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Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

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.

SUBMITTER: Garcia-Romero A

PROVIDER: S-EPMC8693195 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Strain Tuning via Larger Cation and Anion Codoping for Efficient and Stable Antimony?Based Solar Cells

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