Polynuclear halide complexes of Bi(III): From structural diversity to the new properties

•The diversity of structural types of Bi(III) halide complexes is described.•The impact of different parameters on the synthetic routes is discussed.•Several interesting physical properties, related to the materials science, are highlighted.

This review is focused on the chemistry of polynuclear halide complexes of Bi(III) (polyhalidebismuthates, or PHBs). It consists of three parts. The first one is dedicated to the known structural types of PHBs (discrete Bi(III) complexes, coordination polymers and heterometallic compounds), their features and occurrence. The second chapter briefly describes what can be called chemistry of PHBs (synthetic approaches by which they can be obtained, and some reactions they can be involved in). The final, third part is focused on the physical properties of PHBs reported recently, which would be of a special interest for the chemical community.