Cooperative cluster metalation and ligand migration were performed on a Zr‐MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr 6 M 4 (M=Ni, Co) clusters. The M 2+ reacts with the μ 3 ‐OH and terminal H 2 O ligands on an 8‐connected [Zr 6 O 4 (OH) 8 (H 2 O) 4 ] cluster to form a bimetallic [Zr 6 M 4 O 8 (OH) 8 (H 2 O) 8 ] cluster. Along with the metalation of Zr 6 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.
@article{osti_1786111,
author = {Yuan, Shuai and Chen, Ying‐Pin and Qin, Junsheng and Lu, Weigang and Wang, Xuan and Zhang, Qiang and Bosch, Mathieu and Liu, Tian‐Fu and Lian, Xizhen and Zhou, Hong‐Cai},
title = {Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal–Organic Frameworks},
annote = {Abstract Cooperative cluster metalation and ligand migration were performed on a Zr‐MOF, leading to the isolation of unique bimetallic MOFs based on decanuclear Zr 6 M 4 (M=Ni, Co) clusters. The M 2+ reacts with the μ 3 ‐OH and terminal H 2 O ligands on an 8‐connected [Zr 6 O 4 (OH) 8 (H 2 O) 4 ] cluster to form a bimetallic [Zr 6 M 4 O 8 (OH) 8 (H 2 O) 8 ] cluster. Along with the metalation of Zr 6 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. },
doi = {10.1002/ange.201505625},
url = {https://www.osti.gov/biblio/1786111},
journal = {Angewandte Chemie},
issn = {ISSN 0044-8249},
number = {49},
volume = {127},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2015},
month = {10}}