title: A ligand field series for the 4f-block from experimental and DFT computed Ce(IV/III) electrochemical potentials.
abstract: Understanding of the sensitivity of the reduction potential of cerium(IV) cations to ligand field strength has yet to benefit from systematic variation of the ligand environment. Detailed analyses for a series of seven cerium(IV) tetrakis(pyridyl-nitroxide) compounds and their cerium(III) analogues in varying ligand field strengths are presented. Electrochemical, spectroscopic, and computational results reveal a close correlation of electronic properties with ligand substituents. Together with electrochemical data for reported eight-coordinate compounds, DFT calculations reveal a broad range of the cerium(IV/III) redox potentials correlated to ligand field strengths, establishing a semiempirical, predictive model for the modulation of cerium redox thermodynamics and ligand field strengths. Applications over a variety of scientific disciplines make use of the fundamental redox thermodynamics of cerium. Such applications will benefit from a combined experimental and theoretical approach for assessing redox cycling of cerium compounds.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Justin A
authors.initials: JA
authors.lastname: Bogart
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Lewis
authors.forename: Michael A
authors.initials: MA
authors.lastname: Boreen
authors.forename: Heui Beom
authors.initials: HB
authors.lastname: Lee
authors.forename: Scott A
authors.initials: SA
authors.lastname: Medling
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.forename: Corwin H
authors.initials: CH
authors.lastname: Booth
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter