Metal–organic frameworks (MOFs) have demonstrated great potentials toward catalysis, particularly in the establishment of structure–property relationships. Herein, an unusual OOP (out-of-plane) porphyrin-based MOF, synthesized by controlling the metal ion release with an unprecedented In­(OH)3 precursor, possesses high stability and exhibits unexpectedly high photocatalytic hydrogen production activity, far surpassing the isostructural in-plane porphyrin-based MOF counterparts. In the MOF structure, indium ions not only form indium–oxo chains but also metalate the porphyrin rings in situ, locating above the porphyrin plane instead of fitting in a coplanar fashion into the cavity and affording an unusual OOP porphyrin. Control experiments demonstrate that the OOP In­(III) ions readily detach from the porphyrin rings under light excitation, avoiding the fast back electron transfer and thus greatly improving electron–hole separation efficiency and photocatalytic performance. To our knowledge, this is an unprecedented report on boosting MOF photocatalysis on the basis of special metalloporphyrin behavior.

The fabricating of metal−organic frameworks (MOFs) that integrate high stability and functionality remains a long-term pursuit yet a great challenge. Herein, we develop a linker desymmetrization strategy to construct highly stable porphyrinic MOFs, namely, USTC-9 (USTC represents the University of Science and Technology of China), presenting the same topological structure as the well-known PCN-600 that readily loses crystallinity in air or upon conventional activation. For USTC-9, the involved porphyrinic linker (TmCPP-M) with carboxylate groups located in the meta-position presents a chair-shaped conformation with lower C 2h symmetry than that (D 4h ) of the common porphyrinic carboxylate (TCPP) linker in PCN-600. As a result, the wrinkled and interlocked linker arrangements collectively contribute to the remarkable stability of USTC-9. Given the high stability and porosity as well as Lewis acidity, USTC-9(Fe) demonstrates its excellent performance toward catalytic CO 2 cycloaddition with diverse epoxides at moderate temperature and atmospheric pressure.

Cocrystallization is commonly used for its ability to improve the physical properties of APIs, such as solubility, bioavailability, compressibility, etc. The pharmaceutical industry is particularly interested in those cocrystals comprising a GRAS former in connection with the target API. In this work, we focus on the potential of urea as a cocrystal former, identifying three novel pharmaceutical cocrystal systems with catechin, 3-hydroxyl-2-naphthoic and ellagic acid. Interestingly, the stability of catechin under high humidity or high temperature environment is improved upon cocrystallization with urea. Moreover, the solubility of ellagic acid is improved about 17 times. This work displays the latent possibility of urea in improving the physical property of drug molecules using a cocrystallization approach.

Quaternary phase diagram of ionic cocrystals with solid solution formation is generated and dissolution surface is depicted clearly by contour lines.