Tuning the photovoltaic potential of thiazole based materials via incorporation of selenophene and electron acceptors rings at peripheral positions: A DFT approach

The non-fullerene acceptor (NFA) chromophores have sparked scientific and economic interest, due to their rapid advancements in power conversion efficiencies. Therefore, a series of new chlorothiazole based compounds (STM1-STM6) with A1–π–A2–π–A1 configuration was designed using reference chromophore (STMR). Structural modifications were made via incorporating selenophene and extended acceptor units, to enhance photovoltaic response in the designed materials. Density functional theory/time dependent-density functional theory (DFT/TD-DFT) calculations were executed at M06/6-311G (d,p) level to investigate key electronic and photovoltaic properties of STM1-STM6. So, various analyses such as UV–Visible, frontier molecular orbitals (FMOs), transition density matrix (TDM), density of states (DOS), open circuit voltage (V_oc) and binding energy (E_b) were conducted to comprehend the photovoltaic properties. The designing in structural aspects with terminal acceptors and π-linker induced a reduction in energy gaps (ΔE = 2.078–2.237 eV) with an enhancement in the bathochromic shift (λ_max = 744.650–798.250 nm in chloroform) than reference compound. A higher exciton dissociation rate was observed in all the compounds due to lower binding energy values (E_b = 0.525–0.572 eV). Additionally, TDM and DOS findings further endorsed the effective charge delocalization from HOMO to LUMO. Among all the examined compounds, STM3 exhibited the smallest band gap (2.078 eV), highest absorption maxima (798.250 nm), and the lowest exciton binding energy (0.525 eV), indicating significant electronic properties. Moreover, V_oc analysis was conducted with respect to HOMO_PBDBT-LUMO_acceptor for all the designed chromophores; consequently, STM2 demonstrated a substantial V_oc value of 1.647 V. Similarly, electron hole analysis was also conducted and significant electron and hole density was observed in all the investigated compounds, especially in STM2. The entitled compounds with photovoltaic potential would be considered as promising materials for the development of solar energy devices.