Mechanochemical synthesis has recently emerged as a scalable “green” approach for the preparation of MOFs, but current understanding of the underlying reaction mechanisms is limited. In this work, an investigation of the reaction pathway of the mechanochemical synthesis of MOF-74 from ZnO and 2,5-dihydroxyterephthalic acid (H 4 HDTA), using DMF as a liquid additive, is presented. The complex reaction pathway involves the formation of four short-lived intermediate phases, prior to the crystallization of MOF-74. The crystal structures of three of these intermediates have been determined using a combination of single-crystal and powder X-ray diffraction methods and are described here. The initial stages of the reaction are very fast, with a DMF solvate of H 4 HDTA forming after only 2 min of milling. This is followed by crystallization, after only 4 min of milling, of a triclinic one-dimensional coordination polymer, Zn(H 2 DHTA)(DMF) 2 (H 2 O) 2 , which converts into a monoclinic polymorph on additional milling. Highly crystalline MOF-74 appears after prolonged milling, for at least 70 min.

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The solvothermal reaction of Zn(NO3)2·6H2O with 5-aminoisophthalic acid and 4,4/-bipyridyl (4,4/-bipy) led to the self-assembly of the known 3-D hybrid H-bonded/covalent structure {[Zn(5-AIP)(4,4/-bipy)0.5]·DMF}n (1·DMF), but with DMF here (rather than...