Isolation of kinetically-stabilised diarylchalcogenide radical cations

Abstract Chalcogenide radical cations [R2E]•+ (E = S, Se, Te) are commonly short-lived intermediates of fundamental interest. Sulfide radical cations in particular are associated in vivo with oxidative stress and neuropathological processes. Having succeeded in the preparation of meta-terphenyl-base...

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Main Authors: Pascal Komorr, Corina Stoian, Aleksa Radović, Björn A. Meyer, Pim Puylaert, George E. Cutsail III, Emanuel Hupf, Jens Beckmann
Format: Article
Language:English
Published: Nature Portfolio 2025-08-01
Series:Communications Chemistry
Online Access:https://doi.org/10.1038/s42004-025-01613-z
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author Pascal Komorr
Corina Stoian
Aleksa Radović
Björn A. Meyer
Pim Puylaert
George E. Cutsail III
Emanuel Hupf
Jens Beckmann
author_facet Pascal Komorr
Corina Stoian
Aleksa Radović
Björn A. Meyer
Pim Puylaert
George E. Cutsail III
Emanuel Hupf
Jens Beckmann
author_sort Pascal Komorr
collection DOAJ
description Abstract Chalcogenide radical cations [R2E]•+ (E = S, Se, Te) are commonly short-lived intermediates of fundamental interest. Sulfide radical cations in particular are associated in vivo with oxidative stress and neuropathological processes. Having succeeded in the preparation of meta-terphenyl-based dichalcogenide radical cations [R2E2]•+ (E = S, Se, Te), and a telluride analogue [R2Te]•+ in the past, we aimed to complete the series regarding sulfur and selenium. Here we report on the single-electron oxidation of diarylchalcogenides MSFluindPhE (E = S, Se, Te; MSFluind = dispiro[fluorene-9,3’-(1’,1’,7’,7’-tetramethyl-s-hydrindacen-4’-yl)-5’,9”-fluorene]) using XeF2 in the presence of K[B(C6F5)4], which afforded deeply coloured and isolable radical cation salts [MSFluindPhE][B(C6F5)4] (E = S, Se, Te). Structural and electronic properties were characterised by electron paramagnetic spectroscopy, cyclic voltammetry, optical absorption spectroscopy and single crystal X-ray diffraction (E = Se, Te), combined with extensive quantum mechanical computations.
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spelling doaj-art-aba4cff9d26b45eb8ca88b4524a87dbb2025-08-20T04:01:53ZengNature PortfolioCommunications Chemistry2399-36692025-08-01811810.1038/s42004-025-01613-zIsolation of kinetically-stabilised diarylchalcogenide radical cationsPascal Komorr0Corina Stoian1Aleksa Radović2Björn A. Meyer3Pim Puylaert4George E. Cutsail III5Emanuel Hupf6Jens Beckmann7Institute for Inorganic Chemistry and Crystallography, University of BremenInstitute for Inorganic Chemistry and Crystallography, University of BremenMax Planck Institute for Chemical Energy ConversionInstitute for Inorganic Chemistry and Crystallography, University of BremenInstitute for Inorganic Chemistry and Crystallography, University of BremenMax Planck Institute for Chemical Energy ConversionInstitute for Inorganic Chemistry and Crystallography, University of BremenInstitute for Inorganic Chemistry and Crystallography, University of BremenAbstract Chalcogenide radical cations [R2E]•+ (E = S, Se, Te) are commonly short-lived intermediates of fundamental interest. Sulfide radical cations in particular are associated in vivo with oxidative stress and neuropathological processes. Having succeeded in the preparation of meta-terphenyl-based dichalcogenide radical cations [R2E2]•+ (E = S, Se, Te), and a telluride analogue [R2Te]•+ in the past, we aimed to complete the series regarding sulfur and selenium. Here we report on the single-electron oxidation of diarylchalcogenides MSFluindPhE (E = S, Se, Te; MSFluind = dispiro[fluorene-9,3’-(1’,1’,7’,7’-tetramethyl-s-hydrindacen-4’-yl)-5’,9”-fluorene]) using XeF2 in the presence of K[B(C6F5)4], which afforded deeply coloured and isolable radical cation salts [MSFluindPhE][B(C6F5)4] (E = S, Se, Te). Structural and electronic properties were characterised by electron paramagnetic spectroscopy, cyclic voltammetry, optical absorption spectroscopy and single crystal X-ray diffraction (E = Se, Te), combined with extensive quantum mechanical computations.https://doi.org/10.1038/s42004-025-01613-z
spellingShingle Pascal Komorr
Corina Stoian
Aleksa Radović
Björn A. Meyer
Pim Puylaert
George E. Cutsail III
Emanuel Hupf
Jens Beckmann
Isolation of kinetically-stabilised diarylchalcogenide radical cations
Communications Chemistry
title Isolation of kinetically-stabilised diarylchalcogenide radical cations
title_full Isolation of kinetically-stabilised diarylchalcogenide radical cations
title_fullStr Isolation of kinetically-stabilised diarylchalcogenide radical cations
title_full_unstemmed Isolation of kinetically-stabilised diarylchalcogenide radical cations
title_short Isolation of kinetically-stabilised diarylchalcogenide radical cations
title_sort isolation of kinetically stabilised diarylchalcogenide radical cations
url https://doi.org/10.1038/s42004-025-01613-z
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