Bioinspired “Intermolecular Pocket” in Soft Molecular Crystal of Porous Organic Cage Exhibiting Reversible Guest Recognition
Laiyu Zhang, Qiong Lei, Mao Yi, Zhiyuan Zhang, Xin Lian, Jian Xu, Shuo Zhang, Shuo Zhang, Lin Li, Lin Li, Baiyan Li, Xian‐He Bu
Abstract
Abstract Porous Organic Cages (POCs) have gathered a lot of attention in sorts of fields. Previous studies often focused on the functionalization of their intrinsic porosity, while the utilization of the extrinsic porosity has been seldom reported. To date, the rational construction of functionalized extrinsic porosity in POCs is a serious challenge, which still relies on trial and error. Inspired by hydrophobic proteins, in the contribution, a POC (namely NKPOC‐DS) is obtained with hydrophobic “intermolecular pocket” as extrinsic porosity constructed through the assembly of disulfide bonds with hydrophobic groups, facilitating strong supramolecular interactions as confirmed by Electrostatic Potential (ESP) maps and single‐crystal X‐ray diffraction analysis. Notably, NKPOC‐DS exhibits a unique C 2 H 6 ‐selective “breathing behaviour” due to the presence of softness in its extrinsic porosity, which does not extend to other gases such as C 2 H 4 , CH 4 , CO 2 , N 2 , and H 2 . Such specific recognition of C 2 H 6 thus provides NKPOC‐DS with the ability to preferentially adsorb C 2 H 6 from a C 2 H 6 /C 2 H 4 mixture. The innovative approach of biomimicry in the design of functional POCs provides new insights into manipulating the packing of cages, paving the way for potential applications in guest recognition and adsorption separations.