Facile Mechanosynthesis of the Archetypal Zn-Based Metal-Organic Frameworks.

Mechanochemical methods have been successful in providing rapid access to a number of inorganic-organic functional materials under mild conditions. Recently, we demonstrated a novel mechanochemical strategy for metal-organic framework (MOF) preparation based on predesigned oxo-centered secondary building units. Herein, we develop this method for the facile preparation of the isoreticular MOF (IRMOF) family members based on a combination of an oxozinc amidate cluster, [Zn4(μ4-O)(NHOCPh)6], and selected ditopic aminoterephthalate and 4,4'-biphenyldicarboxylate as well as tritopic 1,3,5-benzenetribenzoate ligands. The resulting IRMOF-3, IRMOF-10, and MOF-177 crystalline materials were characterized using powder X-ray diffraction, IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis. We found that the character of the organic linker strongly affects the nature of the resulting MOF crystallites after activation processes. The SEM images demonstrate that IRMOF-3 formed microcrystallites in the range of 400-500 nm, while the two other materials exhibited microstructures of amorphous phases. The porosity of each sample was estimated by N2 sorption measurements at 77 K. These results provide an efficient and general method for the mechanosynthesis of Zn-based MOF materials using a predesigned oxozinc cluster.