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Heavy atom effects on anthracene-rigid-rod excited states anchored to metal oxide nanoparticles

Chemical Physics
Publication Date
DOI: 10.1016/j.chemphys.2007.07.039
  • Anthracene
  • 9-Anthracenecarboxylic Acid
  • Heavy Atom Quenching
  • Thallium
  • Stern–Volmer
  • Titanium Dioxide
  • Zirconium Dioxide


Abstract Two new organic rigid-rod linker compounds, dimethyl 5-(1-anthracenylethynyl)isophthalate and dimethyl 5-(4-(1-anthracenynyl)phenylethynyl)-isophthalate, were used to couple anthracene to the surface of TiO 2 (anatase) and ZrO 2 nanoparticle thin films. These anthracene-rigid-rod molecules have high extinction coefficients and absorbance spectra that are red-shifted relative to 9-anthracenecarboxylic acid (9-AC). The rigid-rod linkers afford high surface coverages, ∼10 −8 mol/cm 2, on the nanostructured films in acetonitrile. Excimer-like emission on ZrO 2 nanoparticles suggests that the rigid-rods do not spatially isolate the anthracene chromophores effectively. On TiO 2 fluorescence was observed for both anthracene-rigid-rods while it was not detected for 9-AC consistent with quantitative electron injection into the semiconductor. Organoiodides and thallium cations (Tl +) were found to be heavy atom quenchers of the anthracene fluorescence in acetonitrile with a concentration dependence that followed the Stern–Volmer model. Fluorescence on ZrO 2 was quenched less efficiently by the organoiodides while Tl + cations exhibited enhanced quenching that followed the Stern–Volmer model at low Tl + concentrations and saturated at higher concentrations, behavior attributed to surface adsorption.

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