Substituent effects in the crystallization of Zr-hydroxamate metal–organic frameworks

Abstract

Halogen substituent effects directed the crystallization of Zr-hydroxamate MOFs, inducing a topology evolution from kagome to square lattice—the first sql net in this MOF family—while preserving chemical robustness. In contrast, it was found that mono-halogenated linkers failed to crystallize with Zr ⁴⁺ into corresponding MOFs. DFT calculations revealed that linker symmetry enables cooperative coordination and ordered framework growth, indicating a symmetry-based crystal engineering principle for these chelation-dominated MOFs.