Journal of Physical Chemistry B, Vol.101, No.49, 10568-10575, 1997
Spectroscopic Properties of 2,5,8,11-Tetra-tert-Butylperylene in Polymer-Films
The spectroscopic properties of 2,5,8,11-tetra-tert-butylperylene in poly(vinyl alcohol) have been studied. To this end, the absorption and fluorescescence excitation and emission spectra have been measured, The shape of the spec;ra in poly(vinyl alcohol) is virtually identical with that in propanediol and lipid systems. The Forster radius calculated from the spectra was found to be 3.7 +/- 0.3 nm, The natural fluorescence lifetime of 2,5,8,11-tetra-tert-butylperylene in poly(vinyl alcohol) was also calculated from the spectra and found to be 5.3 +/- 0.2 ns. The fluorescence decay in paly(vinyl alcohol) exhibits monoexponential behavior with a lifetime of 4.5 +/- 0.3 ns. It is shown that the fluorescence anisotropy of 2,5,8,11-tetra-tert-butylperylene in the polymer matrix does not decay, indicating that its motion is quenched on the time scale of the fluorescence decay. The initial value of the fluorescence anisotropy, r(0), for excitation at 260 nm and emission at 455 nm is -0.16 +/- 0.02 while for excitation at 440 nm and emission at 455 nm it is 0.35 +/- 0.02. The fluorescence transition dipole moments relative to the long molecular axis in the plane of the molecule were determined from angle-resolved fluorescence depolarization measurements. This yields an emission dipole moment al 459 nm of 5 +/- 5 degrees, an excitation dipole moment at 416 nm of -10 +/- 5 degrees, and an excitation dipole moment at 256 nm of 80 +/- 5 degrees.
Keywords:ELECTRONIC-ENERGY TRANSFER;FLUORESCENCE DEPOLARIZATION;CHLOROPHYLL-A;ANISOTROPIC ROTATION;LIQUID-CRYSTALS;PERYLENE;SOLVENTS;SYSTEMS;EXCITATION;MOLECULES