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- W4366991918 abstract "A series of naphthalimide (NI)-phenothiazine (PTZ) electron donor-acceptor dyads were prepared to study the thermally activated delayed fluorescence (TADF) property of the dyads, from a point of view of detection of the various transient species. The photophysical properties of the dyads were tuned by changing the electron donating and the electron withdrawal capability of the PTZ and NI moieties, respectively, by oxidation of the PTZ unit, or by using different arylamines to attach with the NI unit. This tuning effect was manifested in the UV-vis absorption and fluorescence emission spectra, e.g., the change of the charge transfer absorption bands. TADF was observed for the dyads containing native PTZ unit, and the prompt and delayed fluorescence lifetimes changed when different arylamine was used. In polar solvent, no TADF was observed. For the dyads with the PTZ unit oxidized, no TADF was observed as while. Femtosecond transient absorption spectra show that the charge separation takes ca. 0.6 ps, and admixture of locally excited ( 3 LE) state and charge separated ( 1 CS/ 3 CS) states formed (in n -hexane). The subsequent charge recombination from the 1 CS state takes ca. 7.92 ns. Upon oxidation of the PTZ unit, the beginning of charge separation is at 178 fs, and formation of 3 LE state takes 4.53 ns. Nanosecond transient absorption (ns-TA) spectra show that both 3 CS and 3 LE states were observed for the dyads showing TADF, whereas only 3 LE or 3 CS state was observed for the systems lacking of TADF. This is a rare but unambiguous experimental evidence that the spin-vibronic coupling of 3 CS/ 3 LE states is crucial for TADF. Without the mediating effect of the 3 LE state, no TADF is resulted, even the long-lived 3 CS state is populated (lifetime τ CS ≈ 140 ns). This experimental result confirms the 3 CS → 1 CS reverse intersystem crossing (rISC) is slow, without coupling with an approximate 3 LE state. These studies are useful for in-depth understanding of the photophysical mechanisms of the TADF emitters, as well as for molecular structure design of new electron donor-acceptor TADF emitters." @default.
- W4366991918 created "2023-04-27" @default.
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- W4366991918 date "2023-04-25" @default.
- W4366991918 modified "2023-10-01" @default.
- W4366991918 title "Tuning the photophysical property of naphthalimide-phenothiazine dyads by variation of the electron donating and accepting capability: synthesis and study of the intersystem crossing and thermally-activated delayed fluorescence" @default.
- W4366991918 doi "https://doi.org/10.3762/bxiv.2023.18.v1" @default.
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