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Exploiting Pnictogen σ/π-Hole Interactions for Visible-Light-Induced Radical Transformations.

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Pnictogen σ/π-hole interactions enable visible-light-induced generation of diverse organic radicals. This metal-free approach utilizes charge-transfer complexes for single-electron transfer, facilitating new synthetic strategies and bond activations.

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Area of Science:

  • Organic Synthesis
  • Supramolecular Chemistry
  • Photochemistry

Background:

  • Direct and selective chemical bond activation under mild conditions is a key challenge in organic synthesis.
  • Elemental σ/π-hole interactions offer novel noncovalent molecular activation strategies.
  • Pnictogen σ/π-hole interactions are underexplored in photoinduced radical processes.

Purpose of the Study:

  • To leverage pnictogen σ/π-hole interactions for visible-light-induced organic radical generation.
  • To develop general strategies for visible-light-driven radical transformations.
  • To explore the application of N-heterocyclic nitrenium (NHN) and carbene (NHC) systems in these photoreactions.

Main Methods:

  • Tuning pnictogen σ/π-hole properties through element selection, substituents, and acceptors.
  • Assembling charge-transfer complexes (CTCs) that undergo visible-light-induced single-electron transfer (SET).
  • Utilizing NHN and NHC systems to promote photoactive CTC formation and mediate radical transformations.

Main Results:

  • Developed a transition-metal-free, photocatalyst-free strategy for generating various radicals (P(III)-centered, alkyl, carboranyl, etc.) via pnictogen σ-hole interactions.
  • Expanded scope using NHNs for metal-free reductive radical transformations, activating C-I, C-Br, and C-Cl bonds, and enabling controlled radical polymerizations.
  • Extended the concept to NHC-based systems, generating NHC radical anions that activate inert bonds like Caryl-F, Caryl-N, Caryl-S, Caryl-Se, and Caryl-O.

Conclusions:

  • Pnictogen σ/π-hole interactions are powerful tools for visible-light-induced radical generation and organic transformations.
  • The developed strategies offer efficient, metal-free pathways for synthesizing diverse radical species and activating challenging bonds.
  • These findings provide a foundation for designing new reagents and catalysts based on pnictogen interactions in radical chemistry.