NIR-LUMINESCENCE OF YTTERBIUM IONS IN ISOMERIC TETRAPHENYLPORPHYRIN MODIFIED EDTA COMPLEXES

Authors

  • Nikolay M. Semenishyn A.V. Bogatsky Physico-Chemical Institute NASU, Ukraine https://orcid.org/0000-0002-1176-9750
  • Valeriia V. Linnyk A.V. Bogatsky Physico-Chemical Institute NAS of Ukraine, I.I. Mechnikov Odesa National University, Ukraine
  • Serhii S. Smola A.V. Bogatsky Physico-Chemical Institute of National Academy of Sciences of Ukraine, Ukraine
  • Natalya V. Rusakova A.V. Bogatsky Physico-Chemical Institute of National Academy of Sciences of Ukraine, Ukraine

DOI:

https://doi.org/10.15421/jchemtech.v33i1.315032

Keywords:

porphyrins, lanthanides, luminescence, energy transfer

Abstract

New ytterbium complexes were synthesized on the base of tetraphenylporphyrin modified with ethylenediaminetetraacetic acid at the ortho- and para-positions of only one phenyl ring. Such modification avoids the problem of lability of traditional lanthanide-porphyrin core-coordinated complexes. A new selective synthetic route for the mono para-nitro-derivative of tetraphenylporphyrin (the main precursor of the target compound) has been proposed.  4f-Luminescence in the near-infrared range as well as non-quenched molecular fluorescence of porphyrin, are observed in all synthesized complexes, which makes these complexes dual-emissive. Since the obtained results show that both Yb-porphyrin isomers have no changes in terms of fluorescence effectiveness in comparison to their corresponding ditopic porphyrins, it proves the absence of ISC and ISD acceleration in these systems. It was also found that the 4f-luminescence intensity of the ortho-isomer is higher compared to the para-isomer. This is due to changes in the spatial structure, leading to the edta-Yb fragment being closer to the porphyrin core. Additional experiment of luminescence quenching by strong paramagnetic ion was performed. When the copper (II) acetate was added to the modified porphyrin isomers, a significant difference in the efficiency of luminescence quenching was observed as the result of non-core interaction; thus, the luminescence intensity decreased more for the ortho-isomer than for the para-isomer. This also proves that the efficiency of interaction between porphyrin and the peripheral substituent is very sensitive to the distance changes between them. Enhancing of 4f-luminescence effectiveness can be explained simultaneously by both decreasing the donor-acceptor distance and the absence of notable ISD acceleration which is typical for core-coordinated compounds.

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Published

2025-04-15

Issue

Vol. 33 No. 1 (2025): Journal of Chemistry and Technologies

Section

Physical and inorganic chemistry

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Copyright (c) 2025 Oles Honchar Dnipro National University

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