The effect of protonation on the excited state properties of the three positional isomers of E-5-[2-(pyrid-n-yl)ethenyl]oxazole's (n-PyEt-50x with n = 2, 3 and 4) was studied in buffered water by spectrophotometric, fluorimetric and chromatographic measurements. The clear shift to the red of the absorption and emission spectra by protonation indicates that the basicity of these compounds increases strongly (by similar to 7 pH units) under excitation. Ground state pK(a) values (around 5) were measured by absorption (for n = 2 and 4) and fluorescence (for n = 3) titration and excited state pK(a)(*) values were estimated by application of the Forster cycle. For the compound with n = 3, which displays a rather higher fluorescence lifetime, it was possible to perform a direct fluorimetric titration which showed two inflection points corresponding to pK(a) (4.77) and pK(a)(*) (12.27). Previous works on these compounds had shown a marked deactivating effect of the pyridine n,pi(*) states on the emitting and reactive pi,pi(*) states (proximity effect) favouring relaxation by internal conversion with a marked reduction of the competitive fluorescence and trans-cis (E-Z) isomerisation yields, particularly for n = 2 and 4 in non-polar cyclohexane. The new results indicate that the aqueous solvent, and mainly protonation, affect sensibly the spectral, photochemical and photophysical behaviour increasing again the radiative and reactive parameters of compounds with n = 2 and 4. The isomer with n = 3, whose n,pi(*) states play a much smaller deactivating effect, shows a peculiar behaviour with a verylow isomerisation yield-at acid pH, reasonably due to intramolecular charge transfer from the Ox ring to the PyH+ moiety, which hinders the twisting process. All these results are compared with those reported in the,literature for the n-styrylpyridine analogues, to point out the role of the oxazole group.
Proton transfer in the ground and excited state and photobehaviour of the positional isomers of E-5-[2-(pyrid-n-yl)ethenyl]oxazole's (n=2, 3 and 4)
BOTTI, VALENTINA;MAZZUCATO, Ugo;SPALLETTI, Anna
2017
Abstract
The effect of protonation on the excited state properties of the three positional isomers of E-5-[2-(pyrid-n-yl)ethenyl]oxazole's (n-PyEt-50x with n = 2, 3 and 4) was studied in buffered water by spectrophotometric, fluorimetric and chromatographic measurements. The clear shift to the red of the absorption and emission spectra by protonation indicates that the basicity of these compounds increases strongly (by similar to 7 pH units) under excitation. Ground state pK(a) values (around 5) were measured by absorption (for n = 2 and 4) and fluorescence (for n = 3) titration and excited state pK(a)(*) values were estimated by application of the Forster cycle. For the compound with n = 3, which displays a rather higher fluorescence lifetime, it was possible to perform a direct fluorimetric titration which showed two inflection points corresponding to pK(a) (4.77) and pK(a)(*) (12.27). Previous works on these compounds had shown a marked deactivating effect of the pyridine n,pi(*) states on the emitting and reactive pi,pi(*) states (proximity effect) favouring relaxation by internal conversion with a marked reduction of the competitive fluorescence and trans-cis (E-Z) isomerisation yields, particularly for n = 2 and 4 in non-polar cyclohexane. The new results indicate that the aqueous solvent, and mainly protonation, affect sensibly the spectral, photochemical and photophysical behaviour increasing again the radiative and reactive parameters of compounds with n = 2 and 4. The isomer with n = 3, whose n,pi(*) states play a much smaller deactivating effect, shows a peculiar behaviour with a verylow isomerisation yield-at acid pH, reasonably due to intramolecular charge transfer from the Ox ring to the PyH+ moiety, which hinders the twisting process. All these results are compared with those reported in the,literature for the n-styrylpyridine analogues, to point out the role of the oxazole group.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
