Polychalcogen molecules, ligands, and ions Part 2: Catenated acyclic molecules, ions, and p-block element derivatives

Laitinen, Risto S.; Oilunkaniemi, Raija; Chivers, Tristram; McGeachie, Liam; Kelly, Paul F.; King, Roberto S.P.

doi:10.1016/b978-0-12-823144-9.00172-2

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“…•− (n = 2-8) play a pivotal role as intermediates in the sulfur ↔ sulfide redox cycle [1][2][3][4]. The influence of these short-lived species is frequently invoked in contemporary investigations of sulfur chemistry, including alkali-metal-sulfur batteries [5][6][7], organic syntheses [8], biological chemistry [9,10], geochemical processes involving metal transport [11][12][13] and quantum-dot sensitized solar cells [14,15].…”

Section: Polysulfide Radical Anions S Nmentioning

confidence: 99%

Structures and Spectroscopic Properties of Polysulfide Radical Anions: A Theoretical Perspective

Chivers

Oakley

2023

Molecules

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The potential involvement of polysulfide radical anions Sn•− is a recurring theme in discussions of the basic and applied chemistry of elemental sulfur. However, while the spectroscopic features for n = 2 and 3 are well-established, information on the structures and optical characteristics of the larger congeners (n = 4–8) is sparse. To aid identification of these ephemeral species we have performed PCM-corrected DFT calculations to establish the preferred geometries for Sn•− (n = 4–8) in the polar media in which they are typically generated. TD-DFT calculations were then used to determine the number, nature and energies of the electronic excitations possible for these species. Numerical reliability of the approach was tested by comparison of the predicted and experimental excitation energies found for S2•− and S3•−. The low-energy (near-IR) transitions found for the two acyclic isomers of S4•− (C2h and C2v symmetry) and for S5•− (Cs symmetry) can be understood by extension of the simple HMO π-only chain model that serves for S2•− and S3•−. By contrast, the excitations predicted for the quasi-cyclic structures Sn•− (n = 6–8) are better described in terms of σ → σ* processes within a localized 2c-3e manifold.

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