Heterometallic Cu/Co and Cu/Mn oxalate complexes as single-source precursors for spinel-type oxides

Buvailo, Halyna I.; Desiatkina, Oksana; Makhankova, Valeriya G.; Kokozay, Vladimir N.; Domasevitch, Konstantin V.; Omelchenko, Irina V.; Dyakonenko, Viktoriya V.

doi:10.1016/j.jssc.2018.12.033

Cited by 2 publications

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“…Up to now, all known 2D honeycomb anionic layers in the compounds {(A) 2 [M II 2 (C 2 O 4 ) 3 ]} n or {A[M II M III (C 2 O 4 ) 3 ]} n were only interleaved by the templating cations, except in compounds {[Cu(en) 2 ][Mn 2 (C 2 O 4 ) 3 ]} n , {[Cu(en) 2 ][Co 2 (C 2 O 4 ) 3 ]·3H 2 O} n and {[Cu(Me 2 en) 2 ][Mn 2 (C 2 O 4 ) 3 ]·2H 2 O} n (en = ethylenediamine; Me 2 en = N , N -dimethylethylenediamine), in which the cationic units are linked with the layers. , …”

Section: Resultsmentioning

confidence: 82%

“…Additionally, distance between Cu II and Fe II metal centers bridged by oxygen atoms from oxalate bridges are 4.172(3) Å [Cu1···Fe1] and 4.174(4) Å [Cu1···Fe2 i ; symmetry operator ( i ): 1 – x , 1 – y , 1 – z ] in polymorph 4a and 4.1823(4) [Cu1···Fe1 i ; symmetry operator ( i ) − x + 1/2, − y + 1/2, − z + 1] in polymorph 4b . The distance between two honeycomb anionic layers in 4a is 7.544 Å and in 4b 7.553 Å, and these interlayer separations are significantly shorter than in the similar compounds. , …”

Section: Resultsmentioning

confidence: 99%

“…Each honeycomb of the [Fe II 2 (C 2 O 4 ) 3 ] n 2n− layer in 4a and 4b contains 6 oxalate bridges; two diagonal O atoms from each bridge in the [100] direction for 4a and the [101] direction for 4b are coordinated to two copper(II) ions (Figures 5a and 5c The distance between two honeycomb anionic layers in 4a is 7.544 Å and in 4b 7.553 Å, and these interlayer separations are significantly shorter than in the similar compounds. 37,38 The thermal behavior of compounds 1, 2, and 4a has been studied by simultaneous thermogravimetric analysis (TG) and differential thermal analysis (DTA) performed on a crystalline sample in a stream of synthetic air, up to 1000 °C. The corresponding curves are presented in Figure S10 and data in Table S8.…”

Section: ■ Introductionmentioning

confidence: 99%

“…O} n (en = ethylenediamine; Me 2 en = N,N-dimethylethylenediamine), in which the cationic units are linked with the layers 37,38. The average Fe•••Fe separations across the oxalate bridges are 5.534 and 5.5486 Å in 4a and 4b, respectively.…”

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Structural, Electrical, and Magnetic Versatility of the Oxalate-Based [CuFe] Compounds Containing 2,2′:6′,2″-Terpyridine: Anion-Directed Synthesis

et al. 2020

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The heterodimetallic [CuFe] compounds [CuII 4(terpy)4Cl5][FeIII(C2O4)3]·10H2O (1;terpy = 2,2′:6′,2′′-terpyridine), [CuII 2(H2O)2(terpy)2(C2O4)][CuIIFeIII(CH3OH)(terpy)(C2O4)3]2 (2), and {[Cu2 IIFeIII(H2O)(terpy)2(C2O4)7/2]·6H2O} n (3) were obtained using building block approach, from reaction of aqueous solution of [Fe(C2O4)3]3– and a methanol solution containing Cu2+ ions and terpy by the layering technique. Interestingly, by changing only the anion of the starting salt of copper(II), Cu(NO3)2·3H2O instead of CuCl2·2H2O, an unexpected change in the type of bridge, oxalate (2 and 3) versus chloride (1), was achieved, thus affecting the overall structural architecture. Two polymorphs of 3D coordination polymer [CuIIFeII 2(H2O)(terpy)(C2O4)3] n (4), crystallizing in the triclinic (a) and monoclinic (b) space groups, were formed hydrothermally, depending on whether CuCl2·2H2O or Cu(NO3)2·3H2O was added to the water, besides K3[Fe(C2O4)3]·3H2O and terpy, respectively. Under hydrothermal conditions iron(III) from initial building block is reduced to the divalent state, creating 2D honeycomb [FeII 2(C2O4)3] n 2n– layers, which are bridged by [Cu(H2O)(terpy)]2+ cations. Compounds were investigated by single-crystal X-ray diffraction, IR, and impedance spectroscopies, magnetization measurements, and density functional theory (DFT) calculations. In compounds 1 and 2, 0D magnetism is observed, with 1 having a ground-state spin of 1 due to different interactions through chloride bridges of Cu2+ ions in tetramer [CuII 4(terpy)4Cl5]3+ and 2 showing strong antiferromagnetic coupling of Cu2+ ions mediated by oxalate ligand in [CuII 2(H2O)2(terpy)2(C2O4)]2+ and weak ones between Cu2+ and Fe3+ ions through oxalate bridge in [CuIIFeIII(CH3OH)(terpy)(C2O4)3]−. Polymer 4 exhibits antiferromagnetic phase transition at 25 K: The [FeII 2(C2O4)3] n 2n– layers are antiferromagnetically ordered, and a small amount of interlayer interaction is transferred through [Cu(H2O)(terpy)]2+ cations via Oox–Cu–Oox bridges. Additionally, compounds 1 and 2 are electrical insulators, while 4a and 4b show proton conductivity.

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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