Photoexcited triplets of dyes in zeolitic nanostructured channels. A time resolved EPR study

Phys Chem Chem Phys. 2006 Nov 21;8(43):5069-78. doi: 10.1039/b610937n. Epub 2006 Sep 25.

Abstract

Two dyes (4-nitrostilbene, NST and 4-N,N-dimethylamino-4'-nitrostilbene, DANS) included in zeolites with nanometric channels and different Si : Al ratios have been photoexcited and their triplet state studied by time resolved EPR (TR-EPR). This is the first time that a TR-EPR spectrum of photoexcited triplet states of dyes in zeolites has been observed. The zeolites used were ZSM-5 and mordenite, with either protons or lithium as charge compensating ions, and the aluminium-free porosil. The ZFS parameters and the polarized spin populations have been obtained, and compared with those obtained in glassy solutions and in the organic nanostructured matrix perhydrotriphenylene (PHTP). For (3)DANS in neutral solvents and in PHTP the dimethylamino group is pi conjugated, whereas only its acid form is detected in all the zeolites. In the latter the spectra of the radical cations formed by spontaneous oxidation have also been observed both by cw-EPR and TR-EPR, the last spectra being spin polarized in emission. The mobility of the triplets is discussed, taking into account the spin polarization of the radical cations indicating a strong radical-triplet interaction.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chemistry, Physical / methods*
  • Chrysenes / chemistry
  • Coloring Agents / chemistry
  • Coloring Agents / pharmacology*
  • Electron Spin Resonance Spectroscopy / methods*
  • Models, Chemical
  • Spectrophotometry
  • Spectrophotometry, Infrared
  • Spectroscopy, Fourier Transform Infrared
  • Ultraviolet Rays
  • X-Ray Diffraction
  • Zeolites / chemistry*

Substances

  • Chrysenes
  • Coloring Agents
  • perhydrotriphenylene
  • Zeolites