(CN3H6)[FeIIFeIII(SO4)3(H2O)3]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice

Ginga, V.A.; Siidra, O.I.; Tsirlin, A.A.; Setzer, A.; Charkin, D.O.; Börner, M.; Abdulina, V.R.; Ivanov, S.A.; Gorbachevskaya, D.A.; Zolotov, N.A.

Авторы: Ginga Victoria A., Siidra Oleg I., Tsirlin Alexander A., Setzer Annette, Charkin Dmitri O., Börner Martin, Abdulina Veronika R., Ivanov Semen A., Gorbachevskaya Darya A., Zolotov Nikita A.
Журнал: Inorganic Chemistry
Том: 62
Номер: 43
Год издания: 2023
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 17625
Последняя страница: 17633
DOI: 10.1021/acs.inorgchem.3c02109
Аннотация: A new guanidinium-templated hydrated iron sulfate, [CN3H6][FeIIFeIII(SO4)3(H2O)3] (1), was prepared from strongly acidic aqueous solutions. Its crystal structure is comprised from FeIIIO6 and FeIIO3(H2O)3 octahedra linked by sulfate bridges forming a [FeIIFeII(SO4)3(H2O)3]− 3D framework with a layer-bylayer ordering of ferric and ferrous cations. The structural topology of the framework is related to the anhydrous rhombohedral mikasaite Fe2(SO4)3. The removal of part of the sulfate tetrahedra and the partial replacement of the Fe3+ cations in the [Fe3+2(SO4)3]0 framework by Fe2+ provide a negative charge and allow the incorporation of the protonated organic species in the voids. The compound 1 has been characterized by single-crystal Xray diffraction, TG and DSC analyses, UV−vis−NIR spectroscopy, magnetic susceptibility, Mössbauer spectroscopy, IR and Raman spectroscopy, and density functional band-structure calculations. The magnetic behavior of 1 shows an interplay of FeII (S = 2) and FeIII (S = 5/2) sublattices that exhibit different types of antiferromagnetic couplings, one FeIII−FeIII (J1 ∼ 6.1 K) and two FeII−FeIII couplings (J2 ∼ 1 K, J3 ∼ 5.9 K) within corrugated honeycomb layers. These ferrimagnetic layers are coupled antiparallel to each other, resulting in an overall antiferromagnetic order below TN = 31 K.
Добавил в систему: Чаркин Дмитрий Олегович

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(CN<sub>3</sub>H<sub>6</sub>)[Fe<sup>II</sup>Fe<sup>III</sup>(SO<sub>4</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]: A Framework Iron Sulfate with a Mixed <i>S</i> = 2 and <i>S</i> = 5/2 Honeycomb Latticeстатья

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