal Investigator	荻野博東北大学, 理学部, 教授 (00004292)
Co-Investigator(Kenkyū-buntansha)	谷口功熊本大学, 工学部, 教授 (90112391) 松村竹子奈良教育大学, 教育学部, 教授 (60031556) 田中晃二分子科学研究所, 錯体化学実験施設, 教授 (00029274) 佐藤弦上智大学, 理工学部, 教授 (00053546) 佐々木陽一北海道大学, 理学部, 教授 (30004500)
Keywords	金属錯体 / クラスター / 電子移動 / 酸化還元電位 / 混合原子価 / 触媒 / 機能性材料 / 走査トンネル顕微鏡
Research Abstract	本研究の最も基本となる単核、二核および多核錯体やクラスターの合成に大きな進歩があった。特に二核錯体については系統的な錯体の合理的な合成経路の設計がいくつかの系で可能となった。これらの成果にもとづき、錯体の電子状態と酸化還元電位との関連および混合原子価状態の理解を深めることができた。プロント移動と共役した電子移動やCO_2還元を触媒する錯体の開発など、機能性錯体の研究にも大きな進展がみられた。これらはスイッチング機能や電荷を運ぶ分子ワイヤーとしての機能を持つ分子システムへと発展する可能性を持っている。また、振動化学反応のプローブに錯体を利用した研究も行われ、その機能性材料へと発展させる可能性も検討が開始された。昨年度に引き続いて金属錯体の光誘起電子移動反応が理論および実験の両面から研究された。走査トンネル顕微鏡(STM)の発明とその後の急速な発展は、これまでほとんど推測の域を出なかった固液界面の研究状況を一変させつつある。電極と溶液界面における電子移動との関連から、本研究においてもSTMを使った表面化学種の構造解析が行われ、大きな発展があった。以上述べた研究は研究者間の相互の連絡のもとに進められ、さらに平成4年11月11日および12日の両日にわたって分子科学研究所での公開シンポジウムでも総括的な検討が行われた。なお、1992年のノーベル化学賞は「化学系における電子移動理論への貢献」を行った米国カリフォルニア工科大学のマーカス教授が受賞した。我々の研究提案がいかに緊急性があったか、また時宜を得たものであったかを証明したものと自負している。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] Julita C.Robles: "Synthesis and crystal structure of the novel dinuclear vanadium(III) complex K_2[V_2(dpot)_2] 7H_2O containing 1,3-diamino-i-propanol-N,N,N^1,N^1-tetraacetate(dpot)." Chem.Lett.1992. 309-310 (1992)
[Publications] Shinji Inomata: "Synthesis and structure of mixed-ligand iron-sulfur cubane-like clusters[(η-C_5Me_5)_3(Ph_2C_2S_2)Fe_4S_5]^n(n=O and 1+)." Inorg.Chem.31. 722-723 (1992)
[Publications] Julita C.Robles: "Syntheses and structures of vanadium(III) complexes containing 1,3-diaminopropane-N,N,_1,N_1-tetraacetate([V(trdta)]^-)and 1,3-diamino-2-propanol-N,N,,N^1,N^1-tetraacetate[V_4(dpot)_2]^<2->)." Inorg.Chem.32. 13-17 (1993)
[Publications] K.Tohda: "Liquid membrane electrode for guanosine nucleotides using a cytosine-pendant triamine host as the sensory element." Anal.Chem.64. 960-964 (1992)
[Publications] M.Sugawara: "Effect of the memebrane surface charge on the host-guest complex of valinomycin in a synthetic lipid monolayer at the air-water interface." Langmuir. 8. 609-612 (1992)
[Publications] Uichi Akiba: "Electrocatalytic reduction of COaDtDtレ2aCtDtレ on modified electrode with Langmui Blodgett films of nickel(II) complex with long alkyl substiuted cyclam" Thin solid films. 210/211. 381-383 (1992)
[Publications] Masaaki Abe: "X-ray sturcture,substitution,and other poroperties of trinuclear rutheniu complex,[Ru_3(μ_3-O)(μ-C_6H_5COO)_6(py)_3(py=pyridine),and X-ray structure of dinucleare of dinuclear ruthenium complex,[Ru_2(μ-C_6H_5COO)_4Cl]." Bull.Chem.Soc.Jpn.65. 1585-1590 (1992)
