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.

Exploration of effective ways to integrate various functional species into hydrogen‐bonded organic frameworks (HOFs) is critically important for their applications but highly challenging. In this study, according to the “bottle‐around‐ship” strategy, core–shell heterostructure of upconversion nanoparticles (UCNPs) and HOFs was fabricated for the first time via a ligand‐grafting stepwise method. The UCNPs “core” can effectively upconvert near‐infrared (NIR) irradiation (980 nm) into visible light (540 nm and 653 nm), which further excites the perylenediimide‐based HOF “shell” through resonance energy transfer. In this way, the nanocomposite inherits the high porosity, excellent photothermal and photodynamic efficiency, NIR photoresponse from two parent materials, achieving intriguing NIR‐responsive bacterial inhibition toward Escherichia coli. This study may shed light on the design of functional HOF‐based composite materials, not only enriching the HOF library but also broadening the horizon of their potential applications.

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