Linker Enantiomericity Engineering in Reticular Frameworks for Architecting Robust Materials with Synergetic Open Metal Sites for Efficient SF 6 Capture

作者：Pengfu Gao, Weiwei Li, Boxu Dong, Jinli Zhang, Xuefeng Bai, Jingjing Zhang, Geng Yuan, Xin Han, Jiantao Zai, Jiandong Pang, Xin Zhang, Jinqiao Dong, Wei Gong, Yong Cui · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202520576 · 被引用次数：4 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Supramolecular Chemistry and Complexes、Surface Chemistry and Catalysis

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 Cu 2+ sites, which work synergistically to bind SF 6 molecules with outstanding SF 6 /N 2 separation performance, as validated by extensive sorption and breakthrough experiments as well as theoretical simulations. Our work suggests that beyond molecular systems, Wall...