Heterogeneous Interactions Promote Crystallization and Spontaneous Resolution of Chiral Molecules
Heterogeneous Interactions Promote Crystallization and Spontaneous Resolution of Chiral Molecules
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DOI：
10.1021/jacs.0c02097
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发表时间：
2020-06-17
影响因子：
15
通讯作者：
Grunwald, Michael
中科院分区：
文献类型：
--
作者：
Carpenter, John E.;Grunwald, Michael
预测手性分子从溶液中的结晶是化学科学中的一个主要挑战。在本文中，我们使用分子动力学的计算机模拟研究的粗粒模型的手性分子的结晶与广泛的分子形状和相互作用的家庭。我们的模拟再现了实验结晶行为的真实的手性分子，包括外消旋和对映体纯晶体，以及无定形固体。使用有效的算法包装的形状，我们列举了数以百万计的低能量晶体结构的每个模型和分析的热力学景观的多晶型物。与最近的结果一致，我们的分析表明，结晶的容易程度在很大程度上取决于具有低自由能的竞争多晶型物的数量。我们发现，这个数字，因此，结晶的结果取决于分子间的相互作用，在一个简单的方式：强烈的异质性分子间的相互作用促进结晶，有利于自发解决外消旋混合物。我们的研究结果有助于合理化一些实验观察，并可以为所需的结晶结果的分子和实验条件的设计提供指导。
Predicting the crystallization of chiral molecules from solution is a major challenge in the chemical sciences. In this paper, we use molecular dynamics computer simulations to study the crystallization of a family o f coarse-grained models of chiral molecules with a broad range of molecular shapes and interactions. Our simulations reproduce the experimental crystallization behavior of real chiral molecules, including racemic and enantiopure crystals, as well as amorphous solids. Using efficient algorithms for the packing o f shapes, we enumerate millions of low-energy crystal structures for each model and analyze the thermodynamic landscape of polymorphs. In agreement with recent conjectures, our analysis shows that the ease of crystallization is largely determined by the number of competing polymorphs with low free energy. We find that this number and, hence, crystallization outcomes depend on molecular interactions in a simple way: Strongly heterogeneous interactions across molecules promote crystallization and favor the spontaneous resolution of racemic mixtures. Our results help rationalize a number of experimental observations and can provide guidance for the design of molecules and experimental conditions for desired crystallization outcomes.