Impact of Molecular π-Bridge Modifications in Triphenylamine-Based Donor Materials for Organic Photovoltaic Solar Cells

This study presents a computational investigation into the design of triphenylamine-based donor chromophores incorporating 2-(1,1-dicyanomethylene)rhodanine as the acceptor unit. Three molecular architectures (System-1 to System-3) were developed by introducing distinct thiophene-derived π-bridges to modulate their electronic and optical characteristics for potential application in bulk heterojunction organic solar cells (OSCs). Geometrical optimizations were performed at the B3LYP/6-31+G(d,p) level, while excited-state and absorption properties were evaluated using TD-DFT with the CAM-B3LYP functional. Frontier orbital analysis revealed efficient charge transfer from donor to acceptor moieties, with System-3 showing the narrowest HOMO–LUMO gap (1.96 eV) and the lowest excitation energy (2.968 eV). Charge transport properties, estimated from reorganization energies, indicated that System-2 exhibited the most favorable balance for ambipolar transport, featuring the lowest electron reorganization energy (0.317 eV) and competitive hole mobility. Photovoltaic parameters calculated with PC61BM as acceptor predicted superior Voc, Jsc, and fill factor values for System-2, resulting in the highest theoretical power conversion efficiency (10.95%). These findings suggest that π-bridge engineering in triphenylamine-based systems can significantly enhance optoelectronic performance, offering promising donor materials for next-generation OSC devices.