Cationic π-Stacking Columns of Coronene Molecules with Fully Charged and Charge-Disproportionated States
Cationic π-Stacking Columns of Coronene Molecules with Fully Charged and Charge-Disproportionated States
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具有完全带电和电荷歧化态的晕苯分子的阳离子π堆积柱
DOI：
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
G. Saito
中科院分区：
文献类型：
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作者：
Y. Yoshida;K. Isomura;M. Maesato;T. Koretsune;Y. Nakano;H. Yamochi;H. Kishida;G. Saito
在四面体GaCl_4-阴离子存在下，具有D_6h对称性的多环芳烃晕苯的电化学氧化得到两种阳离子盐（晕苯）（GaCl_4）（1）和（晕苯）_5（GaCl_4）_2（2），其电荷排列是前所未有的。盐1涉及以Z字形方式的π堆积柱，其由晶体学上等价的晕苯一价阳离子组成。第一性原理计算表明，二聚晕阳离子引起的费米能级的带隙开放，因此，半导体行为。另一方面，在盐2中，两个晶体学上独立的晕苯分子（A和B）形成具有AABB重复单元的π堆积柱，其侧接另一个晕苯分子（C）。晶体学特征，如晶面间距和由Jahn-Teller效应引起的面内分子畸变，以及第一性原理计算，强烈地表明在π堆积晶体中出现了电荷畸变。
Electrochemical oxidation of a polycyclic aromatic hydrocarbon, coronene, with D6h symmetry in the presence of tetrahedral GaCl4– anions gave two cation salts, (coronene)(GaCl4) (1) and (coronene)5(GaCl4)2 (2), with unprecedented charge arrangements. Salt 1 involves π-stacking columns in a zigzag manner, which are composed of the crystallographically equivalent coronene monocations. First-principle calculations revealed that the dimerization of coronene cations gives rise to a band gap opening at the Fermi level, and thus, semiconducting behavior. On the other hand, in salt 2, two crystallographically independent coronene molecules (A and B) form π-stacking columns with an AABB repeating unit, which are flanked by another coronene molecule (C). The crystallographic features, such as interplanar distances and in-plane molecular distortions arising from the Jahn–Teller effect, as well as the first-principle calculations, strongly suggested the emergence of charge disproportionation within the π-stacking col...