Mono- and tetranuclear Fe(II, III) complexes with primary 1, 3-diaminopropane: Synthetic aspects, magnetic properties and thermal behavior. (15th September 2021)

• Record Type: Journal Article
• Authors: Lutsenko, Irina A.; Yambulatov, Dmitriy S.; Kiskin, Mikhail A.; Nelyubina, Yulia V.; Primakov, Petr V.; Efimov, Nikolay N.; Babeshkin, Konstantin A.; Khoroshilov, Andrey V.; Maksimov, Yurii V.; Novichikhin, Sergey V.; Zueva, Ekaterina M.; Sidorov, Alexey A.; Eremenko, Igor L.
• Is Part Of: Polyhedron. Volume 206(2021)
• Publication Date: 2021-09-15
• Subjects: Iron(II, III) complexes -- Primary diamine -- Crystal structure -- Magnetic properties -- Mossbauer spectroscopy -- Simultaneous thermal analysis; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2021.115354
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: New iron carboxylate complexes with a aliphatic diamine, 1, 3-diaminopropane ( dap ), were obtained under various synthesis conditions: in the air, [Fe III 4 O2 (Piv)8 ( dap )2 ] (1, Piv is the pivalate anion), and in an inert atmosphere, [Fe II (Piv)2 ( dap )2 ] (2 ). Abstract: New iron carboxylate complexes with a aliphatic diamine, 1, 3-diaminopropane ( dap ), were obtained under various synthesis conditions: in the air, [Fe III 4 O2 (Piv)8 ( dap )2 ] (1, Piv is the pivalate anion), and in an inert atmosphere, [Fe II (Piv)2 ( dap )2 ] (2 ). The structure of the compounds was determined by single crystal X-ray diffraction analysis. In mononuclear complex 2, the iron center coordinates two carboxylate ligands and two chelate dap . In the tetranuclear complex 1, the coordination environment of the metal ions is different, and only two ions coordinate the chelate dap . According to Mössbauer spectroscopy data, the Fe 3+ ions in 1 and Fe 2+ ion in 2 are in a high-spin state and in an octahedral environment of donor atoms. A DC magnetic susceptibility study and quantum-chemical analysis of intramolecular pathways using broken-symmetry density functional theory (DFT) showed that the magnetic exchange coupling between the Fe 3+ ions of the central Fe2 (μ-O)2 unit is weak (| J | ≤ 7 cm −1 ), while each of these ions is coupled by fairly strong antiferromagnetic exchange interactions with two other Fe 3+ ions ( J = −32.9/−43.2 cm −1 ). The thermal behavior of 1 and 2 was studied by simultaneous thermal analysis (STA).