Intervalence Charge Transfer in Nonbonding, Mixed-Valence, Homobimetallic Ytterbium Complexes.


Roy, Michael D ORCID: 0000-0002-4613-9361, Gompa, Thaige P, Greer, Samuel M ORCID: 0000-0001-8225-3252, Jiang, Ningxin, Nassar, Lila S, Steiner, Alexander ORCID: 0000-0002-4315-6123, Bacsa, John ORCID: 0000-0001-5681-4458, Stein, Benjamin W ORCID: 0000-0002-0366-5476 and La Pierre, Henry S ORCID: 0000-0002-0895-0655 (2024) Intervalence Charge Transfer in Nonbonding, Mixed-Valence, Homobimetallic Ytterbium Complexes. Journal of the American Chemical Society, 146 (8). pp. 5560-5568.

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Abstract

There are several reports of compounds containing lanthanide ions in two different formal oxidation states; however, there are strikingly few examples of intervalence charge transfer (IVCT) transitions observed for these complexes, with those few occurrences limited to extended solids rather than molecular species. Herein, we report the synthesis, characterization, and computational analysis for a series of ytterbium complexes including a mixed-valence Yb<sub>2</sub><sup>5+</sup> complex featuring a remarkably short Yb···Yb distance of 2.9507(8) Å. In contrast to recent reports of short Ln···Ln distances attributed to bonding through 5<i>d</i> orbitals, the formally Yb<sub>2</sub><sup>5+</sup> complex presented here displays clear localization of Ln<sup>2+</sup> and Ln<sup>3+</sup> character and yet still displays an IVCT in the visible spectrum. These results demonstrate the ability to tune the electronic structure of formally mixed oxidation state lanthanide complexes: the high exchange stabilization of the Yb<sup>2+</sup> 4<i>f</i><sup>14</sup> configuration disfavors the formation of a 5<i>d</i><sup>1</sup> bonding configuration, and the short metal-metal distance enforced by the ligand framework allows for the first observed lanthanide IVCT in a molecular system.

Item Type: Article
Divisions: Faculty of Science and Engineering > School of Physical Sciences
Depositing User: Symplectic Admin
Date Deposited: 20 Feb 2024 15:58
Last Modified: 15 Mar 2024 19:47
DOI: 10.1021/jacs.3c13906
Open Access URL: https://doi.org/10.1021/jacs.3c13906
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URI: https://livrepository.liverpool.ac.uk/id/eprint/3178825
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