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Abstract
Spectral and photophysical characteristics of a number of free bases and zinc complexes of cationic porphyrins that were synthesized in order to modify their specific interaction with biomolecules were studied. It was shown that the electronic excitation-energy intramolecular relaxation rate constants (fluorescent k f and non-fluorescent knf for the photosensitizer S 1 → S 0 transition and also intersystem crossing rate constant kisc for the S 1 → T 1 transition) decreased by ~1.5 times for [3-pyridyl]porphyrin free bases as compared with the [4-pyridyl]-isomers. A chargetransfer state for both the free bases and the Zn-porphyrins impacted directly the shape of the fluorescence spectra and contributed equally to relaxation through the S 1 → S 0, S 1 ~ ~ > S 0, and S 1 ~ ~ > T 1 paths. All studied porphyrins exhibited high quantum yields for singlet-oxygen formation (~80 %) with an intrinsic fluorescence level of several percent. Such photophysical parameters indicated that the examined water-soluble porphyrins were promising compounds for both application in targeted photodynamic therapy and fabrication of luminescent sensors.
Published Version
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