N,N'-diaryl-sulfurdiimides are strongly redox tuned

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dc.contributor.authorHill, Nathan D. D.
dc.contributor.authorBoeré, René T.
dc.date.accessioned2024-06-04T20:21:26Z
dc.date.available2024-06-04T20:21:26Z
dc.date.issued2024
dc.descriptionOpen access article. Creative Commons Attribution 4.0 International license (CC BY 4.0 DEED) applies
dc.description.abstractThe synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar−NSN−Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron-donating and -withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long-standing contention of the solution-state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High-quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H-atoms with accurate C−H bond lengths.
dc.description.peer-reviewYes
dc.identifier.citationHill, N. D. D., & Boeré, R. T. (2024). N,N'-diaryl-sulfurdiimides are strongly redox tuned. Chemistry-A European Journal,30(26), Article e202400563. https://doi.org/10.1002/chem.202400563
dc.identifier.urihttps://hdl.handle.net/10133/6774
dc.language.isoen
dc.publisherWiley
dc.publisher.departmentDepartment of Chemistry and Biochemistry
dc.publisher.facultyArts and Science
dc.publisher.institutionUniversity of Lethbridge
dc.publisher.urlhttps://doi.org/10.1002/chem.202400563
dc.subjectThiazyl chemistry
dc.subjectElectrochemistry
dc.subjectChemical synthesis
dc.subjectEPR spectroelectrochemistry
dc.subjectDFT computation
dc.subjectSC-XRD structure determination
dc.subjectInfrared spectroscopy
dc.subjectUV-vis spectroscopy
dc.subject.lcshUltraviolet-visible action spectroscopy
dc.titleN,N'-diaryl-sulfurdiimides are strongly redox tuned
dc.typeArticle
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