Zeng Le, Huang Ling, Huang Zhi, Mani Tomoyasu, Huang Kai, Duan Chunying, Han Gang
Department of Biochemistry and Molecular Biotechnology, University of Massachusetts Chan Medical School, Worcester, MA, USA.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, PR China.
Nat Commun. 2024 Aug 23;15(1):7270. doi: 10.1038/s41467-024-50795-y.
Consecutive photoinduced electron transfer (conPET) processes accumulate the energies of two photons to overcome the thermodynamic limit of traditional photoredox catalysis. However, the excitation wavelength of conPET systems mainly focused on short wavelength visible light, leading to photodamage and incompatibility with large-scale reactions. Herein, we report on conPET systems triggered by near-infrared (NIR) and red light. Specifically, a blue-absorbing conPET photocatalyst, perylene diimide (PDI) is sensitized by a palladium-based photosensitizer to triplet excited state (PDI), which generates PDI radical anion (PDI) over 100-fold faster than that in the conventional conPET. Accordingly, photoreduction with superior reaction rate and penetration depth, as well as reduced photodamage is detected. More importantly, our work offers comprehensive design rules for the triplet-mediated conPET strategy, whose versatility is confirmed by metal-free dye pairs and NIR-active PtTNP/PDI. Notably, our work achieves NIR-driven atom transfer radical polymerization using an inert aromatic halide as the initiator.
连续光诱导电子转移（conPET）过程积累两个光子的能量以克服传统光氧化还原催化的热力学极限。然而，conPET系统的激发波长主要集中在短波长可见光上，这导致光损伤并与大规模反应不兼容。在此，我们报道了由近红外（NIR）和红光触发的conPET系统。具体而言，一种吸收蓝光的conPET光催化剂，苝二酰亚胺（PDI）被一种钯基光敏剂敏化至三重激发态（PDI），其产生PDI自由基阴离子（PDI）的速度比传统conPET快100倍以上。相应地，检测到具有优异反应速率和穿透深度以及减少光损伤的光还原反应。更重要的是，我们的工作为三重态介导的conPET策略提供了全面的设计规则，其通用性通过无金属染料对和近红外活性的PtTNP/PDI得到证实。值得注意的是，我们的工作使用惰性芳基卤化物作为引发剂实现了近红外驱动的原子转移自由基聚合。
