Mulay Sandip V, Dishi Or, Fang Yuan, Niazi Muhammad R, Shimon Linda J W, Perepichka Dmitrii F, Gidron Ori
Institute of Chemistry , The Hebrew University of Jerusalem , Edmond J. Safra Campus , Jerusalem , Israel . Email:
Department of Chemistry , McGill University , Montreal , QC H3A 0B8 , Canada . Email:
Chem Sci. 2019 Aug 19;10(37):8527-8532. doi: 10.1039/c9sc03247a. eCollection 2019 Oct 7.
We report the first π-conjugated macrocyclic system with an oligofuran backbone. The calculated HOMO-LUMO gap is similar to that of the corresponding linear polymer, indicating a remarkable electron delocalization. The X-ray structure reveals a planar conformation, in contrast to the twisted conformation of macrocyclic oligothiophenes. The intermolecular π-π stacking distance is extremely small (3.17 Å), indicating very strong interactions. The macrocycle forms large π-aggregates in solution and shows a tendency toward highly ordered multilayer adsorption at the solid-liquid interface. The face-on orientation of molecules explains the higher hole mobility observed in the out-of-plane direction.
我们报道了首个具有低聚呋喃主链的π共轭大环体系。计算得到的最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能隙与相应线性聚合物的能隙相似，表明存在显著的电子离域。X射线结构显示出平面构象，这与大环低聚噻吩的扭曲构象形成对比。分子间π-π堆积距离极小（3.17 Å），表明相互作用非常强。该大环在溶液中形成大的π聚集体，并在固液界面表现出向高度有序多层吸附的趋势。分子的面取向解释了在面外方向观察到的较高空穴迁移率。
