Journal
INORGANIC CHEMISTRY
Volume 60, Issue 24, Pages 19206-19218Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03004
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Funding
- Spanish Ministry of Science, Innovation and Universities [MCIU] [PGC2018-096880-A-I00, PGC2018-099470-B-I00]
- Leverhulme Trust [RPG-2017-146]
- Spanish MINECO/AEI
- European Union (ESF) [RYC-2015-19035]
- University of Valladolid
- Santander Bank
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This study reveals the formation of a common hybrid metal-organic framework structure with Cu(I) and Ag(I) salts using tripodal ligands containing antimony and bismuth. It also demonstrates that the greater Lewis acidity of bismuth compared to antimony can lead to the collapse of the MOF structure. This provides insights into how the electronic effects of the bridgehead atoms in these ligand systems can impact their supramolecular chemistry.
The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py)(3)] and [Bi(3-py)(3)] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal-organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF6-, SbF6-, and OTf-), composed of a cationic substructure of rhombic cage (M)(4)(L)(4) units linked by Sb/Bi-M bonding. The greater Lewis acidity of Bi compared to Sb can, however, allows anion-Bi interactions to overcome Bi-metal bonding in the case of BF4-, leading to collapse of the MOF structure (which is also seen where harder metals like Li+ are employed). This study therefore provides insight into the way in which the electronic effects of the bridgehead atom in these ligand systems can impact their supramolecular chemistry.
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