[Publications] Yoechi Sasaki: "Mixed chromium(III)-ruthenium(III)trinuclear complex,[CrRu_2(μ_3-O)(μ-CH_3COO)_6(PYridine)_3]^+." Chem.Lett.1993. 69-72 (1993)
[Publications] N.Ishikawa: "Holedelocalization in naphthalocyanenatophthalocyaninatolutetium(III)." Chem.Phys.Lett.180. 51-56 (1991)
[Publications] Y.Kasahara: "Synthesis of binuclear(β-diketonato)ruthenium(III) complexes through introduction of an ethynyl group at γ-posititon of tris(β-deke-tonato)ruthenium(III) and electrochemistry of the binuclear complexes." Organometallics. 11. 1968-1971 (1992)
[Publications] Toshiaki Kakitani: "Effects of the donor-acceptor distance distribution on the energy gap laws of charge separation and charge recombination reactions in polar solutions." J.Phys.Chem.96. 5385-5392 (1992)
[Publications] Takeshi Ohno: "Photoexcited states of bi-ruthenium(II) compounds bridged by bis-2,2'-(2¨-pyridyl)-bibenzemedazole or di-(2-pyridyl-2'-benzimidazoyl)ethane." Inorg.Chem.31. 548-555 (1992)
[Publications] Uichi Akiba: "Electrocatalytic reduction of CO_2 on a modified electrode with Langmui Blodgett films of nickel(II) complex with long alkyl substiuted cyclam" Thin solid films. 210/211. 381-383 (1992)
[Publications] Takeshi Ohno: "A metal-to-ligand charge-transfer excited state of a biruthenium(II) compound bridged by 2,6-bis(2-pyridyl)benzoimidazole." Inorg.Chem.31. 4256-4261 (1992)
[Publications] V.V.Borovkov: "Evidence for parallil photoinduced electron transfer in diquinone substituted porphyrins." Chem.Lett.1993. 145-148 (1993)
[Publications] Zhi-Hong Zhong: "Solvent effect on redox optential of ferrocene derivatives using a ultramicrelectrode." Anal.Sci.8. 877-879 (1992)
[Publications] Masaru Kimura: "Kinetics and mechanisms of photo-induced reaction of iodine by monoamine-N-polycarboxylate ions in an aqueous solution." Bull.Chem.Soc.Jpn.65. 1812-1816 (1992)
[Publications] Isao Taniguchi: "New simple cell for en situ fluoroelectrochemical measurements." Chem.Lett.1992. 1217-1220 (1992)
[Publications] 荻野博: "第4版実験晃学講座 17 無機錯体・キレート錯体" 日本化学会編, 565 (1991)
[Publications] Masamichi Fujihira K/Honda,editor-in-chief: "Poto-electric conversion with Langmuir-Blodgett films in "Photochemical processes in organized molecular systems"" Elsevier Science Publishers B.V., 20 (1991)
[Publications] Koichi Nozaki: "Dynamics and mechanisms of photoinduced electron transfer and related phenomena" Elsevier Science Publishers B.V., 12 (1992)

