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

Boggiano, Andrew C, Studvick, Chad M, Steiner, Alexander, Bacsa, John, Popov, Ivan A and La Pierre, Henry S (2023) Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce3+ imidophosphorane complexes Chemical Science, 14 (42). pp. 11708-11717.

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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.

Item Type:	Article
Uncontrolled Keywords:	3402 Inorganic Chemistry, 34 Chemical Sciences
Divisions:	Faculty of Science & Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	02 Nov 2023 08:49
Last Modified:	20 Jun 2024 17:06
DOI:	10.1039/d3sc04262f
Open Access URL:	https://pubs.rsc.org/en/content/articlelanding/202...
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3176569
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