Mechanochemistry of Group 4 Element-Based Metal–Organic Frameworks

Mechanochemical synthesis is emerging as an environmentally friendly yet efficient approach to preparing metal-organic frameworks (MOFs). Herein, we report our systematic investigation on the mechanochemical syntheses of Group 4 element-based MOFs. The developed mechanochemistry allows us to synthesize a family of Hf₄O₄(OH)₄(OOC)₁₂-based MOFs. Integrating [Zr₆O₄(OH)₄(OAc)₁₂]₂ and [Hf₆O₄(OH)₄(OAc)₁₂]₂ under the mechanochemical conditions leads to a unique family of cluster-precise multimetallic MOFs that cannot be accessed by the conventional solvothermal synthesis. Extensive efforts have not yielded an effective pathway for preparing Ti^IV-derived MOFs, tentatively because of the relatively low Ti-O bond dissociation energy.