Synergistically Improved Crystallinity and Molecular Doping Ability of Polythiophene-Diketopyrropyrrole Derivatives by m-Trifluoromethylbenzene Containing Side Chains for Improved Thermoelectric Materials

m -Trifluoromethylbenzene (FB) groups have been widely employed in various fields; however, no studies have reported the use of FB in side chains to enhance the carrier mobility and molecular doping of conjugated polymers. In this study, based on density functional theory (DFT) calculations, we discovered that FB groups can effectively bind to [FeCl 4 ] −, the counterion of the p-type dopant FeCl 3, thereby increasing doping ability. Consequently, FB groups were incorporated into the side chains of thiophene-diketopyrrolopyrrole-based donor–acceptor (D-A)-conjugated polymers, and a series of random conjugated polymers were synthesized (denoted as PDPPFB- x, where x represents the molar ratio of the FB side chain). The findings revealed that an appropriate number of FB groups can decrease the π–π stacking distances, enhance the films’ crystallinity, and consequently improve the charge transfer ability. Furthermore, after doping with FeCl 3, the UV–vis–NIR spectra indicated that the doping efficiency was augmented by increasing the molar fraction of the FB side chain. Among these polymers, PDPPFB-10 exhibited the highest conductivity and power factor, which were 2.0 and 1.5 times higher than those of PDPPFB-0, respectively. These results illustrated a straightforward molecular design strategy for enhancing the crystallinity and conductivity of conjugated polymers, thereby expanding the way to optimize their thermoelectric performance.