Modulating Supramolecular Charge-Transfer Interactions in the Solid State using Compressible Macrocyclic Hosts.
Modulating Supramolecular Charge-Transfer Interactions in the Solid State using Compressible Macrocyclic Hosts.
复制标题
使用可压缩大环主体调节固态中的超分子电荷转移相互作用。
DOI：
10.1002/anie.202210579
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发表时间：
2022
影响因子：
--
通讯作者：
Yingwei Yang
中科院分区：
文献类型：
--
作者：
Jiarui Wu;Dongxia Li;Gengxin Wu;Meng Li;Yingwei Yang
在超分子化学和材料科学中，调控主客体体系中特定给体和受体物种之间的分子间电荷转移(ICT)相互作用是一个巨大的挑战，具有很高的研究价值。在这项工作中，发展了一种通过压缩大环主体的结合腔来调节固态超分子ICT相互作用的策略，该结合腔被称为全乙基化斜柱[6]芳烃(p-EtLP6)。P-EtLP6对多种缺电子平面客体的固态ICT亲和力可以通过将大环主链从原始的对位桥联模式转变为混合的对位和偏桥异构体形式(m-EtLP6)来显著增强。与理论计算相结合的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，从而提高了ICT亲和力。
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.