Microscopic, Spectroscopic, and Electrochemical Characterization of Novel Semicrystalline Poly(3-hexylthiophene)-Based Dendritic Star Copolymer.

In this study, electron-donating semicrystalline generation 1 poly(propylene thiophenoimine)-co-poly(3-hexylthiophene) star copolymer, G1PPT-co-P3HT was chemically prepared for the first time. Copolymerization was achieved with high molecular weight via facile green oxidative reaction. H NMR analyses of the star copolymer demonstrated the presence of 84% regioregular (rr) head-to-tail (HT) P3HT, which accounts for the molecular ordering in some grain regions in the macromolecule's morphology, as revealed by the high-resolution scanning electron microscopy (HRSEM) and Selected Area Electron Diffraction (SAED) images, and X-ray diffraction spectroscopy (XRD) measurements. The star copolymer also exhibited good absorption properties in the ultraviolet-visible (UV-Vis) and the near infrared (NIR) spectral regions, which give rise to an optical energy bandgap value as low as 1.43 eV. A HOMO energy level at -5.53 eV, which is below the air-oxidation threshold, was obtained by cyclic voltammetry (CV). Electrochemical impedance spectroscopy (EIS) ascertained the semiconducting properties of the macromolecule, which is characterized by a charge transfer resistance, , value of 3.57 kΩ and a Bode plot-phase angle value of 75°. The combination of the EIS properties of G1PPT-co-P3HT and its highly electron-donating capability in bulk heterojunction (BHJ) active layer containing a perylene derivative, as demonstrated by photoluminescence quenching coupled to the observed Förster Resonance charge transfer, suggests its suitability as an electron-donor material for optoelectronic and photovoltaic devices.