Wu Jia-Rui, Li Dongxia, Wu Gengxin, Li Meng-Hao, Yang Ying-Wei
International Joint Research Laboratory of Nano-Micro Architecture Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, P. R. China.
Key Laboratory of Automobile Materials of Ministry of Education and School of Materials Science and Engineering, Jilin University, 5988 Renmin Street, Changchun, 130025, P. R. China.
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202210579. doi: 10.1002/anie.202210579. Epub 2022 Sep 27.
Modulating intermolecular charge-transfer (ICT) interactions between specific donor and acceptor species in host-guest systems is a big challenge and full of research value in supramolecular chemistry and materials science. In this work, a strategy to modulate the supramolecular ICT interactions in the solid state is developed by compressing the binding cavity of a macrocyclic host named perethylated leaning pillar[6]arene (p-EtLP6). The solid-state ICT affinities of p-EtLP6 toward multi-types of electron-deficient planar guests could be significantly enhanced by transforming the macrocyclic backbone from the original para-bridged mode into a hybrid para- and meta-bridged isomeric form (m-EtLP6). X-ray single-crystal structural analyses incorporating theoretical calculation demonstrate that the improved ICT affinities are mainly attributed to the superior host-guest size fit arising from the compressed binding cavity in m-EtLP6 as compared with p-EtLP6.
在主客体体系中调节特定供体和受体物种之间的分子间电荷转移（ICT）相互作用是一项巨大挑战，在超分子化学和材料科学领域具有很高的研究价值。在这项工作中，通过压缩一种名为全乙基化倾斜柱[6]芳烃（p-EtLP6）的大环主体的结合腔，开发了一种在固态中调节超分子ICT相互作用的策略。通过将大环主链从原来的对桥模式转变为对桥和间桥混合的异构形式（m-EtLP6），p-EtLP6对多种缺电子平面客体的固态ICT亲和力可显著增强。结合理论计算的X射线单晶结构分析表明，与p-EtLP6相比，m-EtLP6中压缩的结合腔产生了更好的主客体尺寸匹配，这是ICT亲和力提高的主要原因。
