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

Area of Science:

• Organic Chemistry
• Photocatalysis
• Materials Science

Background:

• Visible light photoredox catalysis offers sustainable organic synthesis using sunlight.
• A major challenge is performing thermodynamically demanding reactions with low-energy photons.

Purpose of the Study:

• To develop a new reaction framework overcoming the limitations of visible light photocatalysis.
• To enable thermodynamically demanding organic reactions using natural sunlight.

Main Methods:

• Construction of a heterogeneous photocatalyst, Cu@CdS, with in situ-formed surficial polysulfide species (S3•− and S42−).
• Utilizing Cu@CdS for efficient solar energy harvesting via plasmonic absorption and activation of aryl halides.

Main Results:

• The Cu@CdS photocatalyst effectively decouples thermodynamic limits from photoexcitation.
• Demonstrated efficiency in aryl cross-coupling, borylation, hydrogenation, and Birch-type dearomatization reactions.
• Achieved up to 90% product yield using only natural sunlight, with good catalyst recyclability and stability.

Conclusions:

• The Cu@CdS system provides a viable strategy for leveraging natural sunlight in organic synthesis.
• This approach facilitates the production of complex organic molecules, mimicking natural photosynthesis.
• Advances the goal of sustainable chemical synthesis powered by solar energy.