Computational screening for nested organic cage complexes
Computational screening for nested organic cage complexes
复制标题
DOI：
10.1039/c9me00085b
复制
发表时间：
2020-01-01
影响因子：
3.6
通讯作者：
Jelfs, Kim E.
中科院分区：
文献类型：
--
作者：
Berardo, Enrico;Greenaway, Rebecca L.;Jelfs, Kim E.
超分子自组装可以合成美丽而复杂的分子结构，例如笼、大环、结、索烷和轮烷。我们在这里关注多孔有机笼，它们是具有内在空腔和多个窗口的分子。这些笼已被证明在分子分离和封装方面非常有效。我们研究了一个笼子位于另一个笼子的空腔内的复合体的可能性。我们将其称为“巢笼”复合体。此类复合物的设计极具挑战性，因此我们使用计算筛选来探索 8712 种不同的对组合，运行近 50 万次计算来对笼构象的相空间进行采样。通过分析组件的结合能，我们确定了嵌套笼复合物中高度能量有利的笼对。绝大多数最有利的配合物包括 Gawronski 及其同事利用 4-叔丁基-2,6-二甲酰基苯酚和顺式,顺式-1,3,5-三氨基环己烷的 [8 + 12] 反应报道的大亚胺笼。最有利的嵌套笼复合体将 Gawronski 笼与具有六个顶点的十二酰胺笼结合在一起，可以位于较大笼的六个窗口中。我们还确定了具有有利自连接结合能的笼子。
Supramolecular self-assembly has allowed the synthesis of beautiful and complex molecular architectures, such as cages, macrocycles, knots, catenanes, and rotaxanes. We focus here on porous organic cages, which are molecules that have an intrinsic cavity and multiple windows. These cages have been shown to be highly effective at molecular separations and encapsulations. We investigate the possibility of complexes where one cage sits within the cavity of another. We term this a 'nested cage' complex. The design of such complexes is highly challenging, so we use computational screening to explore 8712 different pair combinations, running almost 0.5 million calculations to sample the phase space of the cage conformations. Through analysing the binding energies of the assemblies, we identify highly energetically favourable pairs of cages in nested cage complexes. The vast majority of the most favourable complexes include the large imine cage reported by Gawronski and co-workers using a [8 + 12] reaction of 4-tert-butyl-2,6-diformylphenol and cis,cis-1,3,5-triaminocyclohexane. The most energetically favourable nested cage complex combines the Gawronski cage with a dodecaamide cage that has six vertices, which can sit in the six windows of the larger cage. We also identify cages that have favourable binding energies for self-catenation.