Dynamics of Electron Transfer and Energy Transfer by New Chiral Photosensitizers

新型手性光敏剂的电子转移和能量转移动力学

• 批准号: 09044096
• 负责人: SAKAKI Shigeyoshi
• 金额: $ 5.76万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09044096/
• 关键词: Chiral ruthenium (II) bipyridine complex; Chiral Copper (I) complex; Pulse radiolysis; Laser Flash Photolysis; Photoasymmetric reduction; Photoasymmetric synthesis; Molecular; Mechanics Study; Marcus theory; キラル銅(I)ビピリジン錯体; キラルコバルト錯体; 立体選択的光還元

(1)Chiral photosensitizers, Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 (menbpy=4,4'-bis(1R,2S,5R)-(-)menthoxycarbonyl}-2,2'-bipyridine), Δ-[Ru(phenebpy)ィイD23ィエD2]ィイD12+ィエD1 (phenebpy=4,4'-bis(1-phenethylaminocarbonyl)-2,2'-bipyridine), [Cu(tmdcbpy)(PRィイD23ィエD2)ィイD22ィエD2]ィイD12+ィエD1(tmdcbpy=4,4'-6,6'-tetramethyl-5,5'-bis(S)-(-)-1-phenylcarbamoyl-2,2'-bipyridine) were newly synthesized here. (2) Pulse radiolysis of Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in ethanol yields one-electron reduced species in which ruthenium(I) is not involved but anion radical of menbpy ligand is involved. Reduction of [Co(acac)ィイD23ィエD2] by this Δ-[Ru(menbpy)ィイD23ィエD2]ィイD1+ィエD1 occurs stereoselectively with selectivity of 2.7. (3) [Cu(tmdcbpy)(PPhィイD23ィエD2)]ィイD1+ィエD1 perfomrs stereoselective photoreduction of [Co(edta)]ィイD1-ィエD1 with significantly large enantiomer excess (60% at 10% conversion), under near-UV light irradiation, while [Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 cannot perform stereoselective photoreduction of [Co(edta)] … More ィイD1-ィエD1. (4) Photoreductions of cationic methylviologen and anionic 4,4'-bis(3-carboxyethyl)-1,1'-bipyridinium (dcbpy) by [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 were investigated with laser flash photolysis. The reaction rate significantly depend on the electrostatic interaction; both photoinduced electron transfer from ィイD1*ィエD1[Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 to MVィイD12+ィエD1 and the reverse electron transfer from MVィイD1+ィエD1 to [Ru(bpy)ィイD23ィエD2]ィイD13+ィエD1 occur more slowly than those of dcbpy. (5) Analysis based on Marcus theory showed that the electronic coupling term HィイD2rpィエD2 significantly depends on the electrostatic interaction, suggesting that the electrostatic interaction is important to the stereoselectivity in electron transfer reaction. (5) Photoderacemization of [Co(acac)ィイD23ィエD2] was carried out with Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in acetonitrile-water under visible light irradiation. Quenching reactions and model reaction indicate that this reaction takes place through the oxidative quenching of Δ-ィイD1*ィエD1[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 by[Co(acac)ィイD23ィエD2]. (6) Electron transfer reaction was investigated with molecular mechanics, which shows that [Co(acac)ィイD23ィエD2] approaches [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 along the CィイD23vィエD2 axis. Less

