Issue 42, 2023

Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce3+ imidophosphorane complexes

Abstract

A series of Ce3+ 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 Ce3+ complexes, and provides insight into the rational tuning of the Ce3+ imidophosphorane complex oxidation potential through alkali metal identity.

Graphical abstract: Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce3+ imidophosphorane complexes

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Article information

Article type
Edge Article
Submitted
14 8 2023
Accepted
15 9 2023
First published
25 9 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 11708-11717

Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce3+ imidophosphorane complexes

A. C. Boggiano, C. M. Studvick, A. Steiner, J. Bacsa, I. A. Popov and H. S. La Pierre, Chem. Sci., 2023, 14, 11708 DOI: 10.1039/D3SC04262F

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