Abstract
AbstractCooperative cluster metalation and ligand migration were performed on a Zr‐MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr6M4 (M=Ni, Co) clusters. The M2+ reacts with the μ3‐OH and terminal H2O ligands on an 8‐connected [Zr6O4(OH)8(H2O)4] cluster to form a bimetallic [Zr6M4O8(OH)8(H2O)8] cluster. Along with the metalation of Zr6 cluster, ligand migration is observed in which a Zr–carboxylate bond dissociates to form a M–carboxylate bond. Single‐crystal to single‐crystal transformation is realized so that snapshots for cooperative cluster metalation and ligand migration processes are captured by successive single‐crystal X‐ray structures. In3+ was metalated into the same Zr‐MOF which showed excellent catalytic activity in the acetaldehyde cyclotrimerization reaction. This work not only provides a powerful tool to functionalize Zr‐MOFs with other metals, but also structurally elucidates the formation mechanism of the resulting heterometallic MOFs.
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