RT info:eu-repo/semantics/article T1 Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes A1 García Romero, Álvaro A1 Martín Álvarez, José Miguel A1 Miguel San José, Daniel A1 Wright, Dominic Simon A1 Álvarez González, Celedonio Manuel A1 García Rodríguez, Raúl K1 X-rays K1 Rayos X K1 Cations K1 Cationes K1 Anions K1 Aniones K1 Ligands K1 Ligandos AB 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. PB ACS Publications SN 0020-1669 YR 2021 FD 2021 LK https://uvadoc.uva.es/handle/10324/50935 UL https://uvadoc.uva.es/handle/10324/50935 LA eng NO Inorganic Chemistry, 2021, vol. 60, n. 24. p. 19206–19218 NO Producción Científica DS UVaDOC RD 12-jul-2024