Repozytorium

Synthesis, XRD, EMR, magnetic, and optical studies of trigonal and triclinic dinuclear MNM-analogous Gd3+ complexes

Autorzy

Dawid Marcinkowski

Marta Fik-Jaskółka

Adam Gorczyński

Violetta Patroniak

Maciej Kubicki

Ireneusz Stefaniuk

Magdalena Wencka

Muhammed Açikgöz

Maria Korabik

Mirosław Karbowiak

Czesław Rudowicz

Rok wydania

2025

Czasopismo

Journal of Magnetism and Magnetic Materials

Numer woluminu

628

Strony

173184/1-173184/10

DOI

10.1016/j.jmmm.2025.173184

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Two structurally similar dinuclear Gd3+ complexes are newly synthesized as potential molecular nanomagnets (MNMs): [Gd2(L1)3](NO3)3 (1 symmetric) and [Gd2(L2)3(NO3)3] (2 dissymmetric). Characterization by variety of experimental techniques: XRD, EMR, magnetic measurements, and optical spectroscopy was carried out. The EMR and magnetic measurements reveal that the two Gd3+ complexes show very weak exchange interactions. Hence these complexes can be classified as the MNM-analogous complexes. The zero-field splitting (ZFS) parameters bkq were fitted from EMR spectra using the forms of the zero-field splitting Hamiltonian (HZFS) suitable for Gd3+ ions at various symmetry sites. This enabled exposing the role of site symmetry for proper interpretation of spectroscopic and magnetic properties of these Gd3+ complexes. Several fitting schemes were employed to investigate the relative importance of each k-rank bkq′s for Gd3+ ions. The distinction between actual (low/high) site symmetry and apparent (lower/higher) site symmetry was introduced. Since for triclinic site symmetry (complex 2), infinite number of physically equivalent ZFSP sets exist, to assess equivalence of independently obtained sets, we utilize the invariant quantities and standardization. Our findings clearly demonstrate the importance of the low and high symmetry aspects in EMR studies. This paper prepares grounds for an in-depth study of the symmetry aspects inherent in the modelled ZFSP sets for the two complexes. These aspects are not well recognized as yet and thus are frequently overlooked in literature. Their elucidation is crucial since improper treatment of the low and high symmetry aspects may potentially lead to erroneous interpretations of compounds’ properties.

Słowa kluczowe

EMR/EPR, XRD, Magnetic measurements, Zero-field splitting, Dinuclear Gd3+ complexes, Molecular nanomagnets, Symmetry aspects

Adres publiczny

http://dx.doi.org/10.1016/j.jmmm.2025.173184

Strona internetowa wydawcy

http://www.elsevier.com

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Critical evaluation of ambiguities in computational modelling of zero-field splitting parameters – case study: trigonal and triclinic dinuclear Gd3+ complexes

Marcinkowski Dawid, Fik-Jaskółka Marta, Gorczyński Adam, Patroniak Violetta, Kubicki Maciej, Stefaniuk Ireneusz, Ślusarski Tomasz, Açikgöz Muhammed, Piwowarska Danuta, Gnutek Paweł, Korabik Maria, Karbowiak Mirosław, Rudowicz Czesław