Synthesis, structure, and magnetic properties of heterometallic trinuclear complexes {MII—LnIII—MII} (MII = Ni, Cu; LnIII = La, Pr, Sm, Eu, Gd)

Burkovskaya, N. P.; Orlova, Elena V.; Кискин, М. А.; Ефимов, Н. Н.; Bogomyakov, A. S.; Fedin, Matvey V.; Kolotilov, Sergey V.; Минин, В. В.; Александров, Г. Г.; Сидоров, А. А.; Овчаренко, В. И.; Новоторцев, В. М.; Еременко, И. Л.

doi:10.1007/s11172-011-0384-4

Cited by 17 publications

(7 citation statements)

References 49 publications

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“…The crystallographically established metal cores in Ni 2 Ln complexes found in refs. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] (a), [25][26][27][28][29][30][31][32][33][34] (b), [35][36][37][38] (c), [39] (d), [40][41][42] (e), (f) [43], and (g) [44,45].…”

Section: Introductionmentioning

confidence: 99%

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Georgopoulou¹,

Pissas²,

Psycharis³

et al. 2020

Molecules

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The reaction of the Schiff base ligand o-OH-C6H4-CH=N-C(CH2OH)3, H4L, with Ni(O2CMe)2∙4H2O and lanthanide nitrate salts in a 4 : 2 : 1 ratio lead to the formation of the trinuclear complexes [Ni2Ln(H3L)4(O2CMe)2](NO3) (Ln = Sm (1), Eu (2), Gd (3), Tb (4)). The complex cations contain the strictly linear NiII-LnIII-NiII moiety. The central LnIII ion is bridged to each of the terminal NiII ions through two deprotonated phenolato groups from two different ligands. Each terminal NiII ion is bound to two ligands in distorted octahedral N2O4 environment. The central lanthanide ion is coordinated to four phenolato oxygen atoms from the four ligands, and four carboxylato oxygen atoms from two acetates which are bound in the bidentate chelate mode. The lattice structure of complex 4 consists of two interpenetrating, supramolecular diamond like lattices formed through hydrogen bonds among neighboring trinuclear clusters. The magnetic properties of 1-4 were studied. For 3 the best fit of the magnetic susceptibility and isothermal M(H) data gave JNiGd = +0.42 cm−1, D = +2.95 cm−1 with gNi = gGd = 1.98. The ferromagnetic nature of the intramolecular Ni···Gd interaction revealed ground state of total spin S = 11/2. The magnetocaloric effect (MCE) parameters for 3 show that the change of the magnetic entropy (−ΔSm) reaches a maximum of 14.2 J kg−1 K−1 at 2 K. A brief literature survey of complexes containing the NiII-LnIII-NiII moiety is discussed in terms of their structural properties.

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Section: Introductionmentioning

confidence: 99%

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Georgopoulou¹,

Pissas²,

Psycharis³

et al. 2020

Molecules

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“…To describe the magnetic properties of the Dy III ions in 1 , 4 , and 5 , the axial anisotropy was considered in a model based on Hamiltonian . This approach was used previously to describe the magnetic properties of lanthanide complexes,, in particular, Dy III compounds

\hat{H} = Δ_{Dy} {\overset{J}{true}}_{z}^{2}

…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we studied a series of heterometallic 3d–4f complexes containing M 2 Ln cores [M II = Ni, Cu; Ln III = Nd, Pr, Sm, Eu, Gd, Zn 2 Eu, Cu 2 Ln 2 (Ln III = Sm or Gd), Ni II 2 Gd III 2 ] . In the majority of cases, these complexes (or precursors containing their polynuclear cores) formed through self‐assembly reactions in solution.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Magnetic Properties of a Family of Complexes Containing a {Co^II₂Dy^III} Pivalate Core and a Pentanuclear Co^II₄Dy^III Derivative

et al. 2017

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A series of new Co II -Ln III complexes with polynuclear {Co 2 Ln(NO 3 )(Piv) 6 } (Ln = La, Gd, Dy; Piv = pivalate) cores were prepared by self-assembly reactions or step-by-step assembly.[Co 2 Dy(NO 3 )(Piv) 6 (MeCN) 2 ] was used as the starting compound for the synthesis of the trinuclear analogue [Co 2 Dy(NO 3 )(Piv) 6 -(py) 2 ] (py = pyridine) and the pentanuclear complex [{Co 2 Dy-(NO 3 )(Piv) 6 }{CoL(Piv)(H 2 O)} 2 ][NO 3 ] 2 [L = 2,6-bis(2-pyridyl)-4-(4pyridyl)pyridine]. The effects of the coordination environment and temperature on the distortion of the Ln III coordination polyhedra were analyzed for a series of coordination compounds with M II 2 Ln III cores and close analogues. The distortion of the Ln III polyhedron depends on both the composition of [a] N.

