Bromine-rich complexes of bismuth: experimental and theoretical studies

Three novel polybromide complexes of bismuth(III) - (2,6-MePyH)(3)[BiBr5(Br-3)] (1), (H(2)bpp){[BiBr5](Br-2)} (2) and (3-ClPyH)(2){[BiBr5](Br-2)} (3) - were synthesized. The results of an extended screening involving a set of organic cations resulting in the formation/non-formation of Bi(III) polybromides are presented and discussed. The nature of Br center dot center dot center dot Br interactions in Bi(III) polybromides was investigated by theoretical methods, enabling the estimation of their energies.