The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries

Abstract

The well-known tendency of sulfur to catenate is exemplified by an extensive series of polysulfide dianions [S_n]²⁻ (n = 2–9) and related radical monoanions [S_n]˙⁻. The dianions can be isolated as crystalline salts with appropriate cations and structurally and spectroscopically characterized. Although the smaller radical monoanions may be stabilized in zeolitic matrices, they are usually formed in solution via disproportionation or partial dissociation of the dianions as well as by electrochemical reduction of elemental sulfur. An understanding of the fundamental chemistry of these homoatomic species is key to unravelling their behaviour in a broad variety of chemical environments. This review will critically evaluate the techniques used to characterize polysulfide dianions and radical anions both in solution and in the solid state, i.e. Raman, UV-visible, EPR, NMR and X-ray absorption spectroscopy, X-ray crystallography, mass spectrometry, chromatography and high-level quantum-chemical calculations. This is followed by a discussion of recent advances in areas in which these anionic sulfur species play a crucial role, viz. alkali-metal–sulfur batteries, organic syntheses, biological chemistry, geochemical processes including metal transport, coordination complexes, atmospheric chemistry and materials science.