Photocatalytic Reduction of Nicotinamide Co-factor by Perylene Sensitized RhIII Complexes

Chemistry. 2022 Nov 2;28(61):e202201931. doi: 10.1002/chem.202201931. Epub 2022 Sep 2.

Abstract

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene-based light-harvesting moiety and a catalytic rhodium center (RhIII phenPer). The excited-state dynamics were investigated by means of steady-state and time-resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of RhIII phenPer yields the formation of a charge-separated intermediate, namely RhII phenPer⋅+ , that results in a catalytically active species in the presence of protons.

Keywords: charge separation; perylene; photocatalysis; rhodium catalyst; time-resolved spectroscopy.

MeSH terms

  • Catalysis
  • Niacinamide
  • Perylene* / chemistry
  • Photosynthesis
  • Rhodium* / chemistry

Substances

  • Perylene
  • Niacinamide
  • Rhodium