Halide mediated modulation of magnetic interaction and anisotropy in dimeric Co(ii) complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F24%3A73627686" target="_blank" >RIV/61989592:15310/24:73627686 - isvavai.cz</a>
Result on the web
<a href="https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00927d" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00927d</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d4dt00927d" target="_blank" >10.1039/d4dt00927d</a>
Alternative languages
Result language
angličtina
Original language name
Halide mediated modulation of magnetic interaction and anisotropy in dimeric Co(ii) complexes
Original language description
The burgeoning interest in the field of molecular magnetism is to perceive the high magnetic anisotropy in different geometries of metal complexes and hence to draw a magneto-structural correlation. Despite a handful of examples to exemplify the magnetic anisotropy in various coordination geometries of mononuclear complexes, the magnetic anisotropies for two different coordination geometries are underexplored. Employing an appropriate synthetic strategy utilizing the ligand LH2 [2,2 '-{(1E,1 ' E)-pyridine2,6-diyl-bis(methaneylylidine)}-bis(azaneylylidine)diphenol] and cobalt halide salts in a 1 : 2 stoichiometric ratio in the presence of triethylamine allowed us to report a new family of dinuclear cobalt complexes [(Co2X2)-X-II(L)(P)(Q)]<middle dot>S with varying terminal halides [X = Cl, P = CH3CN, Q = H2O, S = H2O (1), X = Br, P = CH3CN, Q = H2O, S = H2O (2), X = I, P = CH3CN, and Q = CH3CN (3)]. All these complexes are characterized through single crystal X-ray crystallography, which reveals their crystallization in the monoclinic system P2(1)/n space group with nearly identical structural features. These complexes share vital components, including Co(ii) centers, a fully deprotonated ligand [L](2-), halide ions, and solvent molecules. The [L](2-) ligand contains two Co(ii) centers, where phenolate oxygen atoms bridge the Co(ii) centers, forming a Co2O2 four-membered ring. Co1 demonstrates a distorted pentagonal-bipyramidal geometry with axial positions for solvent molecules, while Co2 displays a distorted tetrahedral geometry involving phenolate oxygen atoms and halide ions. Temperature-dependent dc magnetic susceptibility measurements were conducted on 1-3 within a range of 2 to 300 K at 1 kOe. The chi T-m vs. T plots exhibit similar trends, with chi T-m values at 300 K higher than the spin-only value, signifying a significant orbital contribution. As the temperature decreases, chi T-m decreases smoothly in all the complexes; however, no clear saturation at low temperatures is observed. Field-dependent magnetization measurements indicate a rapid increase below 20 kOe, with no hysteresis and a low magnetic blocking temperature. DFT and CASSCF/NEVPT2 theoretical calculations were performed to perceive the magnetic interaction and single-ion anisotropies of Co(ii) ions in various ligand-field environments.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
53
Issue of the periodical within the volume
25
Country of publishing house
GB - UNITED KINGDOM
Number of pages
12
Pages from-to
10499-10510
UT code for WoS article
001239733900001
EID of the result in the Scopus database
2-s2.0-85195422876