Electronic coupling and spin–orbit charge transfer intersystem crossing (SOCT-ISC) in compact BDP–carbazole dyads with different mutual orientations of the electron donor and acceptor
Open Access
- 16 March 2020
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 152 (11), 114701
- https://doi.org/10.1063/1.5145052
Abstract
In order to study the spin–orbit charge transfer induced intersystem crossing (SOCT-ISC), Bodipy (BDP)–carbazole (Cz) compact electron donor/acceptor dyads were prepared. Charge transfer (CT) emission bands were observed for dyads showing strong electronic coupling between the donor and the acceptor (coupling matrix elements VDA, 0.06 eV–0.18 eV). Depending on the coupling magnitude, the CT state of the dyads can be either dark or emissive. Equilibrium between the 1LE (locally excited) state and the 1CT state was confirmed by temperature-dependent fluorescence studies. Efficient ISC was observed for the dyads with Cz connected at the meso-position of the BDP. Interestingly, the dyad with non-orthogonal geometry shows the highest ISC efficiency (ΦΔ = 58%), which is different from the previous conclusion. The photo-induced charge separation (CS, time constant: 0.7 ps) and charge recombination (CR, ∼3.9 ns) were studied by femtosecond transient absorption spectroscopy. Nanosecond transient absorption spectroscopy indicated that the BDP-localized triplet state was exceptionally long-lived (602 µs). Using pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the SOCT-ISC mechanism was confirmed, and we show that the electron spin polarization of the triplet state is highly dependent on the mutual orientation of the donor and acceptor. The dyads were used as triplet photosensitizers for triplet–triplet-annihilation (TTA) upconversion, and the quantum yield is up to 6.7%. TTA-based delayed fluorescence was observed for the dyads (τDF = 41.5 µs). The dyads were also used as potent photodynamic therapy reagents (light toxicity of IC50 = 0.1 µM and dark toxicity of IC50 = 70.8 µM).Funding Information
- the State Key Laboratory of fine chemicals (ZYTS201901)
- the Fundamental Research Funds for the Central Universities (DUT19TD28)
- Foundation for Innovative Research Groups of the National Natural Science Foundation of China (21673031, 21761142005, 21911530095)
- Russian Foundation for Basic Research (19-29-10035)
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