title: Structural and Substituent Group Effects on Multielectron Standard Reduction Potentials of Aromatic N-Heterocycles.
abstract: Aromatic N-heterocycles have been used in electrochemical CO2 reduction, but their precise role is not yet fully understood. We used first-principles quantum chemistry to determine how the molecular sizes and substituent groups of these molecules affect their standard redox potentials involving various proton and electron transfers. We then use that data to generate molecular Pourbaix diagrams to find the electrochemical conditions at which the aromatic N-heterocycle molecules could participate in multiproton and electron shuttling in accordance with the Sabatier principle. While one-electron standard redox potentials for aromatic N-heterocycles can vary significantly with molecule size and the presence of substituent groups, the two-electron and two-proton standard redox potentials depend much less on structural modifications and substituent groups. This indicates that a wide variety of aromatic N-heterocycles can participate in proton, electron, and/or hydride shuttling under suitable electrochemical conditions.
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Mitchell C
authors.initials: MC
authors.lastname: Groenenboom
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Karthikeyan
authors.initials: K
authors.lastname: Saravanan
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Yaqun
authors.initials: Y
authors.lastname: Zhu
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Jeffrey M
authors.initials: JM
authors.lastname: Carr
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: Aude
authors.initials: A
authors.lastname: Marjolin
authors.affiliation: Department of Chemistry, University of Richmond , Richmond, Virginia 23173, United States.
authors.forename: Gabriel G
authors.initials: GG
authors.lastname: Faura
authors.affiliation: Department of Chemistry, University of Richmond , Richmond, Virginia 23173, United States.
authors.forename: Eric C
authors.initials: EC
authors.lastname: Yu
authors.affiliation: Department of Chemistry, University of Richmond , Richmond, Virginia 23173, United States.
authors.forename: Raymond N
authors.initials: RN
authors.lastname: Dominey
authors.affiliation: Department of Chemical and Petroleum Engineering, University of Pittsburgh , Pittsburgh, Pennsylvania 15261, United States.
authors.forename: John A
authors.initials: JA
authors.lastname: Keith