Charge transfer enhances two-photon absorption in transition metal porphyrins

J Am Chem Soc. 2006 Mar 29;128(12):3902-3. doi: 10.1021/ja0588353.


Two-photon absorption processes were investigated in electropolymerized Fe(III), Mn(III), and Co(II) 5,10,15,20-tetrakis-(4-hydroxytetraphenyl)porphyrin films. Degenerate four wave mixing (DFWM) spectroscopy with 100 fs pulses in the near-IR spectral region was used. Metalloporphyrins with strong charge transfer (CT) transitions in the linear absorption spectra also show enhanced two-photon absorption. (Metalloporphyrin two-photon absorption cross section, delta, increases >10 times over that for the metal free porphyrin.) This effect was attributed to a two-photon induced charge transfer between the metal ion's d orbitals and the pi-system of the porphyrin. Correlation of one- and two-photon absorption properties of transition metal porphyrins suggests a new and simple approach to improve organic materials for photonic applications.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cobalt / chemistry
  • Ferric Compounds / chemistry
  • Manganese / chemistry
  • Metalloporphyrins / chemistry*
  • Photons
  • Porphyrins / chemistry
  • Spectrum Analysis / methods


  • Ferric Compounds
  • Metalloporphyrins
  • Porphyrins
  • tetraphenylporphyrin
  • Cobalt
  • Manganese