Synthesis and physicochemical characterization of copolymers of 3-octylthiophene and thiophene functionalized with azo chromophore

Polythiophene derivatives with azo chromophore were synthesized via copolymerization of 3-octylthiophene (3OT) and 2-[N-ethyl-N-[4-[(4-nitrophenyl)azo]phenyl]amino]ethyl 3-thienylacetate (3-DRT). This copolymer has interesting optoelectronic properties and a variety of applications such as electrochromic and electronic devices. The polymerization process of 3OT and the functionalized thiophene was carried out via FeCl3 oxidative polymerization. Thin films of poly(3OT-co-3-DRT) copolymer were prepared by spin-coating technique from toluene. FTIR and 1H NMR spectroscopy revealed the presence of chromophore groups in the copolymer chain. Molecular weight and polydispersity of the polymers were measured by size exclusion chromatography. Changes in the surface topography of copolymers were analyzed by atomic force microscopy; the results showed that the copolymers presented some protuberances of variable size unlike the homogeneous granular morphology of P3OT. It is believed that these changes appeared by the incorporation of 3-DRT in the polymer. P3ATs are electrochromic materials that show color change upon oxidation-reduction process. We report that electrochemical characterization of poly(3OT-co-3-DRT) copolymer films synthesized chemically on indium-tin oxide (ITO) glass substrates showed an additional color to the P3OT homopolymer. Optical absorption properties of the polymer films were analyzed in the undoped and doped states and as a function of 3-DRT concentration in the copolymer. The nonlinear optical properties of the copolymers in the undoped and doped states were analyzed by Z-scan technique. The copolymers showed a change of non-linearity sign when the film was doped and results showed that the copolymers have a positive (self-focusing) and negative (self-defocusing) nonlinear optical properties which make them interesting for application as optoelectronic devices. We determined that the nonlinearity of the polymer films was a Kerr type.