A DFT and Mössbauer spectroscopy investigation of spin‐crossover iron(II) complexes with 2,6‐bis(1H‐imidazol‐2‐yl)pyridines

A DFT and Mössbauer spectroscopy investigation of spin‐crossover iron(II) complexes with 2,6‐bis(1H‐imidazol‐2‐yl)pyridines Full article

Journal

International Journal of Quantum Chemistry
ISSN: 0020-7608 , E-ISSN: 1097-461X

Output data

Year: 2023, Volume: 123, Number: 21, Article number : e27201, Pages count : DOI: 10.1002/qua.27201

Tags

DFT, complexes of iron(II), Mössbauer spectroscopy

Authors

Kozlova Svetlana G. ¹ , Petrov Sergey A. ² , Tikhonov Alexsei Ya. ³ , Lavrenova Lyudmila G. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the RAS
2	Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences
3	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

A quantum chemical study was carried out for a number of iron(II) complexes [FeL2]AinH2O(L=2,6-bis(1H-imidazole-2-yl)pyridine (L1); 2,6-(4,5-dimethyl-1H-imidazole-2-yl)pyridine (L2); 2,6-bis(1H-benzimidazole-2-yl)pyridine (L3); A=ReO4,B10H102,B12H122;n=0–2). These complexes exist in the low spin (LS) form1A1(totalelectron spin S=0) at room temperature and switch to the high spin (HS) form5T2(S=2) upon heating. The experimental isomeric shift and quadrupole splitting valuesfor compounds with L2exceed those for compounds with L1and L3by <0.02> mm/sand <0.1> mm/s, respectively (for LS forms). Such a discrepancy between MS param-eters can be explained by the assumption that chemical bonding between the ironion and the surrounding nitrogen atoms in the compounds with L2may be more ionicin character than that in the compounds with L1and L3. At the same time, the resultsobtained with the TPSSh hybrid meta-GGA functional gave a better agreement withthe experimental data than those obtained with the B3LYP exchange-correlationfunctional.

Kozlova S.G. , Petrov S.A. , Tikhonov A.Y. , Lavrenova L.G.
A DFT and Mössbauer spectroscopy investigation of spin‐crossover iron(II) complexes with 2,6‐bis(1H‐imidazol‐2‐yl)pyridines
International Journal of Quantum Chemistry. 2023. V.123. N21. e27201 . DOI: 10.1002/qua.27201 WOS РИНЦ

Submitted:	Feb 11, 2023
Accepted:	Jul 6, 2023
Published print:	Jul 10, 2023
Published online:	Aug 9, 2023

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