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Efficient Red-to-Blue Triplet-Triplet Annihilation Upconversion Using the C 70 -Bodipy-Triphenylamine Triad as a Heavy-Atom-Free Triplet Photosensitizer.

Yuanming LiJianhui ZhangSan-E ZhuYaxiong WeiFan ZhangLin ChenXiaoguo ZhouShilin Liu
Published in: The journal of physical chemistry. B (2023)
Triplet-triplet annihilation upconversion (TTA-UC) with heavy-atom-free organic triplet photosensitizers has attracted extensive attention recently, however, the successful examples with absorption in red and first near-infrared (NIR-I, 650-900 nm) region are still insufficient. Herein, we conducted a new TTA-UC system of perylene using C 70 -bodipy-triphenylamine triad ( C 70 -BDP-T ) as the heavy-atom-free photosensitizer. Efficient red-to-blue (663 to 450 nm) TTA-UC was achieved in this system with an anti-Stokes shift of 0.88 eV and a quantum yield up to 5.2% (out of a 50% maximum) in deaerated toluene. Notably, this is the highest quantum yield to date in similar TTA-UC systems with heavy-atom-free organic photosensitizers. Using steady-state and transient absorption spectroscopy, together with cyclic voltammogram and quantum chemical calculations, photophysical and photochemical mechanisms were elucidated. Specifically, two triplet triads, C 70 - 3 BDP*-T and 3 C 70 *-BDP-T , were produced efficiently upon photoexcitation, with lifetimes of 2.0 ± 0.1 and 32.2 ± 0.3 μs, respectively. Electron transfer and recombination mechanisms were confirmed to play crucial roles in the formation of these triplets, instead of intersystem crossing. Our results shed light on the superiority of fullerenes in the development of heavy-atom-free photosensitizers.
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