Evaluation of Ultrafast Intramolecular Electron Transfer Rate by Means of NMR Relaxation

通过核磁共振弛豫评估超快分子内电子转移速率

基本信息

  • 批准号:
    08454235
  • 负责人:
  • 金额:
    $ 3.97万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
  • 财政年份:
    1996
  • 资助国家:
    日本
  • 起止时间:
    1996 至 1998
  • 项目状态:
    已结题

项目摘要

The intramolecular electron transfer rates in solution were evaluated in several systems by NMR spin-lattice relaxation measurements. A limitation of this method was confirmed referring the rotational relaxation time and the electron spin relaxation time, etc.The reaction rates with pico second order were observed for three mixed-valence biferrocene derivatives (Fe(II), Fe(III)) and the rates showed a characteristic behavior. The biferrocene monocation showed ca. three times larger rate constant than its 1,1 "'- diiodo derivative, nevertheless these two mixed-valence compounds show similar intervalence band energy and strength. This results can be attributed to difference in the ratio of the outersphere and the innersphere reorganization energy. The frequency difference in the L-M-L stretching modes is another reason of the retardation of the ET rate of diiodo derivatives, On the other hand, an acetylene bridged biferrocene monocation gave three times higher rates than those boferrocene monocation. This result is disagreement with the IT band measurements. The temperature dependence of the rate of the acetylene bridged complex suggested considerable nuclear tunneling effect on the rates. This may be arisen by the rigid bridging structure of the mixed-valence complex.All the rates given in the present studies exceed those predicted any model including solvent dynamical effect as long as solvent is regarded as a dielectric continuum. Faster local solvent dynamics may be, at least partially, responsible to control the rates.
通过核磁共振自旋-晶格弛豫测量,在几个体系中评价了溶液中的分子内电子转移速率。结合转动弛豫时间和电子自旋弛豫时间等数据证实了该方法的局限性,并对三种混合价双二茂铁衍生物(Fe(II),Fe(III))的反应速率进行了研究,发现反应速率均为皮科二级,表现出特征性行为.双二茂铁一价阳离子显示ca。速率常数比其1,1-二碘代衍生物大三倍,然而这两种混合价化合物显示出相似的价带间能量和强度。这一结果可以归因于内外球重组能比值的差异。L-M-L伸缩模的频率差是二碘代衍生物电子转移速率延迟的另一个原因。另一方面,乙炔桥连的双二茂铁一价阳离子的电子转移速率比bofercene一价阳离子高三倍。这一结果与IT带测量结果不一致。乙炔桥络合物的反应速率与温度的关系表明,反应速率受核隧穿效应的影响。这可能是由于混合价络合物的刚性桥连结构引起的.只要溶剂被看作是一个介电连续体,本文所给出的所有速率都超过了任何考虑溶剂动力学效应的模型所预测的速率.更快的局部溶剂动力学可能至少部分地负责控制速率。

项目成果

期刊论文数量(15)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A.Masuda: "First Evaluation of Ultarafast (Ground State)Intramolecular Electron Transfer Rate in Solutoin by NMR Spin-lattice Relaxation" J.Phys.Chem.A. 101. 2245-2253 (1997)
A.Masuda:“通过 NMR 自旋晶格弛豫首次评估溶液中超快(基态)分子内电子转移速率”J.Phys.Chem.A。
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A.MASUDA: "First Evaluation of Ultrafast (Ground State) Intramolecular Electron Transfer Rate in Solution by NMR Spin-lattice Relaxation" J.Phys.Chem.B101(印刷中). (1997)
A.MASUDA:“通过 NMR 自旋晶格弛豫首次评估溶液中的超快(基态)分子内电子转移速率”J.Phys.Chem.B101(出版中)。
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H.Hosoi and Y.Masuda: "Solvent Effect on Intramolecular Electron Transfer Rates of 1,3-dinitrobezene Anion Radical" Chem.Lett.1998. 177-178 (1998)
H.Hosoi 和 Y.Masuda:“溶剂对 1,3-二硝基苯阴离子自由基分子内电子转移速率的影响”Chem.Lett.1998。
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A.MASUDA: "Solvent Effect on Ultrafast Intramolecular Electron Transfer in Mixed-valence Biferrocene monocaton" J.Mol.Liquid.65. 397-406 (1996)
A.MASUDA:“溶剂对混合价联二茂铁单原子中超快分子内电子转移的影响”J.Mol.Liquid.65。
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    0
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H.Hosoi: "Solvent Effect on Rotational Motion of Perchlorate lon" J.Phys.Chem.B. 102. 2995-3002 (1998)
H.Hosoi:“溶剂对高氯酸盐旋转运动的影响”J.Phys.Chem.B。
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    0
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MASUDA Yuichi其他文献

Noncontact Heat Presentation for Whole Body Using High Intensity Ultrasound
使用高强度超声波对全身进行非接触式热呈现
  • DOI:
  • 发表时间:
    2021
  • 期刊:
  • 影响因子:
    0
  • 作者:
    ZHU Qirong;KAMIGAKI Takaaki;MASUDA Yuichi;FUJIWARA Masahiro;MAKINO Yasutoshi;SHINODA Hiroyuki
  • 通讯作者:
    SHINODA Hiroyuki

MASUDA Yuichi的其他文献

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{{ truncateString('MASUDA Yuichi', 18)}}的其他基金

Elucidation of 3D structure and target molecule-recognition mechanism of hypeptin, an antimicrobial cyclic peptide.
阐明抗菌环肽hypeptin的3D结构和靶分子识别机制。
  • 批准号:
    19K05841
  • 财政年份:
    2019
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Conformation analysis and target molecule identification of PF1171 hexapeptides in vivo
PF1171六肽体内构象分析及靶分子鉴定
  • 批准号:
    16K07707
  • 财政年份:
    2016
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
The exploration of cytoprotective effect of dimethyl fumarate on human islet
富马酸二甲酯对人胰岛细胞保护作用的探讨
  • 批准号:
    26461907
  • 财政年份:
    2014
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Action mechanism study of PF1171 hexapeptides focused on their 3D structures
PF1171六肽作用机制研究重点关注其3D结构
  • 批准号:
    26850068
  • 财政年份:
    2014
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
Solvent effect on ultra-fast intramolecular proton tranfer rate by means of spin-lattice relaxation
通过自旋晶格弛豫溶剂对超快分子内质子转移速率的影响
  • 批准号:
    12640489
  • 财政年份:
    2000
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Dynamical Solvent Effect on Intramolecular Electron Transfer Rate of Mixed-Valence Biferrocene Monocation
动态溶剂对混合价联二茂铁单阳离子分子内电子转移速率的影响
  • 批准号:
    06640717
  • 财政年份:
    1994
  • 资助金额:
    $ 3.97万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)

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