Lo Shao-Wei, Kitao Takashi, Nada Yusuke, Murata Kei, Ishii Kazuyuki, Uemura Takashi
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba, 277-8561, Japan.
Angew Chem Int Ed Engl. 2021 Aug 9;60(33):17947-17951. doi: 10.1002/anie.202105967. Epub 2021 Jul 5.
Chiral induction is an emerging topic of interest in various areas of chemistry because of its relationship to the elusive mechanism of spontaneous symmetry breaking in nature. Buckminsterfullerene (C ) with the shape of a highly symmetric truncated icosahedron has rarely been referred for chiral induction due to the difficult symmetry breaking. In this work, we demonstrate that a chiral metal-organic framework (MOF) can provide a key field for chiral induction. C could be incorporated into the chiral nanochannels of the MOF using an in situ self-assembly strategy. The circular dichroism spectra of the resulting nanocomposites showed an intense chiral signal in the absorption region of C . Experimental and theoretical studies showed that this unprecedented chiral induction of C was attributed to hybridization of the molecular orbitals through a close association with the pore surface of the MOF. Our method can endow highly symmetric achiral compounds with chirality, paving the new way toward fabrication of novel chiral nanomaterials.
由于手性诱导与自然界中难以捉摸的自发对称性破缺机制相关，它已成为化学各个领域中一个新兴的研究热点。具有高度对称截角二十面体形状的巴克敏斯特富勒烯（C），由于其对称性破缺困难，很少被用于手性诱导。在这项工作中，我们证明了一种手性金属有机框架（MOF）可以提供一个关键的手性诱导场。利用原位自组装策略，C可以被纳入MOF的手性纳米通道中。所得纳米复合材料的圆二色光谱在C的吸收区域显示出强烈的手性信号。实验和理论研究表明，这种前所未有的C的手性诱导归因于通过与MOF孔表面的紧密结合而导致的分子轨道杂化。我们的方法可以赋予高度对称的非手性化合物手性，为新型手性纳米材料的制备开辟了新途径。
