Thallium(III) trifluoroacetate-trifluoroacetic acid in the chemistry of polythiophenes .2. Treatment of 3-alkylthiophenes and electron paramagnetic resonance results

The treatment of thiophene and 3-alkylthiophenes with thallium(III) trifluoroacetate (TTFA) in trifluoroacetic acid (TFA) gives insoluble and dark powdery solids with oxygen content and electrical conductivities ranging from 10(-4) to 10(-6) Omega(-1) cm(-1). Polar and short fractions are negligible. All of them show semiconductivity (10(-3)-10(-6) Omega(-1) cm(-1)) when doped in iodine atmosphere. Electron paramagnetic resonance (EPR) spectra of either as-synthesized or I-2-treated solids display characteristic single and broad lines (Delta H-pp, 1.84-7.4 G) with Lorentzian shapes and g-values in the range 2.0028-2.0038. Infrared spectra show characteristic C-H out-of-plane deformations (780 cm(-1) for polythiophene and 820-825 cm(-1) for poly(3-alkylthiophenes)) in addition to a strong peak at 1650-1690 cm(-1) which has not been conclusively assigned. EPR spectra of some disubstituted and tetrasubstituted 2,2'-bithiophene radical cations have been observed and their g-values and coupling constants assigned when the corresponding parent compounds-are photolyzed with ultraviolet light in TFA. Photolysis of 3-alkylthiophenes in TFA in the EPR instrument gave the radical cations of 4,4'-dialkyl-2,2'-bithiophenes. In no case, were EPR signals of the isomeric 3,3'-dialkyl- or 3,4'-dialkyl-2,2'-bithiophene radical cations observed, indicating that dimerization of 3-alkylthiophenes occurs through the less sterically hindered 5-position. The presence of two doublet species corresponding to both conformers, syn and anti, in the radical cations is associated with a large barrier to rotation about the C(2)-C(2') bond.