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

[Image: see text] 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 (PF(6)(–), SbF(6)(–), 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 BF(4)(–), 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.