Anodic oxidation of diarylacetylenes and diaryldiacetylenes: electrosynthesis of diaroyl-stilbenes and acetylenic α-and γ -diketones

Cariou, M.

doi:10.1016/s0040-4020(01)87069-1

Cited by 16 publications

(3 citation statements)

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“…The subsequently formed neutral radical then adds to solvent molecules or parent phenylacetylenes finally leading to stilbene derivatives. 24 Such reactivity patterns are very likely the reason for the unexpectedly irreversible shape of the cyclovoltammograms of 1 and 2 where rearrangements have already taken place before the expected Wurster-type radical cation can be formed at amounts detectable for cyclovoltammetry.…”

Section: Resultsmentioning

confidence: 99%

“…It has been reported that arylacetylenes, when oxidized in rigorously dried solvents and under inert conditions, react with even minute traces of moisture and undergo rapid addition of OH – to one of the acetylenic carbon atoms. The subsequently formed neutral radical then adds to solvent molecules or parent phenylacetylenes finally leading to stilbene derivatives . Such reactivity patterns are very likely the reason for the unexpectedly irreversible shape of the cyclovoltammograms of 1 and 2 where rearrangements have already taken place before the expected Wurster-type radical cation can be formed at amounts detectable for cyclovoltammetry.…”

Section: Resultsmentioning

confidence: 99%

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Donor-Substituted Diphenylacetylene Derivatives Act as Electron Donors and Acceptors

et al. 2011

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Despite the predominant electron donor character of p-phenylenediamine, our studies on extended p-phenylenediamine derivatives show that they can not only be chemically oxidized, giving well-known Wurster-type radical cations, but also be chemically reduced, giving radical anions. Making use of EPR/ENDOR spectroscopy and supported by DFT calculations, we were able to reveal the extent of π-electron delocalization in the paramagnetic species and to shed light onto the geometry and bond lengths. While for the radical anions spin was found to be mostly delocalized into the π-system, the radical cations can be described as essentially N-centered. Furthermore, we performed electrochemical characterizations using cyclic voltammetry to gain insight into the thermodynamics of the redox processes. The photophysical properties of the parent extended p-phenylenediamine were investigated by absorption, emission, and excitation spectroscopy. The fluorescence quantum yield and the excited-state lifetime of the neutral precursors in hexane and acetonitrile were determined to establish elementary differences originating from solvent effects.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%