A ligand field series for the 4f-block from experimental and DFT computed Ce(IV/III) electrochemical potentials

Bogart, Justin A.Lewis, Andrew J.Boreen, Michael A.Lee, Heui BeomMedling, ScottCarroll, Patrick J.Booth, Corwin H.Schelter, Eric J.2016-06-140020-1669http://hdl.handle.net/1885/103048Understanding 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.A ligand field series for the 4f-block from experimental and DFT computed Ce(IV/III) electrochemical potentials201510.1021/ic503000z2016-06-14