Rational Synthesis of Mixed-Metal Microporous Metal–Organic Frameworks with Controlled Composition Using Mechanochemistry

Mechanochemistry enables targeted, rapid synthesis of bimetallic metal–organic frameworks (MOFs) with a controlled 1:1 stoichiometric composition of metal nodes. In particular, ball milling enabled the use of specifically synthesized solid coordination complexes of Zn(II), Mg(II), Ni(II), and Co(II) for the assembly of a range of microporous mixed-metal MOF-74 materials composed of pairs of d-block or main group metals in a predetermined 1:1 stoichiometric ratio, including ZnMg-, ZnCo-, ZnCu-, MgZn-, MgCo-, NiZn-, NiMg-, NiCo-, CoZn-, CoMg-, CoCu-, and MgCa-MOF-74. By using specifically prepared precursors in the synthesis of diverse mixed-metal MOF-74 targets, this rational synthesis represents the first entry of mechanochemistry into the target-oriented synthesis of mixed-metal MOFs.