Ionic Hydrogen‐Bonded Organic Frameworks for Ion‐Responsive Antimicrobial Membranes

Functionalization of hydrogen‐bonded organic frameworks (HOFs) for specific applications has been a long‐lasting challenge in HOF materials. Here, an efficient way to integrate functional species in the HOF structure through constructing an anionic framework is presented. The obtained HOFs, taking PFC‐33 (PFC = porous materials from FJIRSM,CAS) as an example, integrate a porphyrin photosensitizer as a porous backbone and a commercial biocide as counterions in the structure. The permanent channels and the electrostatic interaction between the framework and the counterions provide PFC‐33 ion‐responsive biocide‐release behavior in various physiological environments, thus exhibiting synergistic photodynamic and chemical antimicrobial efficiency. The unbonded carboxyl groups residing on the HOF surface further allow for manipulating the interfacial interaction between the PFC‐33 and the polymer matrix for membrane fabrication. Therefore, a polyHOF membrane with high stability, desired flexibility, and good permeability is obtained, which demonstrates noticeable bacterial inhibition toward Escherichia coli. This study may shed light on the functionalization of HOF materials for broad application potentials. The functionalization of hydrogen‐bonded organic frameworks (HOFs) can be achieved in a porphyrin‐based anionic HOF structure, endowing the material with synergistic photodynamic and chemical antimicrobial efficacy. By further taking advantage of the unbonded carboxyl groups on the HOF particle surface, a freestanding flexible membrane that shows high permeability, good stability, and excellent antibacterial activity is successfully fabricated.