Red light-driven electron sacrificial agents-free photoreduction of inert aryl halides via triplet-triplet annihilation

Abstract

Selective photoactivation of inert aryl halides is a fundamental challenge in organic synthesis. Specially, the long-wavelength red light is more desirable than the widely-applied blue light as the excitation source for photoredox catalysis, due to its superior penetration depth. However, the long-wavelength red light-driven photoactivation of inert aryl halides remains a challenge, mainly because of the low energy of the single long-wavelength red photon. Herein, we report the photoreduction of aryl bromides/chlorides with 656 nm LED via triplet-triplet annihilation (TTA) strategy. This method is based on our discovery that the commonly used chromophore of perylene can serve as an efficient and metal-free photocatalyst to enable the photoreduction of inert aryl halides without the conventional need for electronic sacrificial agents. By introducing a red light-absorbing photosensitizer to this perylene system, we accomplish the long-wavelength red light-driven photoreduction of aryl halides via sensitized TTA mechanism. Moreover, the performance of such a TTA-mediated photoreduction can be significantly enhanced when restricting the rotation freedom of phenyl moiety for perylene derivatives to suppress their triplet nonradiative transition, in both small and large-scale reaction settings.