Molecular Structures and Electronic Transitions of 3,6-Diphenyl-1,2-dithiin and Its Radical Cation:  A Spectroelectrochemical and DFT Study

Hennig, H.; Schumer, Frank; Reinhold, J.; Kaden, Heiner; Oelßner, Wolfram; Schroth, Werner; Spitzner, R.; Hartl, František

doi:10.1021/jp0551059

Cited by 15 publications

(5 citation statements)

References 27 publications

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“…Hence, it has been used to study the electron spectra of numerous systems including closed-shell and open-shell systems. The accuracy and reliability of spin-unrestricted time-dependent density functional theory for open-shell systems have been tested by studying both the organic and transition mental compounds [39][40][41][42][43][44][45][46][47][48]. The ground states of these systems studied here have only one unpaired electron and thus doublet states.…”

Section: Methodsmentioning

confidence: 99%

Theoretical investigation of structures, electronic spectra and nonlinear optical properties of gold-pentacene (Au2C22H14) complexes

Sun

Qin

Qiu

et al. 2009

Journal of Organometallic Chemistry

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Section: Methodsmentioning

confidence: 99%

Theoretical investigation of structures, electronic spectra and nonlinear optical properties of gold-pentacene (Au2C22H14) complexes

Sun

Qin

Qiu

et al. 2009

Journal of Organometallic Chemistry

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“…Compounds 1 and 2 2+ are 1,2-dithiins. The electrochemistry of a number of other 1,2-dithiins has been investigated, − but those studies have emphasized oxidations, while the current study will focus on the reduction of these compounds and cleavage of the S–S bond. The reductions of 1 and 2 2+ are of particular interest because they can be viewed as having two sites for reduction: the bipyridine/bipyridinium and disulfide moieties which may interact with each other.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Electron Transfer in Bipyridinium Disulfides

et al. 2014

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Reductive cleavage of disulfide bonds is an important step in many biological and chemical processes. Whether cleavage occurs stepwise or concertedly with electron transfer is of interest. Also of interest is whether the disulfide bond is reduced directly by intermolecular electron transfer from an external reducing agent or mediated intramolecularly by internal electron transfer from another redox-active moiety elsewhere within the molecule. The electrochemical reductions of 4,4'-bipyridyl-3,3'-disulfide (1) and the di-N-methylated derivative (2(2+)) have been studied in acetonitrile. Simulations of the cyclic voltammograms in combination with DFT (density functional theory) computations provide a consistent model of the reductive processes. Compound 1 undergoes reduction directly at the disulfide moiety with a substantially more negative potential for the first electron than for the second electron, resulting in an overall two-electron reduction and rapid cleavage of the S-S bond to form the dithiolate. In contrast, compound 2(2+) is reduced at less negative potential than 1 and at the dimethyl bipyridinium moiety rather than at the disulfide moiety. Most interesting, the second reduction of the bipyridinium moiety results in a fast and reversible intramolecular two-electron transfer to reduce the disulfide moiety and form the dithiolate. Thus, the redox-active bipyridinium moiety provides a low energy pathway for reductive cleavage of the S-S bond that avoids the highly negative potential for the first direct electron reduction. Following the intramolecular two-electron transfer and cleavage of the S-S bond the bipyridinium undergoes two additional reversible reductions at more negative potentials.

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“…It has been found that various types of six membered 1,4-dihydroheterocycles posses a high conformational flexibility using ab initio calculation [6]. Among cyclohexadiene, the dithiine and its derivatives have extensively been studied [7][8][9][10]. In follow up on our works [11][12][13], we are especially interested to study of optimized conformations of 1,4-dithiine and S-oxygenated derivatives.…”

Section: Introductionmentioning

confidence: 99%