Combined Experimental and Theoretical Investigation of the Origin of Magnetic Anisotropy in Pentagonal Bipyramidal Isothiocyanato Co(II), Ni(II), and Fe(III) Complexes with Quaternary-Ammonium-Functionalized 2,6-Diacetylpyridine Bisacylhydrazone
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2019
Authors
Darmanović, DarinkaShcherbakov, Igor N.

Duboc, Carole
Spasojević, Vojislav

Hanžel, Darko
Anđelković, Katarina

Radanović, Dušanka D.
Turel, Iztok

Milenković, Milica R.
Gruden, Maja

Čobeljić, Božidar
Zlatar, Matija
Article (Published version)

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Show full item recordAbstract
Magnetic anisotropy in pentagonal bipyramidal complexes of Co(II) (1 and 2), Fe(III) (3 and 4), and Ni(II) (5) with a 2,2′-[2,6-pyridinediylbis(ethylidyne-1-hydrazinyl-2-ylidene)]bis[N,N,N-trimethyl-2-oxoethanaminium] equatorial ligand and isothiocyanato axial ligands has been investigated by magnetic susceptibility measurements, powder X-band electron paramagnetic resonance (EPR) spectroscopy, Mössbauer spectroscopy, ab initio, and ligand-field density functional theory (LFDFT) calculations. The studied complexes display three distinct types of magnetic anisotropy. Co(II) complexes (1 and 2) show an easy plane anisotropy with large and positive D values and negligible rhombicity. The Ni(II) complex (5) has uniaxial magnetic anisotropy with a negative D value. Fe(III) complexes (3 and 4) have small zero-field splitting (ZFS) parameters. Theoretical modeling is used to rationalize the magnetic anisotropy in these systems and to identify the most important excited states that are respons...ible for the zero-field splitting. These excitations are a consequence of the electronic structure of the central metal ion in ideal pentagonal bipyramidal coordination.
Keywords:
Magnetic properties / Electron paramagnetic resonance spectroscopy / Quantum mechanics / Mössbauer spectroscopy / Magnetic susceptibility measurements / ab initio / Ligand Field Theory / Group theory / Magnetic anisotropy / Zero Field Splitting / LFDFT / DFT / Theoretical modeling / Symmetry / Pentagonal BipyramidalSource:
The Journal of Physical Chemistry C, 2019, 123, 51, 31142-31155Projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
- Interactions of natural products, their derivatives and coordination compounds with proteins and nucleic acids (RS-172055)
- Slovenian Research Agency (P1-0175)
- Slovenian Research Agency (P1-0112)
- Southern Federal University
Note:
- The peer-reviewed version: http://cherry.chem.bg.ac.rs/handle/123456789/3856
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3857
DOI: 10.1021/acs.jpcc.9b08066
ISSN: 1932-7447; 1932-7455
WoS: 000505632900041
Scopus: 2-s2.0-85076722011
URI
http://cherry.chem.bg.ac.rs/handle/123456789/3855http://vinar.vin.bg.ac.rs/handle/123456789/8751