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Cooperatively Interlocked [2+1]-Type π-System-Anion Complexes

机译：协同互锁[2 + 1]型π-系统阴离子复合物

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摘要

As fascinating examples of closely connected multiple π-electronic systems involving noncovalent interactions, the cooperatively interlocked [2+1]-type anion complexes of well-designed π-electronic molecules are reported. The anion-responsive π-electronic molecules investigated in this study are the boron complexes of dipyrrolyldiketones bearing arylethynyl moieties at the pyrrole a-positions. Diverse substituents were introduced at the terminal aryl moieties, thus controlling the cooperativity to form [2+1]-type complexes. Theoretical studies showed that this cooperativity was induced by effective interactions between the introduced arylethynyl moieties. The investigations of the anion-binding processes showed that the first and second bindings to the guest anion were energetically almost equivalent, indicating the fundamental and important features of the electronic states of the halide anions. Furthermore, the interlocked anion complexes, whose geometries were distorted from the orthogonal arrangements, had the racemic states of the chiral conformations, either of which was induced by ion pairing with an appropriate chiral p-electronic cation, resulting in the chiroptical property as shown by circular dichroism.
机译：作为涉及非共价相互作用的紧密连接的多π-电子系统的迷人示例，报道了良好设计的π电子分子的协同互锁的[2 + 1]型阴离子复合物。本研究中研究的阴离子响应性π-电子分子是吡咯并在吡咯的芳基乙炔基部分的硼络合物在吡咯A-位置。在末端芳基部分引入不同的取代基，从而控制合作效应以形成[2 + 1]型复合物。理论研究表明，通过引入的芳基乙炔基部分之间的有效相互作用诱导该合作效应。阴离子结合过程的研究表明，客人阴离子的第一和第二绑定有用几乎相当于，表明卤化物阴离子的电子国家的基本和重要特征。此外，从正交布置中失真的互锁的阴离子复合物具有手性构象的外消旋状态，其中任何一个都是通过离子配对与适当的手性P-Electrong阳离子诱导的，导致毛细管性质如图所示圆形二分。

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  • 来源
    《Chemistry: A European journal》 |2017年第17期|共9页
  • 作者

    Ryohei Yamakado; Yukina Ashida; Ryuma Sato; Yasuteru Shigeta; Nobuhiro Yasuda; Hiromitsu Maeda;

  • 作者单位

    Department of Applied Chemistry College of Life Sciences Ritsumeikan University Kusatsu 525-8577 (Japan);

    Department of Applied Chemistry College of Life Sciences Ritsumeikan University Kusatsu 525-8577 (Japan);

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

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

    Research and Utilization Division Japan Synchrotron Radiation Research Institute Sayo 679-5198 (Japan);

    Department of Applied Chemistry College of Life Sciences Ritsumeikan University Kusatsu 525-8577 (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

    anions; cooperative effects; interlocked complexes; ion pairing; pi interactions;

    机译：阴离子;合作效应;互锁复合物;离子配对;PI相互作用;

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