Synthesis of π-extended porphyrins via intramolecular oxidative coupling

Chem Commun (Camb). 2012 Oct 18;48(81):10069-86. doi: 10.1039/c2cc31279d.

Abstract

Porphyrins fused with other aromatic units at the meso- and β-positions have recently emerged as a hot topic of research. Their synthesis typically starts with preparation of precursors via either Suzuki coupling of a meso-bromoporphyrin or mixed-aldehyde condensation, and is followed by oxidative aromatic coupling, often using high-valent metal reagents (DDQ/Sc(OTf)(3) and Fe(III) salts are among the most popular). In recent years, porphyrins were oxidatively coupled not only with well-known aromatic hydrocarbons such as naphthalene and pyrene, but also with more complex heterocyclic fragments, including indole, phenanthro[1,10,9,8-cdefg]carbazole and BODIPY. A subtle relationship exists between the output of intramolecular oxidative coupling and the nature of the second aromatic moiety, cation in the porphyrin cavity, oxidant, and type of remaining meso-substituent. The extension of the porphyrin chromophore leads to significant change in linear and non-linear optical properties. Very strong bathochromic shifts of absorption (λ(max) reaching 1.5-2 microns in some cases) and increases in two-photon absorption cross-sections are typical for these functional dyes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anthracenes / chemical synthesis
  • Anthracenes / chemistry
  • Hydrocarbons, Aromatic / chemical synthesis
  • Hydrocarbons, Aromatic / chemistry*
  • Models, Molecular
  • Oxidative Coupling*
  • Perylene / chemical synthesis
  • Perylene / chemistry
  • Porphyrins / chemical synthesis*
  • Porphyrins / chemistry
  • Pyrenes / chemical synthesis
  • Pyrenes / chemistry

Substances

  • Anthracenes
  • Hydrocarbons, Aromatic
  • Porphyrins
  • Pyrenes
  • Perylene
  • pyrene
  • anthracene