RESUMEN
Triplet-triplet annihilation upconversion (TTA-UC) has the potential to enhance photoredox catalysis yield. It includes a sensitizer and an annihilator. Efficient and stable annihilators are essential for photoredox catalysis, yet only a few examples are reported. Herein, we designed four novel pyrene annihilators (1, 2, 3 and 4) via introducing aryl-alkynyl groups onto pyrene to systematically modulate their singlet and triplet energies. Coupled with platinum octaethylporphyrin (PtOEP), the TTA-UC efficiency is enhanced gradually as the number of aryl-alkynyl group increases. When combining 4 with palladium tetraphenyl-tetrabenzoporphyrin (PdTPTBP), we achieved the highest red-to-green upconversion efficiency (22.4±0.3 %) (out of a 50 % maximum) so far. Then, this pair was used to activate photooxidation of aryl boronic acid under red light (630â nm), which achieved a great improved reaction yield compared to that activated by green light directly. The results not only provide a design strategy for efficient annihilators, but also show the advantage of applying TTA-UC into improving the photoredox catalysis yield.
RESUMEN
Singlet fission (SF) is considered as a promising strategy to overcome the Shockley-Queisser limit of single-junction solar cells. However, only a handful of chromophores were observed to undergo SF to date. To broaden the number of SF chromophores, we designed a series of phosphorus-doped perylenes based on the diradical character strategy and examined their SF feasibility using theoretical calculations. By analysis of frontier orbitals, diradical character and aromaticity, SF-capable candidates were prescreened. These analyses reveal that the diradical character of perylene is effectively enhanced by P-doping at bay- and peri-positions of perylene, making SF more thermodynamically feasible. However, the diradical character remains nearly unchanged when P atoms are doped at ortho-positions because the spin center cannot be stabilized, leading to a more endothermic SF. This study shows how SF-related energies and diradical character of SF chromophores are altered by P doping, and extends the SF-capable molecular library.