1992 Fiscal Year Annual Research Report

錯体の電子状態と電子移動過程のダイナミックス

Principal Investigator

荻野 博 東北大学, 理学部, 教授 (00004292)

Research Products

[Publications] Julita C.Robles: "Synthesis and crystal structure of the novel dinuclear vanadium(III) complex K_2[V_2(dpot)_2] 7H_2O containing 1,3-diamino-i-propanol-N,N,N^1,N^1-tetraacetate(dpot)." Chem.Lett.1992. 309-310 (1992)

[Publications] Shinji Inomata: "Synthesis and structure of mixed-ligand iron-sulfur cubane-like clusters[(η-C_5Me_5)_3(Ph_2C_2S_2)Fe_4S_5]^n(n=O and 1+)." Inorg.Chem.31. 722-723 (1992)

[Publications] Julita C.Robles: "Syntheses and structures of vanadium(III) complexes containing 1,3-diaminopropane-N,N,_1,N_1-tetraacetate([V(trdta)]^-)and 1,3-diamino-2-propanol-N,N,,N^1,N^1-tetraacetate[V_4(dpot)_2]^<2->)." Inorg.Chem.32. 13-17 (1993)

[Publications] K.Tohda: "Liquid membrane electrode for guanosine nucleotides using a cytosine-pendant triamine host as the sensory element." Anal.Chem.64. 960-964 (1992)

[Publications] M.Sugawara: "Effect of the memebrane surface charge on the host-guest complex of valinomycin in a synthetic lipid monolayer at the air-water interface." Langmuir. 8. 609-612 (1992)

[Publications] Uichi Akiba: "Electrocatalytic reduction of COaDtDtレ2aCtDtレ on modified electrode with Langmui Blodgett films of nickel(II) complex with long alkyl substiuted cyclam" Thin solid films. 210/211. 381-383 (1992)

[Publications] Masaaki Abe: "X-ray sturcture,substitution,and other poroperties of trinuclear rutheniu complex,[Ru_3(μ_3-O)(μ-C_6H_5COO)_6(py)_3(py=pyridine),and X-ray structure of dinucleare of dinuclear ruthenium complex,[Ru_2(μ-C_6H_5COO)_4Cl]." Bull.Chem.Soc.Jpn.65. 1585-1590 (1992)

[Publications] Yoechi Sasaki: "Mixed chromium(III)-ruthenium(III)trinuclear complex,[CrRu_2(μ_3-O)(μ-CH_3COO)_6(PYridine)_3]^+." Chem.Lett.1993. 69-72 (1993)

[Publications] N.Ishikawa: "Holedelocalization in naphthalocyanenatophthalocyaninatolutetium(III)." Chem.Phys.Lett.180. 51-56 (1991)

[Publications] Y.Kasahara: "Synthesis of binuclear(β-diketonato)ruthenium(III) complexes through introduction of an ethynyl group at γ-posititon of tris(β-deke-tonato)ruthenium(III) and electrochemistry of the binuclear complexes." Organometallics. 11. 1968-1971 (1992)

[Publications] Toshiaki Kakitani: "Effects of the donor-acceptor distance distribution on the energy gap laws of charge separation and charge recombination reactions in polar solutions." J.Phys.Chem.96. 5385-5392 (1992)

[Publications] Takeshi Ohno: "Photoexcited states of bi-ruthenium(II) compounds bridged by bis-2,2'-(2¨-pyridyl)-bibenzemedazole or di-(2-pyridyl-2'-benzimidazoyl)ethane." Inorg.Chem.31. 548-555 (1992)

[Publications] Uichi Akiba: "Electrocatalytic reduction of CO_2 on a modified electrode with Langmui Blodgett films of nickel(II) complex with long alkyl substiuted cyclam" Thin solid films. 210/211. 381-383 (1992)

[Publications] Takeshi Ohno: "A metal-to-ligand charge-transfer excited state of a biruthenium(II) compound bridged by 2,6-bis(2-pyridyl)benzoimidazole." Inorg.Chem.31. 4256-4261 (1992)

[Publications] V.V.Borovkov: "Evidence for parallil photoinduced electron transfer in diquinone substituted porphyrins." Chem.Lett.1993. 145-148 (1993)

[Publications] Zhi-Hong Zhong: "Solvent effect on redox optential of ferrocene derivatives using a ultramicrelectrode." Anal.Sci.8. 877-879 (1992)

[Publications] Masaru Kimura: "Kinetics and mechanisms of photo-induced reaction of iodine by monoamine-N-polycarboxylate ions in an aqueous solution." Bull.Chem.Soc.Jpn.65. 1812-1816 (1992)

[Publications] Isao Taniguchi: "New simple cell for en situ fluoroelectrochemical measurements." Chem.Lett.1992. 1217-1220 (1992)

[Publications] 荻野 博: "第4版 実験晃学講座 17 無機錯体・キレート錯体" 日本化学会編, 565 (1991)

[Publications] Masamichi Fujihira K/Honda,editor-in-chief: "Poto-electric conversion with Langmuir-Blodgett films in "Photochemical processes in organized molecular systems"" Elsevier Science Publishers B.V., 20 (1991)

[Publications] Koichi Nozaki: "Dynamics and mechanisms of photoinduced electron transfer and related phenomena" Elsevier Science Publishers B.V., 12 (1992)

荻野博東北大学, 理学部, 教授 (00004292)

[Publications] 荻野博: "第4版実験晃学講座 17 無機錯体・キレート錯体" 日本化学会編, 565 (1991)