This paper describes experiments exploring the role of the redox-inactive counterion in hybrid redox polyether molten salts. Because these materials are undiluted, they intrinsically contain "solvent-separated ion pairs", where the "solvent" is the polyether tail attached to the redox moiety. Measurements on molten salts with polyether-derivatized Co(II) tris(bipyridine) cations show that stronger forms of ionic association can occur between the complex and its counterion, leading in the case of triflate counterion to additional voltammetric waves. The rate of conversion between differently associated Co(II) complexes in the molten salt is sluggish. Ion-association equilibria exist between Co(II) and Fe(II) tris(bipyridine) cations and their perchlorate or triflate counterions even in dilute dimethoxyethane solutions, as shown by solubility and microelectrode voltammetry.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry