Dynamics of Electron Transfer and Energy Transfer by Newly Synthesized Asymmetric Photosensitizer

新合成的不对称光敏剂的电子转移和能量转移动力学

• 批准号: 09305057
• 负责人: SAKAKI Shigeyoshi
• 金额: $ 24.9万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 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-09305057/
• 关键词: Chiral ruthenium (II) bipyridine complex; Chiral Copper (I) complex; Stereoselective photoreduction; Photoderacemization; Photoasymmetric synthesis; Marcus theory; Laser Flush Photolysis; Chiral viologen; キラルルテニウム(II)ビピリジン; 立体選択的光還元反応; 光不斉合成反応 /

We newly synthesized 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).These photosensitizers do not cause photoracemization and their photoexcited states (triplet MLCT excited state) are long-lived, (2) Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 performs effectively stereoselective photoreduction of [Co(acac)ィイD23ィエD2] under visible light irradiation. [Cu(tmdcbpy)(PPhィイD23ィエD2)]ィイD1+ィエD1 also performs stereoselective photoreduction of [Co(edta)]ィイD1-ィエD1 with significantly large enantiomer excess (60% at l0% conversion), under near-UV light irradiation. On the other hand, [Ru(phenebpy)ィイD23ィエD2]ィイD12+ィエD1 cannot perform stereoselective photoreduction. (3) An anionic chiral Cu(I) complex, [Cu(tmdcb … More py){PPhィイD22ィエD2(m-CィイD26ィエD2HィイD24ィエD2SOィイD23ィエD2ィイD1-ィエD1)}ィイD22ィエD2]ィイD1-ィエD1, performs photoreduction of [Co(edta)]ィイD1-ィエD1 with less reactivity and smaller stereoselectivity. The reaction mechanism is different from that of photoreduction of [Co(edta)]ィイD1-ィエD1 by [Cu(tmdcbpy)(PPhィイD23ィエD2)ィイD22ィエD2]ィイD1+ィエD1. The former proceeds through dynamic quenching mechanism, while the latter through static quenching mechanism. (4) We succeeded the photoasymmetric synthesis of [Co(edta)]ィイD1-ィエD1 from CoXィイD22ィエD2 (X=AcOィイD1-ィエD1, NOィイD23ィエD2ィイD1-ィエD1 etc.) and LィイD24ィエD2edta (L=H or Na) with [Cu(tmdcbpy)(PPhィイD23ィエD2]ィイD1+ィエD1 under near-UV light irradiation. Δ-[Co(edta)]ィイD1-ィエD1 is formed in excess when NaィイD24ィエD2edta was used, while ∧-[Co(edta)]ィイD1-ィエD1 is formed when HィイD24ィエD2edta was used. (5) Photoderacemization of [Co(acac)ィイD23ィエD2] was successfully 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. The reaction mechanism was elucidated. (6) Stereoselective photoreduction of chiral viologen was successfully performed with Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 and analysis based on Marcus theory was presented. Less

本文合成了新的手性光敏剂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）（PR P23 P22）P22 P22] P23 P22 + P23 P24（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）。这些光敏剂不引起光外消旋化，它们的光激发态（2）在可见光照射下，Δ-[Ru（menbpy）][D23][D12]+[D11]对[Co（acac）][D23][D12]进行了有效的立体选择性光还原。在近紫外光照射下，[Cu（tmdcbpy）（PPh β D23 β D2）] β D1+ β D1也进行[Co（edta）] β D1-β 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%）。另一方面，[Ru（phenebpy）双D23双D2]双D12+双D1不能进行立体选择性光还原。(3)研究了阴离子手性Cu（I）配合物[Cu（tmdcb ...更多信息 py）{PPh [D22][D2（m-C [D26][D2 H][D24][D2 SO][D23][D2][D1-D1]]}[D22][D2][D1-D1]，进行[Co（edta）][D1-D1]的光还原反应，反应活性和立体选择性较小。反应机理与[Cu（tmdcbpy）（PPh）[D23] D22] D22 [D23] D22] D23 + D24 + D1光还原[Co（edta）] D1-D24的反应机理不同。前者通过动态猝灭机制进行，后者通过静态猝灭机制进行。(4)我们成功地以考克斯配体D22配体D2（X=AcO配体D1-EDTA D1，NO配体D23配体D2配体D1-EDTA D1等）为原料，光不对称合成了[Co（edta）]配体D1-EDTA D1。和LイD24 D2 edta（L=H或Na）与[Cu（tmdcbpy）（PPhイD23 D2]イD1+ D1在近紫外光照射下。当使用Na + D24 + D2 edta时，形成过量的Δ-[Co（edta）]-[D1]-[D1]，而当使用H + D24 + D2 edta时，形成过量的Δ-[Co（edta）]-[D1]-[D1]-[D1]。(5)在乙腈-水体系中，用Δ-[Ru（menbpy）邻苯二甲酰D23邻苯二甲酰D2]邻苯二甲酰D12+邻苯二甲酰D1在可见光照射下成功地对[Co（acac）邻苯二甲酰D23邻苯二甲酰D2]进行了光脱外消旋反应。并对反应机理进行了探讨。(6)用Δ-[Ru（menbpy）双吡啶D23双吡啶D2]双吡啶D12+双吡啶D1对手性紫精进行了立体选择性光还原反应，并进行了Marcus理论分析.少

项目成果

S.Sasaki, T.Hamadaら: "Photoasymmetri Synthesis of [Co(edta)]^- from Co(II) Salt and L_4 edta(L=H^+ or Na^+),Using a Chira] Cu(I) Complex" Chem.Lett.827-828 (1998)

S.Sasaki、T.Hamada 等人：“从 Co(II) 盐和 L_4 edta(L=H^+ 或 Na^+) 光不对称合成 [Co(edta)]^-，使用 Chira] Cu( I) 复合物”Chem.Lett.827-828 (1998)

T.Hamada, S.Sasakiら: "High Enantioselectivity in the Electron Transfer between a Ru(II) Complex of Menbpy Anion Radical,[Ru(menbpy)_3]^+ and [Co(acac)_3]:A Pulse Radiolysis Study" Chem.Lett.1259-1260 (1998)

T. Hamada、S. Sasaki 等人：“Menbpy 阴离子自由基 Ru(II) 络合物之间电子转移的高对映选择性，[Ru(menbpy)_3]^+ 和 [Co(acac)_3]:A 脉冲放射分解研究《化学快报》1259-1260 (1998)

Taisuke Hamada, Masaya Tsukamoto, Hiroshi Ohtsuka, and Shigeyoshi Sakaki: "Charge Effects in Photoinduced Electron-transfer Reactions between [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 and Viologen Derivatives"Bull., Chem. Soc. Jpn.. 71, No.10,99. 2281-2291 (1998)

Taisuke Hamada、Masaya Tsukamoto、Hiroshi Ohtsuka 和 Shigeyoshi Sakaki：“[Ru(bpy)D23D2]D12+D1 和紫罗碱衍生物之间的电荷效应”Bull.，Chem.Soc. 71，No. .10,99。2281-2291（1998）

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。