Effects of Isomorphous Substitution on Photophysical and Magnetic Properties of Complexes [Ln <sub>1‐</sub> <i> <sub>x</sub> </i> Dy <i> <sub>x</sub> </i> (MeDPQ) <sub>2</sub> Cl <sub>3</sub> ] (Ln = Y <sup>3+</sup> , Ho <sup>3+</sup> , and Er <sup>3
This work encompasses the study of magnetic, optical, and structural properties of the coordination compounds [Ln(MeDPQ)<sub>2</sub>Cl<sub>3</sub>] (Ln ─ Ho<sup>3+</sup>, Er<sup>3+</sup>, Dy<sup>3+</sup>, and Y<sup>3+</sup>; MeDPQ - 2-methyldipyrido-[3,2-f:2',3'-h]-quinoxaline) and substituted complexes [Ln<sub>1-</sub> <sub>x</sub>Dy<sub>x</sub>(MeDPQ)<sub>2</sub>Cl<sub>3</sub>] (Ln = Ho<sup>3+</sup>, Er<sup>3+</sup>, and Y<sup>3+</sup>) based on them. Magnetic measurements within the range 5-300 K revealed single ion anisotropy in [Dy(MeDPQ)<sub>2</sub>Cl<sub>3</sub>], with the Curie-Weiss temperature θ being -3.69 ± 0.03 K. Complexes of Ho<sup>3+</sup> and Er<sup>3+</sup> exhibited f-f emission in the visible range, while the latter was also emissive in the NIR. Dilution of the Dy<sup>3+</sup> complex with diamagnetic Y<sup>3+</sup> ions resulted in alterations of magnetic and photophysical properties. The substituted complexes Y<sub>0.5</sub>Dy<sub>0.5</sub> and Y<sub>0.9</sub>Dy<sub>0.1</sub> demonstrated paramagnetic behavior, with θ being 3.06 ± 0.12 K and 9.64 ± 0.23 K, respectively. In both cases, the emission decay times of Dy<sup>3+</sup> changed insignificantly, 21.02 ± 0.41 µs and 14.56 ± 0.22 µs, respectively, compared to the value (18.92 ± 0.03 µs) of the individual Dy<sup>3+</sup> complex. Additional ligand-based emission bands were observed in the Ho<sup>3+</sup> and Er<sup>3+</sup> complexes at room temperature and 77 K and in the substituted complexes Ho<sub>0.5</sub>Dy<sub>0.5</sub> and Er<sub>0.5</sub>Dy<sub>0.5</sub> at room temperature, which were assigned to the exciplex states. The thermal stability of [Er<sub>0.5</sub>Dy<sub>0.5</sub>(MeDPQ)<sub>2</sub>Cl<sub>3</sub>] was determined to be the same as for the individual complexes, starting to oxidize at 410°C.
Authors
- Ildar I. Mirzayanov (ORCID: https://orcid.org/0000-0002-4204-201X)
- Мaxim S. Моlokeev (ORCID: https://orcid.org/0000-0002-8297-0945)
- R. G. Batulin (ORCID: https://orcid.org/0000-0002-0184-6580)
- Valery G. Shtyrlin (ORCID: https://orcid.org/0000-0003-4820-884X)
- В. А. Бурилов (ORCID: https://orcid.org/0000-0001-7089-3340)
- Elza D. Sultanova (ORCID: https://orcid.org/0000-0001-8796-4352)
- Maksim A. Zhernakov (ORCID: https://orcid.org/0000-0002-0339-5365)
- Klaus Müller‐Buschbaum (ORCID: https://orcid.org/0000-0002-2857-8379)
- Yuriy G. Denisenko (ORCID: https://orcid.org/0000-0003-3453-5188)
Institutions
- Justus-Liebig-Universität Gießen (DE)
- Kazan Federal University (RU)
- University of Tyumen (RU)
- Industrial University of Tyumen (RU)
- Institute of Physics (RU)
- Far Eastern State Transport University (RU)
- Siberian Federal University (RU)
- Kazan State Technological University (RU)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-10-23
- DOI
- https://doi.org/10.1002/chem.202502070
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Deutscher Akademischer Austauschdienst
- Kazan Federal University