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Updated: Oct 10, 2025

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes
Álvaro García-Romero1, Jose M Martín-Álvarez1, Daniel Miguel1
1GIR MIOMeT-IU, Cinquima, Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Campus Miguel Delibes, 47011 Valladolid, Spain.
Abstract:
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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