Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion. Issue 24 (21st March 2016)

• Record Type: Journal Article
• Authors: Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; Tomson, Neil C.; Anstey, Mitchell R.
• Is Part Of: Dalton transactions. Volume 45:Issue 24(2016)
• Page Start: 9962
• Page End: 9969
• Publication Date: 2016-03-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt00422a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Homoleptic bis(imino)acenaphthene complexes of aluminum, chromium, and gallium were synthesized, characterized and modeled to compare the orbital contributions of main group elements and transition metals in ligand-based redox events toward increasing energy density of battery electrolytes. Abstract : The redox-active bis(imino)acenapthene (BIAN) ligand was used to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3 M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.