Electrochemical evidence for the existence of three stable oxidation states for heterocycles of the type XC₆H₄CN₂E₂ (E = S, Se). X‐ray crystal structure of the dimer with X = Cl, E = S

Abstract

The preparation and isolation in the solid state of five aryl 1,2,3,5‐dithia‐ and diselenadiazolyls is reported. The structure of the dimer of 4‐ClC6H4CN2S2 in the solid state was obtained: monoclinic, C2/c with Z = 8, a = 20.982(10), b = 10.058(3), c = 15.867(6) Å, β = 93.34(4)°, R = 0.066, Rw = 0.053 for 1 099 data. Cyclic voltammetry shows reversible oxidation to a 6π cation for all 10 compounds in both CH2Cl2 and CH3CN; reversible reduction to an 8π anion is observed in CH2Cl2 for all except X = CF3, E = S. The reductions are only quasi‐reversible in CH3CN for E = Se. The oxidation process is independent of chalcogen type; the reduction process is found to be about 0.2 V more negative for E = S vs E = Se.

Synthesis, properties and crystal structural characterization of diorganotin(IV) derivatives of 2‐mercapto‐6‐nitrobenzothiazole

“…interactions have been investigated for characterization of the molecular structures of a large number of organosulfur compounds, 26 but we have seen little discussion about the Cl· · ·S interaction. In the represented crystalline structure of complex 1, a relatively close contact (3.42, 3.51Å for A and 3.44, 3.56Å for B) between chlorine and sulfur atoms was recognized, which coincides well with that reported in (Ph 2 CH 2 ) 2 SnClS 2 CNC 4 H 8 O 27 and is much shorter than the sum of the van der Waals radii (3.97Å 28 ) for these atoms. And it is the intra-molecular non-bonded Cl· · ·S interaction that favoured the formation of the polymer of complex 1.…”

1,2,4,6-Thiatriazinyls: Stable Free Radicals With Well-Defined Epr Spectra

“…2, 3 We recently have summarized the known electrochemical data on thiazyl compounds, 4 and extensively have investigated 1,2,3,5-dithiadiazolyl radicals, including their characterization by EPR spectroscopy. 5 Much less is known about the sixmembered ring thiatriazinyl system. Kaszinsky has reported recently on a second isomer, but it does not form a stable free radical.…”

Oligothiophene‐Functionalized Benzene and Tetrathienoanthracene: Effect of Enhanced π‐Conjugation on Optoelectronic Properties, Self‐Assembly and Device Performance

“… [b] In CH 2 Cl 2 , 0.1 M n Bu 4 NPF 6 as supporting electrolyte, referenced to the Fc/Fc + couple of ferrocene at +0.48 V vs. SCE 20…”