Electron Push–Pull Effects on Intramolecular Charge Transfer in Perylene-Based Donor–Acceptor Compounds

A series of asymmetric donor–acceptor (D–A) perylene-based compounds, 3-(N,N-bis­(4′-(R)-phenyl)­amino)­perylene (Peri–DPA(R)), were successfully prepared to explore their intramolecular charge transfer (ICT) properties. To induce ICT between the donor and acceptor, diphenylamine (DPA) derivatives (electron donor units) with the same functional groups (R = CN, F, H, Me, or OMe) at both para positions were linked to the C-3 position of perylene to produce five Peri–DPA derivatives. A steady-state spectroscopy study on Peri–DPA(R)­s exhibited a progressively regulated ICT trend consistent with the substituent effect as it progressed from the electron-withdrawing group to the electron-donating group. In particular, a comparative study using a D–A–D (donor–acceptor–donor) system demonstrated that not only the electron push–pull substituent effect but also subunit combinations influence photophysical and electrochemical properties. The different ICT characters observed in Lippert–Mataga plots of D–A(CN) and D–A–D(CN) (CN-substituted D–A and D–A–D) led to the investigation on whether ICT emission of two systems with differences in subunit combinations is of the same type or of a different type. The femtosecond transient absorption (fs-TA) spectroscopic results provided direct evidence of ICT origin and confirmed that D–A(CN) and D–A–D(CN) exhibited the same transition mix of ICT (from donor to acceptor) and reverse ICT (rICT, from arylamine to CN unit). Density functional theory (DFT)/TD-DFT calculations support the presence of ICT for all five compounds, and the experimental observations of rICT presented only for CN-substituted compounds.