Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks. Academic Article uri icon

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 M(2+) reacts with the 3-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. In(3+) 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.

published proceedings

  • Angew Chem Int Ed Engl

altmetric score

  • 3.25

author list (cited authors)

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

citation count

  • 131

complete list of authors

  • Yuan, Shuai||Chen, Ying-Pin||Qin, Junsheng||Lu, Weigang||Wang, Xuan||Zhang, Qiang||Bosch, Mathieu||Liu, Tian-Fu||Lian, Xizhen||Zhou, Hong-Cai

publication date

  • December 2015

publisher