Computational Investigation of Vicinal Disulfoxides and Other Sulfinyl Radical Dimers

Gregory, Daniel D.; Jenks, William S.

doi:10.1021/jp026888q

Cited by 27 publications

(19 citation statements)

References 57 publications

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“…The cyclic compounds (1, 3, 5, and 7) are more stable than the acyclic analogues (2, 4, 6, and 8) at all the oxidation stages, but the oxide derivatives (3, 5, and 7) have weaker disulfide (SAS) bonds than 1,2-dithiolane (1) ], as suggested from a related work [51].…”

Section: Gas-phase 12-dithiolane and Its Oxide Derivativesmentioning

confidence: 71%

A DFT study on molecular junction devices with cyclic disulfide anchors: Effect of anchor oxidation on electron transport

Jang

2010

Int J of Quantum Chemistry

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A molecular-scale electronic device can be built with programmable molecular switches sandwiched between two electrodes. A cyclic disulfide, 1,2-dithiolane, is a promising anchor group for attaching molecules to gold electrodes in such molecular junction devices, since its dithiol-Au linkage (with the disulfide bond broken) can provide added stabilities and reduced current fluctuations. However, operations of the molecular switches under redox conditions might lead to redox processes involving the AuAS bonds at the contact. Formation of the disulfide linkage can be induced, and the dithiolate group (AuS) can be converted into disulfoxide (AuSO) or disulfone (AuSO 2 ) groups. Coexistence of these various oxidation states at the contact or the conversion between them can be a potential source of current fluctuation in the junction. However, our nonequilibrium Green's function calculations combined with the density functional theory show that the molecular junctions with different oxidation states of the 1,2-dithiolane alligator clips to two gold electrodes exhibit essentially the same insulating current-voltage characteristics at moderate bias voltages. Therefore, the robustness of the molecular junctions would not be affected by the state change of the disulfide alligator clips at the contact.

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Section: Gas-phase 12-dithiolane and Its Oxide Derivativesmentioning

confidence: 71%

A DFT study on molecular junction devices with cyclic disulfide anchors: Effect of anchor oxidation on electron transport

Jang

2010

Int J of Quantum Chemistry

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“…However, it is known that the energies of sulfoxides and other oxides of sulfur are significantly overestimated relative to their isomers in the absence of tight d-polarization functions. 15,[35][36][37][38][39][40][41][42][43][44][45][46][47] Thus, use of a larger basis set, such as the aug-cc-pVT(T+d)Z, is highly desirable. However, the correlation consistent basis sets are sufficiently large to make this very costly.…”

Section: Methodsmentioning

confidence: 99%

Computational investigation of the photochemical deoxygenation of thiophene- S-oxide and selenophene- Se-oxide

Stoffregen

Lee

Dickerson

et al. 2014

Photochem Photobiol Sci

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CASSCF and multireference MP2 calculations were carried out on thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO), comparing the energies of the ground state to the first two electronically excited singlet and triplet states, using constrained optimizations and multiple fixed S-O or Se-O distances. For both molecules, one of the two triplet states smoothly dissociates to yield O((3)P) with little or no barrier. Single point calculations are consistent with the same phenomenon occurring for dibenzothiophene-S-oxide (DBTO). This provides an explanation for the inefficient unimolecular photochemical dissociation of O((3)P) from DBTO despite a phosphorescence energy below that of S-O dissociation, i.e., that S-O scission probably occurs from a spectroscopically unobserved triplet (T2) state.

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“…[8] The sulfinyl radicals rapidly recombine in a "head-to-tail" manner to form O,S-sulfenyl sulfinates (again rarely observed [3] ), which subsequently rearrange to the thermally more stable thiosulfonate (Scheme 1). This propensity for dissociation is reflected in the longer S À S bond length of vic-disulfoxides compared with disulfides, thiosulfinates, or thiosulfonates.…”

Section: Richard S Grainger* Bhaven Patel and Benson M Kariukimentioning

confidence: 99%

2,7‐Di‐tert‐butylnaphtho[1,8‐cd][1,2]dithiole 1,2‐dioxides: Thermally Stable, Photochemically Active vic‐Disulfoxides

2009

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Temperaturstabil dank tert‐Butyl: Die thermische Barriere für die Umlagerung eines vic‐Disulfoxids wird durch die Gegenwart sperriger tert‐Butylgruppen in ortho‐Stellung zu den S‐Atomen deutlich erhöht. Dies macht die Titelverbindungen zu den bisher thermisch stabilsten vic‐Disulfoxiden, allerdings gehen sie bei Raumtemperatur eine neuartige Photoepimerisierung ein (siehe Schema).magnified image

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Computational Investigation of Vicinal Disulfoxides and Other Sulfinyl Radical Dimers

Cited by 27 publications

References 57 publications

A DFT study on molecular junction devices with cyclic disulfide anchors: Effect of anchor oxidation on electron transport

A DFT study on molecular junction devices with cyclic disulfide anchors: Effect of anchor oxidation on electron transport

Computational investigation of the photochemical deoxygenation of thiophene- S-oxide and selenophene- Se-oxide

2,7‐Di‐tert‐butylnaphtho[1,8‐cd][1,2]dithiole 1,2‐dioxides: Thermally Stable, Photochemically Active vic‐Disulfoxides

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