Proton-Rocking-Chair-Type Redox Capacitors Based on Indium Tin Oxide Electrodes with Multilayer Films Containing Ru Complexes

A rechargeable proton-rocking-chair-type redox capacitor was fabricated using scalable layer-by-layer-(LbL)-assembled films composed of two dinuclear Ru complexes that exhibit proton-coupled electron-transfer (PCET) reactions with different Ru(II/III) redox potentials (RuNH-OH and RuCH-OH). RuN-HOH and RuCH-OH contain different coordination environments that involve two phosphonate linker ligands at both ends and bridging 2,6,2',6'-tetrakis(benzimidazol-2-yl)-4,4'-bipyridine or 1,3,1',3'-tetrakis(benzimidazol-2-yl)-5,5'-biphenyl ligands, respectively. The molecular units were assembled onto indium tin oxide (ITO) electrodes by complexation between the phosphonate groups and zirconium(IV) ions. The LbL growing process of these multilayer films was monitored by electrochemical or UV-vis spectroscopic measurements. The thus obtained LbL films on the ITO electrodes showed PCET reactions at different potentials, depending on the bridging ligands. The introduction of cyclometalated RuC bonds in the bridging ligand of RuCH-OH led to the stabilization of the ruthenium(III) oxidation state, and therefore, RuCH-OH exhibited lower pK(a) values for the imino N-H protons in the bridging benzimidazole groups compared to those of the corresponding RuNH-OH complex. The proton movements that accompany the redox reaction in the Ru multilayer films on the ITO electrode were confirmed using a pH indicator probe. For the performance test of a proton-rocking-chair-type redox capacitor, a two-electrode system composed of RuNH-OH and RuCH-OH multilayer films on ITO electrodes was examined in an aqueous solution of NaClO4. Under galvanostatic conditions, stable, reversible, and repeatable charging/discharging processes occurred. The capacitance increased with an increasing number of LbL layers. For comparison, a similar redox capacitor composed of two RuNMe-OH and RuCMe-OH analogues, in which all four imino N-H protons on the benzimidazole moieties are protected by N-Me groups, was constructed and examined. In these complexes, the capacitance decreased by 77% compared to the PCET-type capacitor composed of a cell containing RuNH-OH and RuCH-OH; this result strongly suggests that the proton movement plays a more important role for the charge storage than the anion movement. In such LbL films composed of Ru complexes that exhibit PCET-type redox reactions, the capacitance is drastically improved with an increasing number of layers and using protons as charge carriers.