Harnessing Halogen Bonds in Porous Molecular Crystals for Efficient SF <sub>6</sub> /N <sub>2</sub> Separation
Abstract
Abstract Halogen bonding offers a directional and tunable noncovalent interaction that remains underexplored in the design of porous molecular materials. Here, we report FPMC‐1‐β , a porous molecular crystal that uniquely integrates permanent porosity, high thermal stability, solution processability, and halogen bonding capability. Upon desolvation, FPMC‐1‐α undergoes a structural transformation into the denser FPMC‐1‐β phase, featuring distorted 1D channels lined with exposed σ‐holes on bromine atoms. This architecture enables selective halogen bond‐mediated interactions with fluorinated gases. FPMC‐1‐β exhibits a sulfur hexafluoride (SF 6 )/N 2 selectivity of 178.6 at 298 K and 1 bar—setting a new record among all reported porous molecular crystals and soluble porous materials. Combined experimental and computational studies reveal that the high selectivity arises from strong F⋯Br halogen bonding with SF 6 , in contrast to the weak, nonspecific interactions observed for N 2 .
Article Details
Authors (6)
Qi Jia
Chong Zhao
Wenjie Zhu
Nie Fang
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials Shanghai Hongkong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai 200032 China
Xiao He
Yanchuan Zhao
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials Shanghai Hongkong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai 200032 China