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Ground and excited state dipole moments and polarizabilities of 2,5-bis(benzoxazolyl)hydroquinone (BBHQ) and 3,6-bis(benzoxazolyl)pyrocatechol (BBPC) are determined by means of electrooptical absorption and emission measurements. BBHQ is found to exhibit a small, while BBPC a large increase of the static polarizability in the Franck–Condon (FC) excited singlet state. The change of the dipole moments upon excitation to the FC state is zero within experimental error. However, both molecules show dipole moments in the fluorescent states of their phototautomers, of about 5 D, the major component being parallel to the long molecular axis. The experimental and theoretical results strongly suggest that the fluorescent species of BBHQ and BBPC are monoketo-tautomers created by single proton transfer in the course of the excited state relaxation. For BBPC this was confirmed by a comparative photophysical study with its monomethoxy-derivative (MeBBPC), in which one active proton is replaced by the CH3 group. These results lead to the revision of previous conclusions [Grabowska et al., Chem. Phys. Lett. 177 (1991) 17] stating that BBPC undergoes a double proton transfer in the excited state. For BBHQ the previously found single proton transfer mechanism of tautomerization is fully confirmed. |
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