Wolpert Emma H, Jelfs Kim E
Department of Chemistry, Imperial College London, Molecular Sciences Research Hub, White City Campus Wood Lane London W12 0BZ UK
Department of Materials, Imperial College London London SW7 2AZ UK.
Chem Sci. 2024 Sep 18;15(40):16519-28. doi: 10.1039/d4sc04430d.
Molecular cages contain an internal cavity designed to encapsulate other molecules, resulting in applications in molecular separation, gas storage, and catalysis. Introducing chirality in cage molecules can improve the selective separation of chiral molecules and add new functionalities due to the realisation of chiral photophysical properties. It has recently been shown that solid-state supramolecular interactions between achiral cages can result in the formation of chiral cavities. Here, we develop a computational technique to predict when achiral cages form chiral cavities in the solid-state through the combination of atomistic calculations and coarse-grained modelling to predict the crystalline phase behaviour. Our focus is on the achiral cage B11, which contains rotatable arene rings on the vertices of the cage that can form propeller-like orientations, inducing a chiral cavity. We show that by using dimer pair calculations, we can inform coarse-grained models to predict the packing of the cage. Our results reveal how the supramolecular interactions drive chirality in the achiral cages without the need for a chiral guest. These findings are a first step towards understanding how we can design chirality through supramolecular interactions by using abstract coarse-grained models to inform design principles for targeted solid-state phase behaviour.
分子笼包含一个内部空腔，其设计目的是包封其他分子，从而在分子分离、气体储存和催化等领域得到应用。在笼状分子中引入手性可以改善手性分子的选择性分离，并由于手性光物理性质的实现而增加新的功能。最近的研究表明，非手性笼之间的固态超分子相互作用可导致手性空腔的形成。在此，我们开发了一种计算技术，通过结合原子计算和粗粒度模型来预测结晶相行为，从而预测非手性笼在固态时何时形成手性空腔。我们关注的是非手性笼B11，它在笼的顶点含有可旋转的芳烃环，这些环可形成螺旋桨状取向，从而诱导出手性空腔。我们表明，通过使用二聚体对计算，可以为粗粒度模型提供信息，以预测笼的堆积情况。我们的结果揭示了超分子相互作用如何在无需手性客体的情况下驱动非手性笼中的手性。这些发现是迈向理解如何通过超分子相互作用设计手性的第一步，即利用抽象的粗粒度模型为目标固态相行为提供设计原则。
