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Direct Observation of the Ultrafast Evolution of Open-Shell Biradical in Photochromic Radical Dimer

机译:直接观察光致变色自由基二聚体中开壳双自由基的超快速演化

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摘要

Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry. In this study, we directly probe the ultrafast dynamics of the delocalized biradical of a photochromic radical dimer, pentaarylbiimidazole (PABI), by time-resolved visible and infrared spectroscopies and quantum chemical calculations with the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). While the photogenerated transient species was considered to be a single species of the biradical, the present ultrafast spectroscopic study revealed the existence of two transient isomers differing in the contributions of biradical character. The origin of the two metastable isomers is most probably due to the substantial van der Waals interaction between the phenyl rings substituted at the imidazole rings. Unraveling the temporal evolution of the biradical contribution will stimulate to explore novel delocalized biradicals and to develop biradical-based photofunctional materials utilizing the dynamic properties.
机译:由于对单线态双基自由基的基本兴趣和诸如双光子吸收材料的若干潜在应用,对离域双基自由基进行了广泛的研究。但是,许多双自由基研究仅关注刚性分子结构的静态特性。预期离域双基的双基性质对分子结构及其局部环境的细微变化敏感。因此,对系统动力学性质的研究将对稳定的自由基化学有进一步的了解。在这项研究中,我们通过时间分辨的可见光谱和红外光谱以及利用扩展的多态完整活性空间二阶扰动理论进行量子化学计算,直接研究了光致变色自由基二聚体五芳基联咪唑(PABI)的离域双自由基的超快动力学( XMS-CASPT2)。虽然光生瞬态物质被认为是双自由基的单一物种,但本超快光谱研究显示存在两种瞬态异构体,它们在双自由基特性方面有所不同。两种亚稳态异构体的起源很可能是由于在咪唑环上取代的苯环之间存在大量的范德华相互作用。阐明双基贡献的时间演变将刺激探索新颖的离域双基,并利用动力学性质开发基于双基的光功能材料。

著录项

  • 来源
    《Journal of the American Chemical Society》 |2017年第18期|6382-6389|共8页
  • 作者单位

    Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan;

    Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan;

    Division of Frontier Materials Science and Center for Promotion of Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan;

    Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan;

    Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan;

    Division of Frontier Materials Science and Center for Promotion of Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan;

    Department of Physics, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8577, Japan;

    Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan;

    Division of Frontier Materials Science and Center for Promotion of Advanced Interdisciplinary Research, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan;

    Department of Chemistry, School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, Japan;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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  • 正文语种 eng
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  • 入库时间 2022-08-18 03:07:58

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