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Substrate-Dependent Electron-Transfer Rate of Mixed-Ligand Electrolytes: Tuning Electron-Transfer Rate without Changing Driving Force

Journal Article


Abstract


  • To meet various requirements for electron transfer (ET) at the substrate/electrolyte interface, mixed redox couples assigned to different functions have been applied. While in all studies the mixed redox species had different redox potentials, such redox systems inherently lose energy by ET between the species. We report interfacial ET kinetics employing mixed-ligand electrolytes based on Co2+/3+ complexes with mixtures of dimethyl- and dinonyl-substituted bipyridyl (bpy) ligands with the same redox potential. The ET rates of the mixed electrolytes decrease with the increasing ratio of the dinonyl-bpy ligand, with substrates adsorbed by molecules without alkyl chains due to a blocking effect. However, when the molecules on substrates have four alkyl chains, the ET rate between the molecules and the electrolytes with increasing ratio of the dinonyl-bpy ligand is enhanced. The substrate-dependent behavior is explained by selective intermolecular interactions. The results open design flexibility for mixed-redox electrolyte systems to control ET at multi-substrate interfaces and provide a novel means to tune ET rates simultaneously for various ET processes in a system without losing energy by the ET.

Publication Date


  • 2021

Citation


  • Cho, I., Wagner, P., Innis, P. C., Mori, S., & Mozer, A. J. (2021). Substrate-Dependent Electron-Transfer Rate of Mixed-Ligand Electrolytes: Tuning Electron-Transfer Rate without Changing Driving Force. Journal of the American Chemical Society, 143(1), 488-495. doi:10.1021/jacs.0c12050

Scopus Eid


  • 2-s2.0-85099084138

Start Page


  • 488

End Page


  • 495

Volume


  • 143

Issue


  • 1

Abstract


  • To meet various requirements for electron transfer (ET) at the substrate/electrolyte interface, mixed redox couples assigned to different functions have been applied. While in all studies the mixed redox species had different redox potentials, such redox systems inherently lose energy by ET between the species. We report interfacial ET kinetics employing mixed-ligand electrolytes based on Co2+/3+ complexes with mixtures of dimethyl- and dinonyl-substituted bipyridyl (bpy) ligands with the same redox potential. The ET rates of the mixed electrolytes decrease with the increasing ratio of the dinonyl-bpy ligand, with substrates adsorbed by molecules without alkyl chains due to a blocking effect. However, when the molecules on substrates have four alkyl chains, the ET rate between the molecules and the electrolytes with increasing ratio of the dinonyl-bpy ligand is enhanced. The substrate-dependent behavior is explained by selective intermolecular interactions. The results open design flexibility for mixed-redox electrolyte systems to control ET at multi-substrate interfaces and provide a novel means to tune ET rates simultaneously for various ET processes in a system without losing energy by the ET.

Publication Date


  • 2021

Citation


  • Cho, I., Wagner, P., Innis, P. C., Mori, S., & Mozer, A. J. (2021). Substrate-Dependent Electron-Transfer Rate of Mixed-Ligand Electrolytes: Tuning Electron-Transfer Rate without Changing Driving Force. Journal of the American Chemical Society, 143(1), 488-495. doi:10.1021/jacs.0c12050

Scopus Eid


  • 2-s2.0-85099084138

Start Page


  • 488

End Page


  • 495

Volume


  • 143

Issue


  • 1