Insight into the Magnetic Exchange Interactions and Anisotropy in Heterobimetallic CuII-LnIII Complexes: A Rare Example of Cu-Gd Single-Molecule Magnets

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F24%3A73627712" target="_blank" >RIV/61989592:15310/24:73627712 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c00752" target="_blank" >https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c00752</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.cgd.4c00752" target="_blank" >10.1021/acs.cgd.4c00752</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Insight into the Magnetic Exchange Interactions and Anisotropy in Heterobimetallic CuII-LnIII Complexes: A Rare Example of Cu-Gd Single-Molecule Magnets

Popis výsledku v původním jazyce

The exploration of heterometallic complexes containing both 3d and 4f metal ions has been on the rise with advancements in the field of 3d-4f single-molecule magnets. The motivation stemmed from early investigations into the Cu-II-Ln(III) systems, particularly the Cu-II/Gd-III one, that revealed a ferromagnetic interaction between these ions, irrespective of the complex&apos;s topology or nuclearity. In this context, we have synthesized three new isostructural and isomorphous [CuLn(L)(NO3)(3)(H2O)] complexes (Ln = Gd (&lt;bold&gt;1&lt;/bold&gt;), Tb (2), and Dy (3)) derived from a compartmental Schiff base ligand H2L. All three complexes were structurally characterized in which Cu-II and Ln(III) ions occupy inner N2O2 and outer O2O &apos;(2) compartments of the doubly deprotonated Schiff base ligand, respectively. Moreover, another closely related complex [Cu(L)](2)[CuDy(L)(OAc)(NO3)(H2O)](NO3)&lt;middle dot&gt;5H(2)O (4) has been synthesized starting from the same Schiff base ligand H2L to examine the effect of the coordination environment around the Dy-III ion on the dynamic magnetic behavior in these systems. Variable-temperature direct-current magnetic susceptibility measurements suggest a ferromagnetic exchange interaction between Cu-II and Ln(III) ions, especially in 1-3, which is further supported by DFT calculations. However, alternating-current magnetic susceptibility measurements resulted in the most interesting part of this report. Remarkably, despite the isotropic nature of the Gd-III ion, compound 1 displayed slow relaxation of the magnetization in the presence of an applied field together with its anisotropic counterparts Tb-III (2) and Dy-III (3). Based on the literature study, this is a rare system in which Cu-II-Gd-III complexes showed single-molecule magnet behavior. Moreover, theoretical calculations were also performed by means of DFT and CASSCF levels of theory to obtain precise information on the magnetic exchange coupling between Cu-II and Ln(III) ions together with the distinct magnetic dynamics in these systems.

Název v anglickém jazyce

Insight into the Magnetic Exchange Interactions and Anisotropy in Heterobimetallic CuII-LnIII Complexes: A Rare Example of Cu-Gd Single-Molecule Magnets

Popis výsledku anglicky

The exploration of heterometallic complexes containing both 3d and 4f metal ions has been on the rise with advancements in the field of 3d-4f single-molecule magnets. The motivation stemmed from early investigations into the Cu-II-Ln(III) systems, particularly the Cu-II/Gd-III one, that revealed a ferromagnetic interaction between these ions, irrespective of the complex&apos;s topology or nuclearity. In this context, we have synthesized three new isostructural and isomorphous [CuLn(L)(NO3)(3)(H2O)] complexes (Ln = Gd (&lt;bold&gt;1&lt;/bold&gt;), Tb (2), and Dy (3)) derived from a compartmental Schiff base ligand H2L. All three complexes were structurally characterized in which Cu-II and Ln(III) ions occupy inner N2O2 and outer O2O &apos;(2) compartments of the doubly deprotonated Schiff base ligand, respectively. Moreover, another closely related complex [Cu(L)](2)[CuDy(L)(OAc)(NO3)(H2O)](NO3)&lt;middle dot&gt;5H(2)O (4) has been synthesized starting from the same Schiff base ligand H2L to examine the effect of the coordination environment around the Dy-III ion on the dynamic magnetic behavior in these systems. Variable-temperature direct-current magnetic susceptibility measurements suggest a ferromagnetic exchange interaction between Cu-II and Ln(III) ions, especially in 1-3, which is further supported by DFT calculations. However, alternating-current magnetic susceptibility measurements resulted in the most interesting part of this report. Remarkably, despite the isotropic nature of the Gd-III ion, compound 1 displayed slow relaxation of the magnetization in the presence of an applied field together with its anisotropic counterparts Tb-III (2) and Dy-III (3). Based on the literature study, this is a rare system in which Cu-II-Gd-III complexes showed single-molecule magnet behavior. Moreover, theoretical calculations were also performed by means of DFT and CASSCF levels of theory to obtain precise information on the magnetic exchange coupling between Cu-II and Ln(III) ions together with the distinct magnetic dynamics in these systems.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

CRYSTAL GROWTH &amp; DESIGN

ISSN

1528-7483

e-ISSN

1528-7505

Svazek periodika

24

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

7537-7548

Kód UT WoS článku

001306527600001

EID výsledku v databázi Scopus

2-s2.0-85203165865