Validation of Ab‐Initio‐Predicted Magnetic Anisotropies and Magneto‐structural Correlations in Linear Hetero‐trinuclear DyIII‐NiII2 Compounds

Reported are single crystal SQUID and single crystal high‐frequency/high‐field EPR data of a trinuclear complex with a rare six‐coordinate coordination sphere of a DyIII center coupled to two terminal six‐coordinate NiII ions. The analysis of the single crystal spectroscopic parameters allows for an...

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Veröffentlicht in:Chemistry : a European journal Jg. 27; H. 36; S. 9372 - 9382
Hauptverfasser: Comba, Peter, Enders, Markus, Großhauser, Michael, Hiller, Markus, Klingeler, Rüdiger, Koo, Changhyun, Müller, Dennis, Rajaraman, Gopalan, Swain, Abinash, Tavhelidse, Msia, Wadepohl, Hubert
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim Wiley Subscription Services, Inc 25.06.2021
Schlagworte:
ab initio quantum-chemical calculations
Chemistry
Electron spin
Field theory
Ground state
Ligands
Magnetic properties
NMR
Nuclear magnetic resonance
paramagnetic NMR spectroscopy
Parameters
single crystal HF-EPR spectroscopy
single crystal SQUID magnetometry
Single crystals
six-coordinate dysprosium(III)
Wave functions
ISSN:0947-6539, 1521-3765
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Zusammenfassung:Reported are single crystal SQUID and single crystal high‐frequency/high‐field EPR data of a trinuclear complex with a rare six‐coordinate coordination sphere of a DyIII center coupled to two terminal six‐coordinate NiII ions. The analysis of the single crystal spectroscopic parameters allows for an accurate description of the ground state wavefunction. The experimental analysis is supplemented by the analysis of the paramagnetic NMR spectra, allowing for a thorough description of the DyIII center. The experimental data are interpreted on the basis of an ab initio ligand field analysis, and the computed parameters are in good agreement with the experimental observations. This supports the quality of the theoretical approach based on a pseudo‐spin Hamiltonian for the electronic ground state. Further support emerges from the ab initio ligand field theory based analysis of a structurally very similar system that, in contrast to the complex reported here, shows single molecule magnetic properties, and this is in agreement with the quantum‐chemical prediction and analysis. Discussed is a linear trinuclear DyIIINiII2 complex with a rare hexacoordinate DyIII center. The magnetic properties were studied experimentally by single crystal SQUID magnetometry, single crystal high‐frequency/high‐field EPR and paramagnetic NMR spectroscopy. Parameters describing the ground state multiplet splitting have also been computed by ab‐initio quantum‐chemical calculations, and the large variety of experimental techniques allows for a thorough validation of the computational analysis.
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202100626