Interdigited π-stacked low band gap polymers through Friedel Crafts post functionalization of Suzuki coupled phenylene-alt-thiophene copolymers

Abstract

Friedel Crafts post functionalization, a new molecular engineering approach, is experimented on structures of two semiconducting polymers (i.e., 1,4-dihexyloxy and dioctyloxy-phenylene-alt-thiophene copolymers) obtained through Suzuki cross coupling reaction to increase molecular weight and lowering of band gap. This unique post treatment demonstrates two and half fold increase of molecular weight and significant reduction of band gap (1.8–1.5eV); the pre-functionalized value is above 2eV. AFM and SEM micrograph before and after post functionalization show a clearer, smoother, more compact and interconnected biphasic nanostructure for post functionalized polymers in solid state. Significant red shifting of absorption onset (Δλabsonset≈85–210nm) and emission peak maxima (Δλem.max≈175nm) at solid state is attributed to the formation of more rigid planar interdigited π-stack 3D structure. Exfoliation of polymers layers to single polymer wire in polar solvent is clearly demonstrated by comparing the photophysical properties in solid and solution.