Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 152, Issue 11, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.5145052
Keywords
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Funding
- NSFC [21673031, 21761142005, 21911530095]
- State Key Laboratory of Fine Chemicals [ZYTS201901]
- Fundamental Research Funds for the Central Universities [DUT19TD28]
- RFBR [19-29-10035]
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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 V-DA, 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 (LE)-L-1 (locally excited) state and the (CT)-C-1 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 (Phi(Delta) = 58%), which is different from the previous conclusion. The photo-induced charge separation (CS, time constant: 0.7 ps) and charge recombination (CR, similar to 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 mu s). 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 (tau(DF) = 41.5 mu s). The dyads were also used as potent photodynamic therapy reagents (light toxicity of IC50 = 0.1 mu M and dark toxicity of IC50 = 70.8 mu M). Published under license by AIP Publishing.
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