Advanced Soft Porous Organic Crystal with Multiple Gas‐Induced Single‐Crystal‐to‐Single‐Crystal Transformations for Highly Selective Separation of Propylene and Propane
Lin Li, Shuhong Zhao, Huiming Huang, Muyao Dong, Jie Liang, Hui Li, Jian Hao, Engui Zhao, Xinggui Gu
Abstract
Abstract Soft porous organic crystals with stimuli‐responsive single‐crystal‐to‐single‐crystal (SCSC) transformations are important tools for unraveling their structural transformations at the molecular level, which is of crucial importance for the rapid development of stimuli‐responsive systems. Carefully balancing the crystallinity and flexibility of materials is the prerequisite to construct advanced organic crystals with SCSC, which remains challenging. Herein, a squaraine‐based soft porous organic crystal (SPOC‐SQ) with multiple gas‐induced SCSC transformations and temperature‐regulated gate‐opening adsorption of various C1‐C3 hydrocarbons is reported. SPOC‐SQ is featured with both crystallinity and flexibility, which enable pertaining the single crystallinity of the purely organic framework during accommodating gas molecules and directly unveiling gas‐framework interplays by SCXRD technique. Thanks to the excellent softness of SPOC‐SQ crystals, multiple metastable single crystals are obtained after gas removals, which demonstrates a molecular‐scale shape‐memory effect. Benefiting from the single crystallinity, the molecule‐level structural evolutions of the SPOC‐SQ crystal framework during gas departure are uncovered. With the unique temperature‐dependent gate‐opening structural transformations, SPOC‐SQ exhibits distinctly different absorption behaviors towards C 3 H 6 and C 3 H 8 , and highly efficient and selective separation of C 3 H 6 /C 3 H 8 (v/v, 50/50) is achieved at 273 K. Such advanced soft porous organic crystals are of both theoretical values and practical implications.