近日，上海交通大学崔勇团队研究了网状框架中的连接体对映异构体工程用于构建具有协同开放金属位点的坚固材料，以实现有效的SF₆捕获。相关论文发表在2025年10月29日出版的《德国应用化学》杂志上。

手性连接剂能够提供固有的对映异构特性，可用于调控孔道微环境甚至调控网状框架的整体尺寸与拓扑结构。尽管已有研究表明，纯对映体与外消旋连接剂在金属配位组装过程中会形成显著不同的结构，但此类实例仍极为罕见，且大多源于偶然发现而非理性设计。

研究组基于网状框架中的本征手性拓扑概念，结合超分子体系中"外消旋晶体密度高于手性晶体"的沃拉赫规则，成功构建了一个独特案例：在室温水相中与铜离子结晶时，纯对映体连接剂形成了具有本征手性(10,3)-a srs拓扑的三维多孔稳定框架（S-TAMOF-3D），而外消旋连接剂则专一性地生成二维致密无孔层状结构（race-TAMOF-2D）。这一实验现象表明，连接剂的对映异构特性可能导致的结构多样性远超既往认知。

进一步研究表明，活化后的S-TAMOF-3D框架内存在修饰有裸露Cu²⁺开放位点的三角形空腔，这些结构要素通过协同作用实现了对SF₆分子的高效捕获，并展现出卓越的SF₆/N₂分离性能——该结论已通过系统吸附实验、穿透实验及理论模拟验证。该研究证明，沃拉赫规则的适用性可超越分子体系，进一步指导拓展网状材料的设计，实现传统连接剂工程策略无法获得的结构，从而为构建功能增强的网状材料提供了新方法论。

附：英文原文

Title: Linker Enantiomericity Engineering in Reticular Frameworks for Architecting Robust Materials with Synergetic Open Metal Sites for Efficient SF6 Capture

Author: Pengfu Gao, Weiwei Li, Boxu Dong, Jinli Zhang, Xuefeng Bai, Jingjing Zhang, Yuan Geng, Xin Han, Jiantao Zai, Jiandong Pang, Xin Zhang, Jinqiao Dong, Wei Gong, Yong Cui

Issue&Volume: 2025-10-29

Abstract: Chiral linkers offer built-in enantiomericity capable of regulating pore microenvironments or even net dimensions and topologies of the resulting reticular frameworks. Whereas it has been established that enantiopure and racemic linkers can form significantly different structures upon metal directed coordination assembly, such examples are still extremely rare and occur largely through serendipity rather than rational design. In this work, guided by the intrinsically chiral topology concept established in reticular frameworks and the Wallach's rule that racemic crystals are denser than chiral ones in supramolecular systems, we target a unique example where enantiopure linker gives a homochiral 3D porous and robust framework (S-TAMOF-3D) with intrinsically chiral (10,3)-a srs topology while the racemic linker exclusively produces a 2D dense and non-porous layered structure (race-TAMOF-2D), upon crystallization with Cu ions in water at room temperature. This experimental observation points to the fact that linker enantiomericity could lead to structural diversity much greater than has hitherto been suspected. Moreover, the activated S-TAMOF-3D shows triangle-shaped cavities decorated with exposed open Cu2+ sites, which work synergistically to bind SF6 molecules with outstanding SF6/N2 separation performance, as validated by extensive sorption and breakthrough experiments as well as theoretical simulations. Our work suggests that beyond molecular systems, Wallach's rule can also be leveraged to guide the design of extended reticular materials that otherwise are unachievable via traditional linker engineering strategies, thus offering a new methodology for architecting reticular materials with enhanced functions.

DOI: 10.1002/anie.202520576

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202520576