（1）手性光敏剂，Δ-[Ru（menbpy）双吡啶D23双吡啶D2]双吡啶D12+双吡啶D1（menbpy= 4，4'-bis（1R，2S，5R）-（-）mentoxycarbonyl}-2，2'-bipyridine），Δ-[Ru（phenebpy）苯并D23苯并D2]苯并D12+苯并D1（phenebpy= 4，4 '-双（1-苯乙基氨基羰基）-2，2'-联吡啶），[Cu（tmdcbpy）本文合成了一种新的化合物（PR-[D23] D2, 2] D2, 2] D12+ D1（tmdcbpy= 4，4 '-6，6'-四甲基-5，5 '-双（S）-（-）-1-苯基氨基甲酰基-2，2'-联吡啶）。(2)在乙醇中，Δ-[Ru（menbpy）d_23 d_2D_2] d_2D_1_2 + d_2D_1的脉冲辐解反应产生了单电子还原产物，其中不涉及钌（I），但涉及配体menbpy的阴离子自由基.通过该Δ-[Ru（menbpy）双金属D23双金属D2]双金属D1+双金属D1立体选择性地发生[Co（acac）双金属D23双金属D2]的还原，选择性为2.7。(3)在近紫外光照射下，[Cu（tmdcbpy）（PPh）D23 d2 D2）] d2 D1+ d2 D1进行[Co（edta）] d2 D1-d2 D1的立体选择性光还原，具有显著大的对映体过量（在10%转化率下60%），而[Ru（menbpy）D23 d2 D2] d2 D12+ d2 D1不能进行[Co（edta）] d2 D1-d2 D1的立体选择性光还原。 ...更多信息 D1-D2-D1. (4)用激光闪光光解法研究了阳离子甲基紫精和阴离子4，4 ′-双（3-羧乙基）-1，1 ′-联吡啶（dcbpy）在[Ru（bpy）双吡啶D23双吡啶D2]双吡啶D12+双吡啶D1光还原反应中的光催化活性。反应速率明显依赖于静电相互作用，光诱导电子从Ru（bpy）D1* Ru D1[Ru（bpy）D23] D12+ Ru D12转移到MV D12+ Ru D1，以及MV D12 + Ru D1转移到[Ru（bpy）D23] D13+ Ru D1的反向电子转移都比dcbpy慢. (5)基于Marcus理论的分析表明，电子耦合项H D2 rp D2显著依赖于静电相互作用，表明静电相互作用对电子转移反应的立体选择性有重要影响. (5)在乙腈-水溶液中，用Δ-[Ru（menbpy）配体D23]配体D12+ Ru配体D1对[Co（acac）配体D23]配体D2进行了可见光催化去外消旋化反应。猝灭反应和模型反应表明，该反应是通过[Co（acac）配体D23配体D2]氧化猝灭Δ-钌D1 * 钌D1 [Ru（menbpy）配体D23配体D2]而发生的. (6)用分子力学方法研究了电子转移反应，结果表明：[Co（acac）配体D23配体D2]沿着C配体D23 v配体D2轴向[Ru（bpy）配体D23配体D2]配体D12+配体D1方向靠近。少

项目成果

Shigeyoshi Sakaki: "Synthesis of a new chiral copper (I) complex and its application to stereoselective photoreduction of [Co(edta)]^- (H_4edta=ethylene dinitrilo tetraacetic acid)" J. Chem. Soc., Dalton Trans.1997. 1815-1820 (1997)

Shigeyoshi Sakaki：“一种新型手性铜 (I) 配合物的合成及其在 [Co(edta)]^- (H_4edta=乙二胺四乙酸) 立体选择性光还原中的应用” J. Chem.

T. Hamada,B. S. Brunschwig,K. Eifuki,E. Fujita,M. Korner,S. Sakaki,R. van Eldik,J. F. Wishart: "Enantioselectivities in Electron-Transfer and Excited State Quenching Reactions of Chiral Ruthenium Complex Possessing a Helical Structure"J. Phys> Chem. A. 10

T.滨田，B.

S. Sakaki: The Transition State.

S. Sakaki：过渡国家。

Taisuke Hamada, B. S. Brunschwig, Kenji Eifuku, Etsuko Fujita, Manuela Korner, Shigeyoshi Sakaki, R. Eldik, and James Wishart: "Enantioselectivities in Electron-Transfer and Excited State Quenching Reactions of a Chiral Ruthenium Complex Possessing a Heli

Taisuke Hamada、B. S. Brunschwig、Kenji Eifuku、Etsuko Fujita、Manuela Korner、Shigeyoshi Sakaki、R. Eldik 和 James Wishart：“具有 Heli 的手性钌络合物的电子转移和激发态淬灭反应中的对映选择性

K.Sakanoue,M.Motoda,M.Sugimoto,and S.Sakaki: "A Molecular Orbital Study on the Hole Transport Property of Organic Amine Compounds"J. Phys. Chem. A. 103,No.28. 5551-5556 (1999)

K.Sakanoue、M.Motoda、M.Sugimoto 和 S.Sakaki：“有机胺化合物空穴传输特性的分子轨道研究”J。