0000000000602834
AUTHOR
Massimo Zambianchi
New n-dopable thiophene based polymers
Abstract New conjugated polymers containing variable amounts of thienyl and thienyl-S,S-dioxide units have been prepared by chemical or electrochemical polymerization of the appropriate substrates. The presence of the thienyl S,S-dioxide units leads to the decrease of the LUMO energies with respect to those of the ‘all thienyl’ counterparts. Electrochemical and spectro electrochemical data of n-doping of these materials are reported.
Spectroscopic signatures for planar equilibrium geometries in methyl-substituted oligothiophenes
In recent studies it was demonstrated that temperature-dependent optical spectroscopy is a valuable tool for revealing the differences in the geometries of flexible molecules like oligothiophenes (OTs) in the ground (S0) and first excited (S1) electronic states, by examining the symmetry relations between the absorption and emission spectra: while at low temperature the spectra show mirror symmetry, pointing to planar geometries in S0 and S1, the symmetry relation breaks down at ambient temperature due to thermal population of torsional modes. In the present joint spectroscopic and theoretical study, we demonstrate that this behavior is also observed for di- and tetramethyl-substituted OTs,…
Controlling the electronic properties of polythiophene through the insertion of nonaromatic thienyl S,S-dioxide units
A new class of thiophene-based polymers characterized by the presence of one nonaromatic thienyl S,S-dioxide moiety (O) to every two, four, and six aromatic thienyl units (T) was prepared from the newly synthesized precursors TOT, TTOTT, and TTTOTTT, and electrochemically characterized. The polymers displayed remarkably greater electron affinities than that of polythiophene and could be reversibly n-doped at moderate potentials, while still maintaining the property of also being p-doped at moderate potential values. All polymers were characterized by good p-doping/undoping cyclability, while at least four aromatic units to every nonaromatic one were needed to ensure good n-doping/undoping c…