Structural Distortion by Alkali Metal Cations Modulates the Redox and Electronic Properties of Ce Imidophosphorane Complexes

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 Nov 3

PMID 37920331

Authors

Andrew C Boggiano

Chad M Studvick

Alexander Steiner

John Bacsa

Ivan A Popov

Henry S La Pierre

Affiliations

Soon will be listed here.

Abstract

A series of Ce complexes with counter cations ranging from Li to Cs are presented. Cyclic voltammetry data indicate a significant dependence of the oxidation potential on the alkali metal identity. Analysis of the single-crystal X-ray diffraction data indicates that the degree of structural distortion of the secondary coordination sphere is linearly correlated with the measured oxidation potential. Solution electronic absorption spectroscopy confirms that the structural distortion is reflected in the solution structure. Computational studies further validate this analysis, deciphering the impact of alkali metal cations on the Ce atomic orbital contributions, differences in energies of Ce-dominant molecular orbitals, energy shift of the 4f-5d electronic transitions, and degree of structural distortions. In sum, the structural impact of the alkali metal cation is demonstrated to modulate the redox and electronic properties of the Ce complexes, and provides insight into the rational tuning of the Ce imidophosphorane complex oxidation potential through alkali metal identity.

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