Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal–Organic Frameworks |
| |
| Authors: | Shuai Yuan Ying‐Pin Chen Dr. Junsheng Qin Dr. Weigang Lu Xuan Wang Dr. Qiang Zhang Mathieu Bosch Dr. Tian‐Fu Liu Xizhen Lian Prof. Dr. Hong‐Cai Zhou |
| |
| Affiliation: | Department of Chemistry, Texas A&M University, College Station, TX 77843 (USA) http://www.chem.tamu.edu/rgroup/zhou/ |
| |
| Abstract: | Cooperative 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. |
| |
| Keywords: | cluster metalation heterometallic MOFs ligand migration metal– organic frameworks zirconium |
|
