Interplay of Intramolecular Noncovalent Coulomb Interactions for Semicrystalline Photovoltaic Polymers

Abstract

Four different kinds of photovoltaic polymers were synthesized by controlling the intrachain noncovalent coulomb interactions through the incorporation of alkoxy- or alkylthio-substituted phenylene, 4,7-di(furan-2-yl)benzothiadiazole, and 4,7-di(thiophen-2-yl)benzothiadiazole as a building block. Fine modulation of the interplay of dipole–dipole, H-bond, and chalcogen–chalcogen interactions (O···S, O···H, S···S, S···F, etc.) along the polymeric backbone influenced the chain planarity, interchain organization, film morphology, and electrical and photovoltaic properties significantly. By replacing the alkoxy substituents with alkylthio groups, the torsional angle increased (136–168°) due to the absence of an O···S attractive coulomb interaction (and/or increased S···S steric hindrance), enhancing the amorphous nature with hindered interchain packing. The alkoxy-substituted polymers exhibited nanofibrillar structures, showing strong interlamellar scattering peaks up to (300) with tight face-on π–π stacking i...