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 Научная публикация

Журнал

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

Вых. Данные

Год: 2023, Том: 123, Номер: 21, Номер статьи : e27201, Страниц : DOI: 10.1002/qua.27201

Ключевые слова

DFT, complexes of iron(II), Mössbauer spectroscopy

Авторы

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

Организации

1	Институт неорганической химии им. А.В. Николаева СО РАН
2	Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук
3	Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН

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

Поступила в редакцию:	11 февр. 2023 г.
Принята к публикации:	6 июл. 2023 г.
Опубликована в печати:	10 июл. 2023 г.
Опубликована online:	9 авг. 2023 г.

Web of science	WOS:001044787300001
РИНЦ	54974861
OpenAlex	W4385704928