4.8 Article

Plasmon-Generated Solvated Electrons for Chemical Transformations

Journal

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c07768

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Funding

  1. Welch Foundation [C-1220, C-1222]
  2. Air Force Office of Science and Research under MURI [FA9550-15-1-0022]
  3. National Institutes of Health [R01DK122784]
  4. Department of Defense's National Defense Science and Engineering Graduate fellowship

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This study demonstrates the generation of solvated electrons by exciting the plasmon resonance of Al nanocrystals with visible light, leading to quantifiable and controlled reductive organic chemical reactions. The quantum efficiency of plasmon absorbed photon to solvated electron generation is inferred to be at least 1.1% based on measured reactions concentration.
Methods for generating solvated electrons-free electrons in solution-have focused primarily on alkali metal ionization or high-energy electrons or photons. Here we report the generation of solvated electrons by exciting the plasmon resonance of Al nanocrystals suspended in solution with visible light. Two chemical reactions were performed: a radical-addition reaction with the spin-trap 2-methyl-2-nitrosopropane, and a model cyclization reaction with the radical clock 6-bromohex-1-ene. A quantum efficiency of at least similar to 1.1% for plasmon absorbed photon to solvated electron generation can be inferred from the measured radical clock reaction concentration. This study demonstrates a simple way to generate solvated electrons for driving reductive organic chemical reactions in a quantifiable and controlled manner.

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