Halides: Solid‐State ChemistryBased in part on the article Halides: Solid State Chemistry by Gordon J. Miller which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Abstract

This review on binary metal halides demonstrates their enormous richness of structural topologies as well as compositions. It emphasizes thermodynamic stabilities, influences of size and electronegativity effects, the intricate balance of ionic and covalent metal–halide and metal–metal interactions, and effects of excess valence electrons of atoms with nonclosed shells, in order to outline relationships of structure and bonding. The most important structure types of the main group metal halides are given and pressure effects are discussed. Selected examples show the influence of the stereochemical activity of lone pairs of electrons in reduced halides. Halides of the transition elements are discussed according to their empirical formulas in order to correlate structure and properties with d electron concentration at the metal atoms, which are based on typical Jahn‐Teller distortions or the formation of metal–metal bonded units. Finally, a summary of the rare earth element halides is given.