Shen Chao, Gong Zhenyu, Gao Lei, Gu Minglong, Huan Long, Wang Sicong, Xie Ju
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, Jiangsu, China.
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071, China.
J Mol Model. 2018 Jul 9;24(8):199. doi: 10.1007/s00894-018-3736-2.
In order to systematically explore the general rule of the host-guest chemistry for pillararenes, this work investigates the weak interactions between pillar[4]arene and some typical guests (anions, cations, and dumbbell-shaped molecules) by using density functional theory (DFT) calculations at the ωB97XD/6-311G(d,p) level. The strong molecular recognition ability of pillar[4]arene has been discussed based on the geometry structure, electronic structure, and thermodynamic properties of the host-guest complexes. The results show that the equivalent lower and upper rims of the pillar[4]arene can be combined with both anion and cation, and its cavity can accommodate the alkyl part of the dumbbell-shaped molecule. The main host-guest interactions between pillar[4]arene and guests are hydrogen bond, cation-π, anion-π, and hydrophobic interaction by visualization of weak interactions using the Multiwfn program. Pillar[4]arene will form a more stable host-guest complex with the guest, which possesses conjugate structure and weak steric repulsion. This work intends to provide a theoretical basis for enriching the host-guest chemistry, understanding the supramolecular morphology, and expanding the applications of the pillararenes.
为了系统地探索柱芳烃主客体化学的一般规律，本工作采用ωB97XD/6-311G(d,p)水平的密度泛函理论（DFT）计算方法，研究了柱[4]芳烃与一些典型客体（阴离子、阳离子和哑铃状分子）之间的弱相互作用。基于主客体配合物的几何结构、电子结构和热力学性质，讨论了柱[4]芳烃强大的分子识别能力。结果表明，柱[4]芳烃的上下边缘等效部位均可与阴离子和阳离子结合，其空腔能够容纳哑铃状分子的烷基部分。利用Multiwfn程序对弱相互作用进行可视化分析可知，柱[4]芳烃与客体之间的主要主客体相互作用为氢键、阳离子-π、阴离子-π和疏水相互作用。柱[4]芳烃与具有共轭结构且空间位阻较小的客体形成的主客体配合物更加稳定。本工作旨在为丰富主客体化学、理解超分子形态以及拓展柱芳烃的应用提供理论依据。
