Herein, a series of diazaborinin based derivatives (FABD1–FABD8) having D-π-D configuration was designed by inserting different types of rigid fused and unfused π-bridges into reference molecule (FABR) to explore their photovoltaic characteristics. To determine the optoelectronic and charge transport characteristics of these analogues, DFT/TD-DFT based calculations were conducted at the MPW1PW91/6-31G (d,p) level. For this, various analyses were performed such as transition density matrix (TDM), global reactivity parameters (GRP), open-circuit voltage (Voc), optical properties (UV–Vis), binding energy (Eb), hole-electron and frontier molecular orbital (FMO) energies. Their insights indicate that a rigid fused π-bridge greatly lowers the band gap as compared to an unfused π-spacers. Particularly, FABD7 showed the lowest energy gap of 2.20 eV owing to the presence of a rigid fused central core as compared to FABR with a band gap of 2.65 eV. Similarly, the entitled designed derivatives demonstrated a redshift absorption in the range of 585.7–704.6 nm while FABR is reported with 558.7 nm in the solvent phase. Furthermore, these derivatives displayed significant Voc with blending of PC61BM acceptor. This observation was also supported by DOS and TDM based insights. Interestingly, FABD7 seemed as a viable photovoltaic material due to its strong optical properties and small band gaps. These results uncover that the designed chromophores may be considered as efficient to enhance the performance of OSCs.