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Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes
journal contribution
posted on 2021-12-09, 21:16 authored by Álvaro García-Romero, Jose M. Martín-Álvarez, Daniel Miguel, Dominic S. Wright, Celedonio M. Álvarez, Raúl García-RodríguezThe 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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