Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2(
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 Zr6cluster, 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.
more » « less- NSF-PAR ID:
- 10236562
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 54
- Issue:
- 49
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 14696-14700
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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