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首页> 外文期刊>Chemistry: A European journal >Thermodynamics and Photodynamics of a Monoprotonated Porphyrin Directly Stabilized by Hydrogen Bonding with Polar Protic Solvents
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Thermodynamics and Photodynamics of a Monoprotonated Porphyrin Directly Stabilized by Hydrogen Bonding with Polar Protic Solvents

机译：用极性质子溶剂直接通过氢键直接稳定的单议突卟啉的热力学和光学动力学

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摘要

Addition of 1 equiv of TFA to an acetone solution containing dodecaphenylporphyrin (H2DPP) in the presence of 10% MeOH (v/v) resulted in selective formation of a monoprotonated form (H_3DPP~+), in sharp contrast to protonation of H2DPP directly affording a diprotonated form (H_4DPP~(2+)) in acetone in the absence of MeOH. The crucial role of MeOH for selective H_3DPP~+ formation was interpreted as hydrogen-bonding stabilization of H_3DPP~+, since a MeOH molecule was found to form hydrogen bonds with an NH proton of H_3DPP~+ in the crystal. The selectivity of H_3DPP~+ formation was evaluated by the formation yield of H_3DPP~+, which increased when elevating the portion of MeOH (0-10%) in acetone with saturation behavior, suggesting that H_3DPP~+ is stabilized by hydrogen bonding with MeOH even in solution, together with the thermodynamic parameters determined from a van't Hoff plot based on the spectroscopic titration. Femto- and nanosecond laser flash photolysis allowed us to elucidate the photodynamics of H_3DPP~+ in intermolecular photoinduced electron transfer (ET) from ferrocene derivatives as one-electron donors to the triplet excited state of H_3DPP~+ as an electron acceptor. The second-order rate constants of the ET reactions were evaluated in light of the Marcus theory of ET. The reorganization energy of ET was determined to be 1.87 eV, which is slightly larger than that of H_4DPP~(2+) in acetonitrile (1.69 eV), due to larger structural change upon ET than that of H_4DPP~(2+).
机译：在10％MeOH（v / v）存在下，将1当量的TFA加入含有十二烷基卟啉（H2DPP）的丙酮溶液，导致单议议形式（H_3DPP〜+）的选择性形成，与直接提供的H2DPP的质子化鲜明对比在没有MeOH的丙酮中，丙酮中的双胞突出形式（H_4DPP〜（2+））。 MeOH用于选择性H_3DPP〜+形成的关键作用被解释为H_3DPP〜+的氢键键合，因为发现MeOH分子形成氢键，其在晶体中的NH质子〜+的NH质子。通过H_3DPP〜+的形成产率评价H_3DPP〜+形成的选择性，当用饱和行为升高MeOH（0-10％）的MeOH（0-10％）的部分增加，表明H_3DPP〜+通过与MeOH的氢键稳定而稳定即使在溶液中，也与基于光谱滴定的Vace Not Hoff图确定的热力学参数一起。毫微和纳秒激光闪光光解允许我们阐明从二茂铁衍生物的分子间光诱导的电子转移（ET）中的H_3DPP〜+的光动力学作为一种电子供体，以作为电子受体的三重态激发态。根据ET的Marcus理论评估ET反应的二阶速率常数。 ET的重组能量确定为1.87eV，其略高于乙腈（1.69eV）的H_4DPP〜（2+），由于等于等的结构变化而不是H_4DPP〜（2+）。

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  • 来源
    《Chemistry: A European journal》 |2017年第19期|共11页
  • 作者

    Wataru Suzuki; Hiroaki Kotani; Tomoya Ishizuka; Kei Ohkubo; Yoshihito Shiota; Kazunari Yoshizawa; Shunichi Fukuzumi; Takahiko Kojima;

  • 作者单位

    Department of Chemistry Faculty of Pure and Applied Sciences University of Tsukuba and CREST (JST) 1-1-1 Tennoudai Tsukuba Ibaraki 305-8571 (Japan);

    Department of Chemistry Faculty of Pure and Applied Sciences University of Tsukuba and CREST (JST) 1-1-1 Tennoudai Tsukuba Ibaraki 305-8571 (Japan);

    Department of Chemistry Faculty of Pure and Applied Sciences University of Tsukuba and CREST (JST) 1-1-1 Tennoudai Tsukuba Ibaraki 305-8571 (Japan);

    Department of Applied Chemistry Graduate School of Engineering Osaka University Suita Osaka 565-0871 (Japan);

    Institute for Materials Chemistry and Engineering Kyushu University Motooka Nishi-Ku Fukuoka 819-0395 (Japan);

    Institute for Materials Chemistry and Engineering Kyushu University Motooka Nishi-Ku Fukuoka 819-0395 (Japan);

    Department of Chemistry and Nano Science Ewha Womans University Seoul 120-750 (South Korea);

    Department of Chemistry Faculty of Pure and Applied Sciences University of Tsukuba and CREST (JST) 1-1-1 Tennoudai Tsukuba Ibaraki 305-8571 (Japan);

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 应用化学;
  • 关键词

    hydrogen bonds; monoprotonated porphyrins; nonplanar porphyrins; electron transfer; polar protic solvents;

    机译：氢键;单议突卟啉;非平面卟啉;电子转移;极性质子溶剂;

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