Chalcogen controlled redox behaviour in peri-substituted S, Se and Te naphthalene derivatives

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dc.contributor.authorRoemmele, Tracey L.
dc.contributor.authorKnight, Fergus R.
dc.contributor.authorCrawford, Ellis
dc.contributor.authorRobertson, Stuart D.
dc.contributor.authorBode, Bela E.
dc.contributor.authorBühl, MIchael
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorWoollins, J. Derek
dc.contributor.authorBoeré, René T.
dc.date.accessioned2024-07-12T21:15:16Z
dc.date.available2024-07-12T21:15:16Z
dc.date.issued2022
dc.descriptionAccepted author manuscript.
dc.description.abstractCyclic and square wave voltammetry of (PhE)2peri-disubstituted naphthalene[1,8-cd]dichalcoganyls and acenaphthene[5,6-diyl]dichalcoganyls (E = S, Se, Te, 12 compounds) is reported. Mixed (E1 = Se, Te; E2 = Br, I) naphthalene[1,8-cd]halochalcoganyls were also investigated, as well as an exemplar bearing two PhS([double bond, length as m-dash]O) groups and another bearing one PhSe and one Ph2P([double bond, length as m-dash]S) substituent. The voltammetry, in CH2Cl2/0.4 M [nBu4N][PF6] at both platinum and glassy carbon macro-disk working electrodes, shows two sequential chemically reversible and electrochemically quasi-reversible oxidation processes, and the lack of accessible reductions. Additional oxidations above +1.5 V vs. Fc+/0 have not been investigated in detail. In situ and ex situ EPR spectroscopy conclusively demonstrate that both anodic processes are 1e transfers; persistent radical cations could be generated for all the dichalcoganyls except when E1 = E2 = Te; for the latter case thermally stable dications are generated instead. The complex possible solution conformations of these compounds in 0, +1 and +2 charge states were modelled with DFT at the B3LYP-D3(BJ)/6-31+G(d) level of theory in a CH2Cl2 PCM continuum solution model and adiabatic ionisation energies calculated, which correlate linearly (R = 0.88) with the Ea1p values. Crystal structures of four solvolysis and hydrolysis products of the ditellurium dications are reported and were modelled computationally. Interpretative comparisons to unsubstituted naphthalene[1,8-cd]dichalcogenoles are reported and the crystal structure of naphtho(1,8-cd)(1,2-dithiolium) tetrafluoroborate has been obtained. This is the first structure reported for any salt of this cation radical. Electron transfer mechanisms of both the (PhE)2 and E2peri-disubstituted naphthalene series are correlated using a redox molecular orbital interpretative framework.
dc.description.peer-reviewYes
dc.identifier.citationRoemmele, T. L., Knight, F. R., Crawford, E., Robertson, S. D., Bode, B. E., Bühl, M., Slawin, A. M. Z., Woollins, J. D., & Boeré, R. T. (2022). Chalcogen controlled redox behaviour in peri-substituted S, Se and Te naphthalene derivatives. New Journal of Chemistry, 46, 22363-22383. https://doi.org/10.1039/D2NJ04737C
dc.identifier.urihttps://hdl.handle.net/10133/6821
dc.language.isoen
dc.publisherRSC Publishing
dc.publisher.departmentDepartment of Chemistry and Biochemistry
dc.publisher.facultyArts and Science
dc.publisher.institutionUniversity of Lethbridge
dc.publisher.institutionUniversity of St. Andrews
dc.publisher.institutionUniversity of Strathclyde
dc.publisher.institutionKhalifa University
dc.publisher.urlhttps://doi.org/10.1039/D2NJ04737C
dc.subjectChalcogen
dc.subjectNaphthalene
dc.subjectRedox behavior
dc.subjectPeri-interactions
dc.subjectOxidation
dc.subjectVoltammetry
dc.titleChalcogen controlled redox behaviour in peri-substituted S, Se and Te naphthalene derivatives
dc.typeArticle
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