57Fe Mössbauer and DFT study of the electronic and spatial structure of the iron(II) (pseudo)clathrochelates: the effect of a ligand field strength

Balatskiy, D.V.; Chuprin, A.S.; Dudkin, S.V.; Desdín García, L.F.; Corcho-Valdés, A.L.; Antuch, M.; Buznik, V.M.; Bratskaya, S.; Voloshin, Y.Z.

Авторы: Balatskiy Denis V., Chuprin Alexander S., Dudkin Semyon V., Desdín García Luis Felipe, Corcho-Valdés Angel Luis, Antuch Manuel, Buznik Vyacheslav M., Bratskaya Svetlana, Voloshin Yan Z.
Журнал: Physical Chemistry Chemical Physics
Том: 25
Год издания: 2023
Издательство: Royal Society of Chemistry
Местоположение издательства: United Kingdom
Первая страница: 18679
Последняя страница: 18690
DOI: 10.1039/D3CP01887C
Аннотация: Combined experimental 57Fe Mössbauer and theoretical DFT study of a series of iron(II)-centered (pseudo)macrobicyclic analogs and homologs was performed. The field strength of the corresponding (pseudo)encapsulating ligand was found to affect both the spin state of a caged iron(II) ion and the electron density at its nucleus. In a row of the iron(II) tris-dioximates, passing from the non-macrocyclic complex to its monocapped pseudomacrobicyclic analog, caused an increase both in the ligand field strength and in the electron density at Fe2+ ion, and, therefore, a decrease in the isomer shift (IS) value (so-called “semiclathrochelate effect”). Its macrobicyclization, giving the quasiaromatic cage complex, caused a further increase in two former parameters and a decrease in IS (so-called “macrobicyclic effect”). The trend of their IS values was successfully predicted using the performed quantum-chemical calculations and the corresponding linear correlation with an electron density at their 57Fe nuclei was plotted. Variety of the different functionals can be successfully used for such excellent prediction. The slope of this correlation was found to be unaffected by the used functional. Contrary, the predictions of both the sign and the values of quadrupole splitting (QS) for them, basing on the theoretical calculations of EFG tensors, were found to be a real great challenge, which could not be solved at the moment even in the case of these C3-pseudosymmetric iron(II) complexes with known XRD structures. The latter experimental data allowed to deduce a sign of QSs for them. The strainforwarded molecular design of a (pseudo)encapsulating ligand is proposed to control of both the spin state and the redox characteristics of an encapsulated metal ion.
Добавил в систему: Чуприн Александр Сергеевич

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57Fe Mössbauer and DFT study of the electronic and spatial structure of the iron(II) (pseudo)clathrochelates: the effect of a ligand field strengthстатья Исследовательская статья

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