Preparation and spectral characterization of fluorescence probes based on 4-N,N-dimethylamino benzoic acid and sterically hindered amines.

The adducts of simple chromophore 4-N,N-dimethylamino benzoic acid with 2,2,6,6-tetrametyl-4-hydroxy- or 4-amino-piperidine were examined as fluorescence probes (spin double sensors) to monitor radical processes. The links in the adducts were either an ester or amide group, and the sterically hindered amines were in the form of -NH, -NO• and -NOR. The spectral properties of the three related derivatives (esters or amides) were quite similar. The maxima of the absorption spectra were in the range of 295-315 nm, and the maximum of fluorescence was located in the range of 330-360 nm, depending on the polarity of the solvent. In polar solvents, a red-shifted fluorescence band at 460-475 nm was observed. The fluorescence of these derivatives was rather weak as compared to anthracene under the same conditions. The Stokes shift was large, as high as 6,000 cm(-1), indicating the formation of a twisted intra-molecular charge transfer (TICT) state. No large differences in Stokes shifts were observed in polymer matrices of poly(methyl methacrylate), polystyrene and poly(vinyl chloride). The extent of intramolecular quenching was expressed as Φ(NX)/Φ(NO) (X = H, NOR) and was in the range of 1-3 in solution and as high as 8 in polymer matrices. The low efficiency of intramolecular quenching limits the application of these new adducts as fluorescence probes for the monitoring of radical processes in solution but favors their application in polymer matrices.