Enhancing the Rate of Quantum-Dot-Photocatalyzed Carbon-Carbon Coupling by Tuning the Composition of the Dot's Ligand Shell

J Am Chem Soc. 2017 Mar 29;139(12):4246-4249. doi: 10.1021/jacs.6b13220. Epub 2017 Mar 16.

Abstract

This Communication describes the photoredox catalysis of a C-C coupling reaction between 1-phenylpyrrolidine (PhPyr) and phenyl trans-styryl sulfone by visible-light-absorbing colloidal CdS quantum dots (QDs), without a sacrificial oxidant or reductant, and without a co-catalyst. Simple kinetic analysis reveals that photo-oxidation of PhPyr by the QDs is the rate-limiting step. Disordering of the ligand shell of the QDs by creating mixed monolayers of oleate and octylphosphonate increases the initial rate of the reaction by a factor of 2.3, and the energy efficiency (mol product/joule of incident photons) of the reaction by a factor of 1.6, by facilitating the hole-transfer step.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon / chemistry*
  • Catalysis
  • Ligands
  • Light*
  • Molecular Structure
  • Photochemical Processes*
  • Quantum Dots*

Substances

  • Ligands
  • Carbon