中国科学院福建物质结构研究所结构化学国家重点实验室洪茂椿院士团队， 揭示了由非手性前体构建的金属-有机框架(MOF)中手性的诱导机制。该项研究成果发表在2020年11月13日的《德国应用化学》。

从非手性组装系统中诱导手性面临巨大的挑战，因为其涉及生命起源和手性材料合理设计。

在该研究中，实现了从非手性前体构建的MOF中手性的起源和控制。组装非手性 H3 BTB配体和Zn（II）/Cd（II）簇形成2D配位聚合物（FJI-H16），而将非手性吡啶引入该组装系统则形成3D手性MOF（FJI-H27（M）或（P））。FJI-H27手性源的驱动力是吡啶参与的动力学控制组装过程，它可以通过改变吡啶的用量和温度，实现从无诱导到部分诱导到完全诱导的控制。手性生成和扩增过程已通过吡啶相关关键中间体（FJI-H28）进行了详细的识别。吡啶的靶向修饰可选择性地形成FJI-H27（M）或FJI-H27（P），从而控制FJI-H27样品主体的手性取向和分布。

该研究不仅代表了一种新的、高度可控的与手性的本质有关的手性诱导过程，而且首次揭示了非手性外部刺激是如何从非手性前体中产生手性的，为手性MOFs的合理制备提供了指导。

附：英文原文

Title: Induction of chirality in a metal‐organic framework (MOF) built from achiral precursors

Author: Dong Wu, Kang Zhou, Jindou Tian, Caiping Liu, Jiayue Tian, Feilong Jiang, Daqiang Yuan, Jian Zhang, Qihui Chen, Maochun Hong

Issue&Volume: 13 November 2020

Abstract: Induction of chirality from achiral assembly system remains a huge challenge related to the origin of life and rational design of chiral materials. Here, both origin and control of chirality in a MOF built from achiral precursors have been realized. Assembling achiral H  3  BTB ligands and Zn(II)/Cd(II) 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 origin of  FJI‐H27  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 and amplification 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 and highly controllable 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.

DOI: 10.1002/anie.202013885

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202013885