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“…Such rearrangement reactions lead to the formation of certain polynuclear cores, which are most stable under the reaction conditions. For example, binuclear cores M2(O2CR)4 (M II = Cu, Zn, Co, Ni) [28], trinuclear cores Fe III 3 or Fe III 2M II (M = Ni, Co, Mn) [29][30][31][32], M II 2Ln III (M II = Zn, Co, Ni; Ln is lanthanide) [33][34][35] often form due to their exceptional stability in various media. However, the result of such rearrangements is not always predictable, since many factors may influence the reaction pathway.…”

Section: Introductionmentioning

confidence: 99%

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates

et al. 2021

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Reaction of 2,2′-bipyridine (2,2′-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2′-bipy (1), phen (2); Piv- is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear MnII/III complexes [Mn4O2(Piv)6L2] (L = 2,2′-bipy (3), phen (4)). The hexanuclear complex [Mn6(OH)2(Piv)10(pym)4] (5) was formed in the reaction of [Mn(Piv)2(EtOH)]n with pyrimidine (pym), while oxidation of 5 produced the coordination polymer [Mn6O2(Piv)10(pym)2]n (6). Use of pyrazine (pz) instead of pyrimidine led to the 2D-coordination polymer [Mn4(OH)(Piv)7(µ2-pz)2]n (7). Interaction of [Mn(Piv)2(EtOH)]n with FeCl3 resulted in the formation of the hexanuclear complex [MnII4FeIII2O2(Piv)10(MeCN)2(HPiv)2] (8). The reactions of [MnFe2O(OAc)6(H2O)3] with 4,4′-bipyridine (4,4′-bipy) or trans-1,2-(4-pyridyl)ethylene (bpe) led to the formation of 1D-polymers [MnFe2O(OAc)6L2]n·2nDMF, where L = 4,4′-bipy (9·2DMF), bpe (10·2DMF) and [MnFe2O(OAc)6(bpe)(DMF)]n·3.5nDMF (11·3.5DMF). All complexes were characterized by single-crystal X-ray diffraction. Desolvation of 11·3.5DMF led to a collapse of the porous crystal lattice that was confirmed by PXRD and N2 sorption measurements, while alcohol adsorption led to porous structure restoration. Weak antiferromagnetic exchange was found in the case of binuclear MnII complexes (JMn-Mn = −1.03 cm−1 for 1 and 2). According to magnetic data analysis (JMn-Mn = −(2.69 ÷ 0.42) cm−1) and DFT calculations (JMn-Mn = −(6.9 ÷ 0.9) cm−1) weak antiferromagnetic coupling between MnII ions also occurred in the tetranuclear {Mn4(OH)(Piv)7} unit of the 2D polymer 7. In contrast, strong antiferromagnetic coupling was found in oxo-bridged trinuclear fragment {MnFe2O(OAc)6} in 11·3.5DMF (JFe-Fe = −57.8 cm−1, JFe-Mn = −20.12 cm−1).

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Synthesis, structure, and magnetic properties of heterometallic trinuclear complexes {MII—LnIII—MII} (MII = Ni, Cu; LnIII = La, Pr, Sm, Eu, Gd)

Cited by 17 publications

References 49 publications

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Synthesis, Structure, and Magnetic Properties of a Family of Complexes Containing a {Co^II₂Dy^III} Pivalate Core and a Pentanuclear Co^II₄Dy^III Derivative

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates

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Synthesis, structure, and magnetic properties of heterometallic trinuclear complexes {MII—LnIII—MII} (MII = Ni, Cu; LnIII = La, Pr, Sm, Eu, Gd)

Cited by 17 publications

References 49 publications

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Trinuclear NiII-LnIII-NiII Complexes with Schiff Base Ligands: Synthesis, Structure, and Magnetic Properties

Synthesis, Structure, and Magnetic Properties of a Family of Complexes Containing a {CoII2DyIII} Pivalate Core and a Pentanuclear CoII4DyIII Derivative

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates

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Synthesis, Structure, and Magnetic Properties of a Family of Complexes Containing a {Co^II₂Dy^III} Pivalate Core and a Pentanuclear Co^II₄Dy^III Derivative