Bioinspired “Intermolecular Pocket” in Soft Molecular Crystal of Porous Organic Cage Exhibiting Reversible Guest Recognition

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