Affiliation: | 1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 P. R. China;2. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 P. R. China These authors contributed equally to this work.;3. LENS (European Laboratory for Non-Linear Spectroscopy), via N. Carrara 1, 50019 Sesto Fiorentino (FI), Italy These authors contributed equally to this work.;4. LENS (European Laboratory for Non-Linear Spectroscopy), via N. Carrara 1, 50019 Sesto Fiorentino (FI), Italy;5. International Tomography Center, SB RAS, and, Novosibirsk State University, 630090 Novosibirsk, Russia;6. College of Chemistry, Beijing Normal University, Beijing, 100875 P. R. China;7. Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024 P. R. China;8. Light Industry and Chemical Engineering College, Guangdong University of Technology, Guangzhou, 510006 P. R. China;9. State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640 P. R. China |
Abstract: | We prepared an orthogonal compact electron-donor (phenoxazine, PXZ)-acceptor (naphthalimide, NI) dyad ( NI-PXZ ), to study the photophysics of the thermally-activated delayed fluorescence (TADF), which has a luminescence lifetime of 16.4 ns (99.2 %)/17.0 μs (0.80 %). A weak charge transfer (CT) absorption band was observed for the dyad, indicating non-negligible electronic coupling between the donor and acceptor at the ground state. Femtosecond transient absorption spectroscopy shows a fast charge separation (CS) (ca. 2.02∼2.72 ps), the majority of the singlet CS state is short-lived, especially in polar solvents (τCR = 10.3 ps in acetonitrile, vs. 1.83 ns in toluene, 7.81 ns in n-hexane). Nanosecond transient absorption spectroscopy detects a long-lived transient species in n-hexane, which is with a mixed triplet local excited state (3LE) and charge separated state (3CS), the lifetime is 15.4 μs. In polar solvents, such as tetrahydrofuran and acetonitrile, a neat 3CS state was observed, whose lifetimes are 226 ns and 142 ns, respectively. Time-resolved electron paramagnetic resonance (TREPR) spectra indicate the existence of strongly spin exchanged 3LE/3CT states, with the effective zero field splitting (ZFS) |D| and |E| parameters of 1484 MHz and 109 MHz, respectively, much smaller than that of the native 3NI state (2475 and 135 MHz). It is rare but solid experimental evidence that a closely-lying 3LE state is crucial for occurrence of TADF and this 3LE state is an essential intermediate state to facilitate reverse intersystem crossing in TADF systems. |