Mechanochemistry of Group 4 Element-Based Metal–Organic Frameworks
Fillipp Edvard Salvador, Vance Miller, Kaoru Shimada, Chen‐Hao Wang, Joshua Wright, Milton Das, Ying‐Pin Chen, Yu‐Sheng Chen, Chris J. Sheehan, Wenqian Xu, Gayan Rubasinghege, Wen‐Yang Gao
Abstract
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 TiIV-derived MOFs, tentatively because of the relatively low Ti–O bond dissociation energy.