Effect of TiO2 colloids on the fluorescence behavior of two cyanine dyes.

The photophysical properties of two typical cyanine dyes [3,3′-diethyl-9-methyl-thiacarbocyanine iodide (dye A) and anhydro-3,3′-disulfopropyl-5,5′-diphenyl-9-ethyloxacarbocyanine hydroxide (dye B)] in the absence and presence of TiO2 colloids have been investigated by UV–visible spectroscopy, 1H-NMR spectroscopy, fluorescence spectroscopy, fluorescence lifetime measurements, and ESR measurements. It was found from the absorption spectra and NMR results that there are two isomers in the ground state of these dyes. Steady-state fluorescence spectra show that the fluorescence intensities of dye A and dye B are enhanced and quenched by TiO2 colloids, respectively. Time-resolved fluorescence lifetime measurements indicate that the lifetimes of dye A and dye B in the presence of TiO2 colloids are longer and shorter than those obtained in the absence of TiO2 colloids, respectively. ESR measurements demonstrate that the electron transfer efficiency from 1dye B* to the conduction band of TiO2 is much larger than that from 1dye A* to the conduction band of TiO2. The different fluorescence behavior of dye A and dye B can be intepreted in terms of whether φTr,nr0–φTr,nr (the reduction of the quantum yield for radiationless transition in the excited singlet state 1dye* caused by the TiO2 colloids) is larger or smaller than φET (the quantum yield of electron transfer from 1dye* to the conduction band of TiO2 colloids).