Binuclear heterometallic {M-Ln} pivalate complexes (M = Co, Ni, Cu; Ln = Sm, Gd): synthesis, structure, and thermolysis

Orlova, Elena V.; Goldberg, A. E.; Кискин, М. А.; Koroteev, Pavel S.; Емелина, А. Л.; Bykov, M. A.; Александров, Г. Г.; Доброхотова, Ж. В.; Новоторцев, В. М.; Еременко, И. Л.

doi:10.1007/s11172-011-0343-0

Cited by 8 publications

(3 citation statements)

References 28 publications

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“…In the TGA experiment, the complexes decompose at high temperature, low pressure, and in the absence of air; therefore, low molecular weight compounds could be formed of metal-containing pivalate which in turn could be volatile. This phenomenon has been reported previously a number of times. − A consequence of this, 1 mol of GdFeO 3 will form instead of two. Hence, the mechanism of thermolysis under the TGA conditions may proceed differently to that of the melt method and the resulting gadolinium orthoferrite powders are therefore different.…”

Section: Resultssupporting

confidence: 68%

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

et al. 2020

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Four 3d−4f hetero-polymetallic complexes [Fe 2 Ln 2 ((OCH 2 ) 3 CR) 2 (O 2 C t Bu) 6 (H 2 O) 4 ] (where Ln = La (1 and 2) and Gd (3 and 4); and R = Me (1 and 3) and Et (2 and 4)) are synthesized and analyzed using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and SQUID magnetometry. Crystal structures are obtained for both methyl derivatives and show that the complexes are isostructural and adopt a defective dicubane topology. The four heavy metals are connected with two alkoxide bridges. These four precursors are used as single-source precursors to prepare rare-earth orthoferrite pervoskites of the form LnFeO 3 . Thermal decomposition in a ceramic boat in a tube furnace gives orthorhombic LnFeO 3 powders using optimized temperatures and decomposition times: LaFeO 3 formed at 650 °C over 30 min, whereas GdFeO 3 formed at 750 °C over 18 h. These materials are structurally characterized using powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray map spectroscopy, and SQUID magnetometry. EDX spectroscopy mapping reveals a homogeneous spatial distribution of elements for all four materials consistent with LnFeO 3 . Magnetic measurements on complexes 1−4 confirm the presence of weak antiferromagnetic coupling between the central Fe(III) ions of the clusters and negligible ferromagnetic interaction with peripheral Gd(III) ions in 3 and 4. Zero-field-cooled and field-cooled measurements of magnetization of LaFeO 3 and GdFeO 3 in the solid-state suggest that both materials are ferromagnetic, and both materials show open magnetic hysteresis loops at 5 and 300 K, with M sat higher than previously reported for these nanomaterials. We conclude that this is a new and facile low temperature route to these important magnetic materials that is potentially universal, limited only by what metals can be programmed into the precursor complexes.

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Section: Resultssupporting

confidence: 68%

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

et al. 2020

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“…Since pivalic acid (pivH) has been shown to be an excellent co-ligand, preventing extensive hydrolysis of the metal centres, for the synthesis of 3d/4f polynuclear CCs, 19 CRYSALIS CCD and RED software was used respectively for data collection and processing. Reflection intensities were corrected for absorption by the multi-scan method.…”

Section: Introductionmentioning

confidence: 99%

“…Since pivalic acid ( pivH) has been shown to be an excellent co-ligand, preventing extensive hydrolysis of the metal centres, for the synthesis of 3d/4f polynuclear CCs, [19][20][21][22][23][24][25] we decided to incorporate it in the reaction system that afforded the two isoskeletal Co II 3 Dy III 4 CCs (1 and 2), resulting in the synthesis of seven new compounds formulated as [Co II 2 Dy III 2 (µ 3 -MeO) 2 (L) 2 -( piv 9) with robust and unprecedented topologies. These show that the temperature and reaction time influence the formation of the final product.…”

Section: Introductionmentioning

confidence: 99%

A new family of high nuclearity Co^II/Dy^III coordination clusters possessing robust and unseen topologies

et al. 2015

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Mixing Co(NO3)2·6H2O/Dy(NO3)3·6H2O/(E)-4-(2-hydroxy-3-methoxybenzylideneamino)-2,3-dimethyl-1-phenyl-1,2-dihydropyrazol-5-one (HL)/pivalic acid/Et3N in various solvents results in the synthesis of seven compounds formulated as [CoII2DyIII2(μ3-MeO)2(L)2(piv)4(NO3)2] (3), [CoIIDyIII3(μ3-MeO)2(μ2-MeO)2(L)2(piv)2(NO3)3]·2(CH3OH) (4·2CH3OH), 2[CoII4DyIII4(μ2-O)2(μ3-OH)4(L)4(piv)8][CoII2DyIII5(μ3-OH)6(L)2(piv)8(NO3)4] (5), [CoII4DyIII4(μ2-O)2(μ3-OH)4(L)4(piv)8]·2(CH3CN) (6·2CH3CN), [CoII2DyIII5(μ3-OH)6(L)2(piv)8(NO3)4]·4(CH3CN) (7·4CH3CN), [CoII2DyIII2(μ3-OH)2(L)2(piv)2(NO3)2(EtOH)2(H2O)2](NO3)2·(EtOH) (8·EtOH) and [CoII4DyIII4(μ2-O)2(μ3-OH)4(L)4(piv)8] (9) with robust and unseen topologies. These show that the temperature and reaction time influence the formation of the final product. Preliminary magnetic studies, performed for 6 and 7 in the temperature range 2–300 K, are indicative of Single Molecule Magnet (SMM) behaviour. Moreover, analysis of the catalytic properties of compound 3 as an efficient catalyst for the synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary amines has been carried out.

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Thermolysis of Polymeric Metal Chelates

Uflyand

Джардималиева

2018

Nanomaterials Preparation by Thermolysis of Metal Chelates

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Binuclear heterometallic {M-Ln} pivalate complexes (M = Co, Ni, Cu; Ln = Sm, Gd): synthesis, structure, and thermolysis

Cited by 8 publications

References 28 publications

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

A new family of high nuclearity Co^II/Dy^III coordination clusters possessing robust and unseen topologies

Thermolysis of Polymeric Metal Chelates

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Binuclear heterometallic {M-Ln} pivalate complexes (M = Co, Ni, Cu; Ln = Sm, Gd): synthesis, structure, and thermolysis

Cited by 8 publications

References 28 publications

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

Heterometallic 3d–4f Complexes as Air-Stable Molecular Precursors in Low Temperature Syntheses of Stoichiometric Rare-Earth Orthoferrite Powders

A new family of high nuclearity CoII/DyIII coordination clusters possessing robust and unseen topologies

Thermolysis of Polymeric Metal Chelates

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Product

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A new family of high nuclearity Co^II/Dy^III coordination clusters possessing robust and unseen topologies