A comprehensive analysis of charge transfer effects on donor‐pyrene (bridge)‐acceptor systems using different substituents

The alternant polycyclic aromatic hydrocarbon pyrene has photophysical properties that can be tuned with different donor and acceptor substituents. Recently, a D (donor)‐Pyrene (bridge)‐A (acceptor) system, DPA, with the electron donor N,N‐dimethylaniline (DMA), and the electron acceptor trifluoromethylphenyl (TFM), was investigated by means of time‐resolved spectroscopic measurements ( J. Phys. Chem. Lett. 2021, 12, 2226–2231). DPA shows great promise for potential applications in organic electronic devices. In this work, we used the ab initio second‐order algebraic diagrammatic construction method ADC(2) to investigate the excited‐state properties of a series of analogous DPA systems, including the originally synthesized DPAs. The additionally investigated substituents were amino, fluorine, and methoxy as donors and nitrile and nitro groups as acceptors. The focus of this work was on characterizing the lowest excited singlet states regarding charge transfer (CT) and local excitation (LE) characters. For the DMA‐pyrene‐TFM system, the ADC(2) calculations show two initial electronic states relevant for interpreting the photodynamics. The bright S 1 state is locally excited within the pyrene moiety, and an S 2 state is localized ~0.5 eV above S 1 and characterized as a donor to pyrene CT state. HOMO and LUMO energies were employed to assess the efficiency of the DPA compounds for organic photovoltaics (OPVs). HOMO‐LUMO and optical gaps were used to estimate power conversion and light‐harvesting efficiencies for practical applications in organic solar cells. Considering the systems using smaller D/A substituents, compounds with the strong acceptor NO 2 substituent group show enhanced CT and promising properties for use in OPVs. Some of the other compounds with small substituents are also found to be competitive in this regard.