4f-LUMINESCENCE OF 3d-4f HETERONUCLEAR PORPHYRIN COMPLEXES
DOI:
https://doi.org/10.15421/jchemtech.v30i3.261538Keywords:
lanthanides; porphyrins; 4f-luminescence; sensitization; heteronuclear complexesAbstract
Porphyrin compounds with Nd(III), Yb(III) and Cu(II), Zn(II), Pd(II) were obtained on the basis of ditopic porphyrins, the structure of which allowed obtaining various heterometallic complexes. Specified f-metals were chosen due to the fact that the infrared luminescence of these metal ions can be sensitized by porphyrins, on the other hand, the presented d-metal ions have a very different effects on the porphyrin chromophore. Photosensitized 4f-luminescence in the near-infrared region and molecular fluorescence in the visible region of 3d-4f heteronuclear complexes are extremely sensitive to the nature of d- and f-metal ions. Thus, effective molecular fluorescence (quantum yield 4–11 %) is characteristic for the cases of free porphyrin cores and complexes with Zn(II). Moreover, these cases reveal three types of emission – fluorescence, phosphorescence and 4f-luminescence at the same time. We found out that the molecular fluorescence effectiveness and the values of its band maxima did not depend on the nature of the peripheral chelate fragments. Fluorescence of copper and palladium complexes is almost completely quenched, but Pd(II)-porphyrin serves as 4f-sensitizer in contrast to Cu(II)-porphyrin. The effect of oxygen on the luminescence of the complexes was considered. It was found that only Pd-Nd complexes are sensitive to its presence – deoxygenation led to 20 % enhancement of 4f-luminescence effectiveness.
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