Photophysics of Carbazole-Containing Systems. 3 Fluorescence of Carbazole-Containing Oligoethers in Dilute Solution

Fluorescence techniques, including quenching and anisotropy measurements, have been used to study the photophysical behavior of the carbazole-based oligoethers poly{9-(2,3-epoxypropyl)carbazole}, PEPCz, and poly{1,2-epoxy-6-(9-carbazolyl)-4-oxahexane}, PECzOH, and their model compounds, in dilute fluid solutions in THF. These compounds show no evidence of excimer formation under these conditions and their fluorescences exhibit first-order decay behavior regardless of the degree of polymerization of the oligomer. Both steady-state and time-resolved anisotropy measurements upon dilute, glassy solutions show that intramolecular energy migration occurs in the oligomers. Fluorescence quenching experiments, using both dimethylterephthalate and oxygen as quenchers, produced evidence which supports the supposition that in the absence of excimer trapping sites, intramolecular energy migration will be encouraged in dilute fluid solutions of the oligoethers. Unfortunately, the fluorescence quenching data did not permit evaluation of the extents of energy migration in the various polymers or the relative efficiencies with which migration occurs in the two different types of oligoether. This limitation would appear to be a general feature of fluorescence quenching measurements, despite their frequent adoption, in the past, in studies of energy migration in polymers.