Synthesis of hyperbranched conjugated polymers based on 3-hexylthiophene, triphenylamine and benzo [c] [1,2,5] thiadiazole moieties: convenient synthesis through suzuki polymerization and impact of structures on optical properties

Abstract

Novel 3-hexylthiophene-based hyperbranched conjugated polymers containing triphenylamine and benzo [c] [1, 2, 5] thiadiazole moieties were synthesized by Suzuki coupling polymerization of tris (4-bromophenyl) amine, 2,2′-(3-hexylthiophene-2,5-diyl) bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) and 4,7-dibromobenzo [c] [1, 2, 5] thiadiazole. Organic solvent-soluble polymers with number-average molecular weights of 24,000 and 42,000 g/mol were obtained in 54–57 % yields. Their structures, molecular weights and thermal properties were characterized via proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FT-IR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle powder X-ray diffraction (XRD) measurements. Optical investigation by UV–vis and fluorescence spectroscopies revealed that the incorporation of the benzo [c] [1, 2, 5] thiadiazole moiety in the hyperbranched polymer structure resulted in a red-shift of the maximum absorption wavelength and an increase in the solution-photoluminescence quantum yield, indicating an extension of the conjugation length. The UV–vis, DSC and XRD results demonstrated that the aggregation of conjugated polymer chains could effectively be reduced by the hyperbranched structures and that conjugation length extension via the introduction of benzo [c] [1, 2, 5] thiadiazole units led to the coexistence of both crystalline and amorphous phases in the solid state and in solution upon addition of a non-solvent.