1. Spiro rhodamine-coumarin compact electron donor–acceptor dyads: synthesis and spin–orbit charge transfer intersystem crossing.
- Author
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Liu, Dongyi, Imran, Muhammad, Xiao, Xiao, and Zhao, Jianzhang
- Subjects
ELECTRON donors ,CHARGE transfer ,COUMARINS ,FLUORESCENCE yield ,DYADS ,REACTIVE oxygen species ,DIHEDRAL angles - Abstract
We prepared spiro rhodamine (RB)-coumarin (Cou) compact electron donor–acceptor dyads (RB-Cou-CF
3 and RB-Cou-CN), to study the charge transfer (CT) and spin–orbit CT intersystem crossing (SOCT-ISC). The π-conjugation planes of the rhodamine and coumarin units in both dyads are in nearly orthogonal geometry (dihedral angle: 86.3°). CT state emission was observed for RB-Cou-CF3 (at 550 nm) and RB-Cou-CN (at 595 nm). Although the fluorescence of the pristine coumarin units (fluorescence quantum yields ΦF = 59%) was quenched in the dyads (ΦF = 0.5 ~ 1.1% in n-hexane), the triplet state quantum yields of the dyads are also low (singlet oxygen quantum yield, ΦΔ = 2.3–7.5% in n-hexane). Nanosecond transient absorption spectra show that the3 Cou* state was formed, which shows a triplet state lifetime of 11–15.6 μs. The proposed photophysical path for the dyads is as follows: RB-1 Cou* → RB+• -Cou−• → RB-3 Cou*. The low SOCT-ISC yield is attributed to the slightly lower charge-transfer state energy (1.94 eV in toluene) as compared to the3 Cou* state energy (2.23 eV) and the shallow potential energy curve (PEC) at energy minima of the dyads. This work indicates that orthogonal conformation of donor–acceptor units is inadequate for achieving efficient SOCT-ISC. These results are useful for studying charge separation and intersystem crossing of electron donor/acceptor dyads. [ABSTRACT FROM AUTHOR]- Published
- 2022
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