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Preparation and Spectral Characterization of Fluorescence Probes Based on 4-N,N-Dimethylamino Benzoic Acid and Sterically Hindered Amines

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Abstract

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 ΦNX/ΦNO (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.

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Acknowledgments

The authors are greatly acknowledged to Grant agency VEGA for financial support through the project 2/0074/10 and Slovak Research and Development Agency through projects APVV-0109-10 and APVV-0562-07. For NMR measurements provided by the Slovak State Program Project No. 2003SP200280203 are gratefully acknowledged as well. This publication is the result of the project implementation: Centre for materials, layers and systems for applications and chemical processes under extreme conditions supported by the Research & Development Operational Programme funded by the ERDF.

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  1. Polymer Institute, Center of excellence GLYCOMED, Slovak Academy of Sciences, Dubravska cesta 9, 845 41, Bratislava 45, Slovakia

    Csaba Kósa, Martin Danko & Pavol Hrdlovič

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  1. Csaba Kósa
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Correspondence to Csaba Kósa.

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Supplementary data associated (NMR, FTIR spectra and Figures S1–S4) with this article can be found in the online version of the journal.

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Kósa, C., Danko, M. & Hrdlovič, P. Preparation and Spectral Characterization of Fluorescence Probes Based on 4-N,N-Dimethylamino Benzoic Acid and Sterically Hindered Amines. J Fluoresc 22, 1371–1381 (2012). https://doi.org/10.1007/s10895-012-1076-7

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