RADICAL IONS 56<sup>1,2</sup>ONE-ELECTRON OXIDATION OF 1,2-DITHIETE DERIVATIVES

Bock, Hans; Rittmeyer, Peter; Krebs, Adolf; Schütz, A.; Voß, Jürgen; Köpke, Brigitte

doi:10.1080/03086648408077571

Cited by 23 publications

(8 citation statements)

References 16 publications

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“…In sulfur-based organic solids like, e.g., poly(bis-alkylthioacetylene) and poly(tetrathiafulvalene) in which electrons are localized mainly on the sulfur atom the effective g-factor of the PC is 2.014 ~< giso ~< 2.020 [52,[54][55][56][57].…”

Section: Magnetic Resonance Parameters Of Polarons In P30tmentioning

confidence: 99%

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

Krinichnyi

Roth

2004

Appl. Magn. Reson.

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An initial virgin plasticine-like poly(3-octylthiophene) (P3OT) and this sample modified by annealing and recrystallization were investigated at X-band (10 GHz) and mainly at D-band (140 GHz) electron paramagnetic resonance (EPR) in a wide temperature region. Paramagnetie centers with anisotropic magnetic-resonance parameters were proved to exist in all polymers, namely, mobile polarons whose concentration and susceptibility depend on the temperature and the polymer treatment. Superslow torsional motion of the polymer chains and layers was studied by the saturation transfer method at D-band EPR. Spin-spin and spin-lattice relaxation times were measured separately by the steady-state saturation method at the same waveband EPR. Intrachain and interchain spin diffusion coefficients and conductivity due to polaron dynamics were calculated. It was shown that the charge transport in P3OT is determined by the strong spin-spin interaction and is stimulated by torsion motion of the polymer chains. The total conductivity of P3OT is determined mainly by dynamics of paramagnetic charge carriers. Magnetic, relaxation and dynamics parameters of P3OT were also shown to change during the polymer treatment.

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Section: Magnetic Resonance Parameters Of Polarons In P30tmentioning

confidence: 99%

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

Krinichnyi

Roth

2004

Appl. Magn. Reson.

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“…This value seems to be too high for a sulfur containing radical. The average g-factor for the sample Iis in the range of the values for RCCSSSCCR and RCCS'SCCR cation radicals, 2.014 < (g) < 2.017 [2,10,11] but exceeds that of tetrathiafulvalene derivatives, 2.011 < (g) < 2.014 [12,13], in which an unpaired electron is localized near four central sulfur atoms of the TTF group. This additional circumstance confirms the supposition of the localization of non-interacting spins on the lateral trisulfur groups of the molecule I.…”

Section: Resultsmentioning

confidence: 99%

Spin relaxation and magnetic properties of benzo-1,2,3-trithiolium radical cations

et al. 1997

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Magnetic and dynamics properties of paramagnetic centers in various trithiolium cations were characterized by static magnetic susceptibility measurements and EPR spectroscopy. Magnetically correlated units consisting of at least pairs of spins with ferromagnetic exchange coupling were found in some trithioles. The rates of intramolecular spin diffusion and intermolecular spin hopping were estimated separately. The rates and the anisotropy (vJv• = 20-300) of spin dynamics were shown to depend on the molecular structure.

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“…Gegenüber dem durch 2F : ,CAkzeptorsubstituenten elektronisch stabilisierten 3,4-Bis(trifluormethyl)-l.2-dithiet mit IE, = 10.2 eV [9] sind ihre ersten Ionisierungsenergien auf 7.95 eV [9] erniedrigt, und sie können daher mit dem Sauerstoff-freien und selektiven Einelektronentransfer-Svstem A1C1 3 /H 2 CC1 2 , das in H 2 CC1 2 /0.1 M R 4 N®-Lö-sung ein Oxidationspotential von +1.6 V aufweist [10], in ihre Radikalkationen überführt werden [11] Die oxidative Schwefelung von rm-Butyl-acetylen (3) liefert über das ESR-spektroskopisch charakterisierte Dithiet-Radikalkation-Zwischenprodukt ein Gemisch der isomeren 2.3-und 2.6-Di(rm-butyl)-1.2-dithiin-Radikalkationen [7], welches unter gleichen Bedingungen auch aus isoliertem 2.5-Di(rmbutyl)-l,2-dithiin erhalten wird [7]: Die ferr-ButylGruppen können somit AlCl 3 -katalysiert wandern.…”

Section: Das Unsubstituierteunclassified

“…2: @>) Rotation der Methylthio-Gruppen um die SC-Bindungen zur C-C-Einheit zurückzuführen [19], Im Konformeren-Gleichgewicht (Abb. 2: (g)) wird für das 'H-Tridezett eine Kopplungskonstante an N1° = 0,28 mT berechnet [11,20] …”

Section: Das Unsubstituierteunclassified

Radikalionen, 79 [1, 2] ESR-Nachweis von Tetra(methylthio)thiophen- und Tetra(methylthio)ethen-Radikalkationen bei der oxidativen Schwefelung von H₃CS-C=C-SCH₃ mit S₂Cl₂/AlCl₃ und H₃CSCl/AlCl₃ / Radical Ions, 79 [1, 2] ESR Evidence for Tetra(methylthio)thiophene and Tetra(methylthio)ethene Radical Cations During the Oxidative Sulfuration of H₃CS-C=C-SCH₃ by S₂Cl₂/AlCl₃ and H
Bock
¹
,
Rittmeyer
²

1988
Zeitschrift Für Naturforschung B
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AbstractDi(methylthio)acetylene H3CS-C≡C-SCH3 reacts with S2C12 in AlCl3/H2CCl2 solution to the tetra(thiomethyl)thiophene radical cation (H3CS)4C4S·⊕ and with H3CSCl to the tetra(thiomethyl)ethene radical cation (H3CS)2C·=⊕C(SCH3)3. Their ESR spectra are assigned by comparison with literature data or those of analogous products obtained from other acetylene derivatives R-C≡C-R with R = SCH2CH3, CH3, C6H5 as well as based on HMO arguments. The possible course of the oxidative sulfuration is discussed.

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RADICAL IONS 56^1,2ONE-ELECTRON OXIDATION OF 1,2-DITHIETE DERIVATIVES

Cited by 23 publications

References 16 publications

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

Spin relaxation and magnetic properties of benzo-1,2,3-trithiolium radical cations

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RADICAL IONS 561,2ONE-ELECTRON OXIDATION OF 1,2-DITHIETE DERIVATIVES

Cited by 23 publications

References 16 publications

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

EPR study of spin and charge dynamics in slightly doped poly(3-octylthiophene)

Spin relaxation and magnetic properties of benzo-1,2,3-trithiolium radical cations

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Product

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RADICAL IONS 56^1,2ONE-ELECTRON OXIDATION OF 1,2-DITHIETE DERIVATIVES