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

我们新合成了手性光敏剂，Δ-[Ru(menbpy)D23D2]D12+D1 (menbpy=4,4'-bis(1R,2S,5R)-(-)menthoxycarbonyl}-2 ,2'-bipyridine), Δ -[Ru(phenebpy)D23D2]D12+D1 (phenebpy=4,4'-双(1-苯乙氨基羰基)-2,2'-联吡啶), [Cu(tmdcbpy)(PRD23D2)D22D2]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）。这些光敏剂不会引起光外消旋化，并且不会引起光激发态（三重态 MLCT 激发态）寿命较长，(2) Δ-[Ru(menbpy)D23D2]D12+D1在可见光照射下有效地进行[Co(acac)D23D2]的立体选择性光还原。 [Co(edta)]D1-D1 在近紫外光照射下具有显着大的对映异构体过量（10%转化率为60%）。另一方面，[Ru(phenebpy)D23D2]IID12+IED1不能进行立体选择性光还原。 (3) 阴离子手性 Cu(I) 络合物，[Cu(tmdcb … 更多py){PPhD22D2(m-CD26D2HD24D2SOD23D2D1-D1)}D22D2]D1-D1，以较低的反应活性和较小的立体选择性进行[Co(edta)]D1-D1的光还原，反应机理不同于。 [Co(edta)]D1-D1 通过 [Cu(tmdcbpy)(PPhD23D2)D22D2]D1+D1 进行光还原，前者通过动态猝灭机制进行，而后者通过静态猝灭机制进行（4）。 [Co(edta)]IiD1-IeD1 的光不对称合成CoX D22 D2 (X=AcO D1-D1、NO D23 D2 D1-D1 等) 和 L D24 D2edta (L=H 或 Na ) 与 [Cu(tmdcbpy)(PPhiiD23ieD2]iiD1+ieD1 在近紫外光照射下。当使用 D24D2edta 时，会过量形成 Δ-[Co(edta)]D1-D1，而当 H (5) [Co(acac)D23D2] 的光去消旋化成功时，会形成 ∧-[Co(edta)]D1-D1进行与阐明了可见光照射下的Δ-[Ru(menbpy)IID23IeD2]IiD12+IeD1在乙腈-水中的反应机理。 (6)成功地用Δ-[Ru(menbpy)D23D2]D12+进行了手性紫精的立体选择性光还原。 D1和基于Marcus理论的分析较少。

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)

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。

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