A new approach to the synthesis of porphyrin-fullerene dyads

Mol Divers. 2003;6(3-4):315-21. doi: 10.1023/b:modi.0000006864.22321.2e.

Abstract

A new synthetic approach to porphyrin-fullerene dyads utilizing tetraphenylporphyrin (TPP) and three novel reactions (vicarious nucleophilic substitution, metathesis, and [4+2]-cycloaddition to fullerene) is described. 5-(4-Nitrophenyl)-10,15,20-triphenylporphyrin zinc complex reacts with the carbanion of chloromethyl para-tolyl sulphone (which bears a leaving group Cl at the carbanionic center), affording the nucleophilic substitution of hydrogen product containing a CH2SO2Tol group. The product obtained when alkylated with an alkyl halide (bearing an acetylenic function in the terminal position), followed by the cross-enyne metathesis reaction (with the use of an efficient ruthenium catalyst), resulted in the formation of a TPP-diene building block. Its Diels-Alder reaction with C60-fullerene led to the title dyad--a new artificial photosynthetic model. This method opens up the possibility for synthesis of dyads with variable distances between chromophores, depending on the type of the alkyl halides used.

MeSH terms

  • Bridged-Ring Compounds / chemistry*
  • Molecular Structure
  • Porphyrins / chemical synthesis*
  • Porphyrins / chemistry*
  • Zinc / chemistry

Substances

  • Bridged-Ring Compounds
  • Porphyrins
  • tetraphenylporphyrin
  • Zinc