Natural Sunlight‐Driven Activation of Inert Aryl Halides Using Plasmonic Cu@CdS with Polysulfide Active Sites

Visible light photoredox catalysis has become a rapidly emerging area owing to its potential of using sunlight to tame previously hard‐to‐harness radicals for organic synthesis. At present, such blueprint faces a significant challenge, namely how to accomplish thermodynamically demanding reactions with sunlight encompassing a wide range of low energy photons. Here, we report a new reaction framework to overcome this bottleneck through decoupling the thermodynamic limits of photoreduction from photoexcitation. This is fulfilled based on the construction of a heterogeneous photocatalyst Cu@CdS possessing in situ‐formed surficial polysulfide species (including S3•‐ and S42‐), which can efficiently harvest solar energy via plasmonic absorption of Cu, whilst manifest sufficient redox potential for activating inert aryl bromides/chlorides enacted by excited polysulfides. Our findings introduce a straightforward yet viable way to progress toward the century‐long dream of leveraging natural sunlight to produce structurally complex organic molecules, just like plants on Earth.