Wu Dong, Zhou Kang, Tian Jindou, Liu Caiping, Tian Jiayue, Jiang Feilong, Yuan Daqiang, Zhang Jian, Chen Qihui, Hong Maochun
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Angew Chem Int Ed Engl. 2021 Feb 8;60(6):3087-3094. doi: 10.1002/anie.202013885. Epub 2020 Dec 21.
Induction of chirality from an achiral assembly system remains a huge challenge related to the origin of life. Here, induction of chirality in a metal-organic framework (MOF) built from achiral precursors has been realized. Assembling achiral H BTB ligands and Zn /Cd clusters leads to a 2D coordination polymer (FJI-H16), while introduction of achiral pyridine into such assembly system leads to a 3D chiral MOF (FJI-H27 (M) or (P)). The driven force for chiral generation has been proved to be a pyridine participated kinetic-control assembly process, which can be controlled by changing the amount of pyridine and temperature, from no induction to partial induction to complete induction. The chiral generation process has been identified in detail through a pyridine-involved key intermediate (FJI-H28). The targeted modification of pyridine can selectively lead to FJI-H27 (M) or FJI-H27 (P), making the chiral orientation and distribution of bulk FJI-H27 samples can be controlled. Our work not only represents a new chiral induction process that may relate to the chiral origin in nature, but also firstly reveals how achiral external stimuli generate chirality from achiral precursors, and offers a guide for rational preparation of chiral MOFs.
从非手性组装体系诱导产生手性仍然是一个与生命起源相关的巨大挑战。在此,已实现了在由非手性前体构建的金属有机框架(MOF)中诱导手性。将非手性的H BTB配体与Zn/Cd簇组装可得到二维配位聚合物(FJI-H16),而将非手性吡啶引入该组装体系则可得到三维手性MOF(FJI-H27(M)或(P))。已证明手性产生的驱动力是一个吡啶参与的动力学控制组装过程,该过程可通过改变吡啶的量和温度来控制,从无诱导到部分诱导再到完全诱导。通过一个涉及吡啶的关键中间体(FJI-H28)详细确定了手性产生过程。对吡啶的靶向修饰可选择性地得到FJI-H27(M)或FJI-H27(P),使得块状FJI-H27样品的手性取向和分布能够被控制。我们的工作不仅代表了一种可能与自然界手性起源相关的新手性诱导过程,而且首次揭示了非手性外部刺激如何从非手性前体产生手性,并为合理制备手性MOF提供了指导。