Cooperative Cluster Metalation and Ligand Migration in Zirconium MetalOrganic Frameworks Academic Article uri icon

abstract

  • AbstractCooperative cluster metalation and ligand migration were performed on a ZrMOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr6M4 (M=Ni, Co) clusters. The M2+ reacts with the 3OH and terminal H2O ligands on an 8connected [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 Zrcarboxylate bond dissociates to form a Mcarboxylate bond. Singlecrystal to singlecrystal transformation is realized so that snapshots for cooperative cluster metalation and ligand migration processes are captured by successive singlecrystal Xray structures. In3+ was metalated into the same ZrMOF which showed excellent catalytic activity in the acetaldehyde cyclotrimerization reaction. This work not only provides a powerful tool to functionalize ZrMOFs with other metals, but also structurally elucidates the formation mechanism of the resulting heterometallic MOFs.

published proceedings

  • Angewandte Chemie

author list (cited authors)

  • Yuan, S., Chen, Y., Qin, J., Lu, W., Wang, X., Zhang, Q., ... Zhou, H.

citation count

  • 27

publication date

  • December 2015

publisher