New luminescent pH-responsive europium complex for multimodal sensing in extremely wide pH range

Kharcheva, A.V.; Charyshnikova, Z.A.; Borisova, N.E.; Sumyanova, T.B.; Farat, O.K.; Kharitonov, D.A.; Patsaeva, S.V.

Авторы: Kharcheva Anastasiia V., Charyshnikova Zinaida A., Borisova Nataliya E., Sumyanova Tsagana B., Farat Oleg K., Kharitonov Dmitriy A., Patsaeva Svetlana V.
Журнал: Journal of Luminescence
Том: 243
Год издания: 2022
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Номер статьи: 118678
DOI: 10.1016/j.jlumin.2021.118678
Аннотация: The new water-soluble europium complex, {(4,7-dichloro-1,10-phenanthroline-2,9-diyl)bis[carbonylnitrilodi(methylene)]}-tetrakis(phosphonato) europium (III), was synthesized and characterized in details spectroscopically. The complex emits narrow lines in the red region of the spectrum when irradiated with the UV radiation. Various luminescence characteristics of this complex dissolved in light and heavy water, as well as in the solid form at room temperature and at the temperature of liquid nitrogen, have been determined. Each independent luminescent characteristic showed individual behavior on pH alteration in aqueous solutions. Below pH = 2.5, we found sharp changes in the luminescence quantum yield and the area ratio for the Gaussian components within the band 5D0→7F4. The changes in the asymmetry coefficient, luminescence lifetime and the Gaussian components area ratio (reversed trend compared to pH < 2.5) were the most visible in the pH range from 2.5 to 3.5. Above pH = 3.5 we observed changes in the asymmetry coefficient (reversed trend compared to lower pH values), luminescence quantum yield and luminescence lifetime. From pH 3 to 10.1, the intensities ratio I290/I325 (ratio of luminescence intensity of the band corresponding to “hypersensitive” transition 5D0 → 7F2 excited at 290 nm to that excited at 325 nm) is monotonically decreasing, which makes possible to suggest this luminescence characteristic for pH sensing in the pH range above 3. We resume that in different protonated environments, there exist three species of the europium complex differing in luminescence characteristics (luminescence quantum yield and lifetime, asymmetry coefficient, band shape corresponded to the 5D0→7F4 transition). This finding makes possible application of a luminescent probe as a multimodal pH sensor in the wide range of aqueous environments, from pH 0.5 to 10.1, using specific luminescent characteristics in each pH sub-range.
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