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 $\pi$-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 $V_{oc}$, $J_{sc}$, and fill factor values for System-2, resulting in the highest theoretical power conversion efficiency (10.95%). These findings suggest that $\pi$-bridge engineering in triphenylamine-based systems can significantly enhance optoelectronic performance, offering promising donor materials for next-generation OSC devices.

The theoretical design of donor chromophores based on triphenylamine and 2-(1,1-dicyanomethylene)rhodanine (\textbf{DCRD-DCRD-2}) is proposed through structural adaptation with several molecular bridges derived from thiophene that can be used as new organic materials for organic solar cells (OSC). The optoelectronics properties and geometries of the \textbf{DCRD-DCRD-2} organic molecules are characterized using the B3LYP and CAM-B3LYP functional, with the basis set 6-31G(d,p). Consequently, the UV-Visible results revealed that a good relationship was found between the experimental values and the calculated using the DFT and TD-DFT level of theory. The study involved the prediction of photo-physical descriptors such as frontier molecular orbitals, ionization potential, electron affinity, molecular electrostatic potential, reorganization energy, open circuit voltage ($V_{oc}$), fill factor (FF), and short-circuit current ($J_{sc}$) in the ground state geometry, using the B3LYP/6-31G(d,p) basis set. Structural tailoring with various molecular bridges resulted in a narrowing of the energy gap (2.130--1.96eV) with broader absorption spectra (525.55--417.69 nm). An effective charge transfer toward the lowest unoccupied molecular orbitals (LUMO) from the highest occupied molecular orbitals (HOMO) was studied, which played a crucial role in conducting materials. \textbf{DCRD-2} exhibited $λ_{max}$ at $417.69$~nm in EtOH (ethanol) solvent with the lowest band gap (1.96 eV) and the lowest excitation energy of 2.968 eV. The highest mobility of holes and electrons is determined in all the designed molecules due to their low reorganization energy values that validated preferable photovoltaic properties in the \textbf{DCRD-1} molecular system.