Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Nat Commun. 2021 Nov 25;12(1):6841. doi: 10.1038/s41467-021-27236-1.
Hierarchically ordered chiral crystals have attracted intense research efforts for their huge potential in optical devices, asymmetric catalysis and pharmaceutical crystal engineering. Major barriers to the application have been the use of costly enantiomerically pure building blocks and the difficulty in precise control of chirality transfer from molecular to macroscopic level. Herein, we describe a strategy that offers not only the preferred formation of one enantiomorph from racemic solution but also the subsequent enantiomer-specific oriented attachment of this enantiomorph by balancing stereoselective and non-stereoselective interactions. It is demonstrated by on-demand switching the sign of fan-shaped crystal aggregates and the configuration of their components only by changing the molar mass of tailored polymeric additives. Owing to the simplicity and wide scope of application, this methodology opens an immediate opportunity for facile and efficient fabrication of one-handed macroscopic aggregates of homochiral organic crystals from racemic starting materials.
具有分级有序结构的手性晶体在光学器件、不对称催化和药物晶体工程等领域具有巨大的应用潜力,因此受到了广泛的关注。目前,主要的应用障碍在于使用昂贵的对映体纯构建块,以及难以从分子水平精确控制手性转移到宏观水平。在此,我们描述了一种策略,不仅可以从外消旋溶液中优先形成一种对映异构体,而且可以通过平衡立体选择性和非立体选择性相互作用,随后对这种对映异构体进行特定的对映体定向附着。通过改变定制聚合物添加剂的分子量,按需切换扇形晶体聚集体的符号和其组成部分的构型,证明了这一点。由于方法简单,适用范围广,这种方法为从外消旋起始原料简便、高效地制备手性有机晶体的单一宏观聚集体提供了一个直接的机会。