A Strongly Blue-Emitting Heptametallic [Dy<sup>III</sup><sub>7</sub>] Centered-Octahedral Single-Molecule Magnet

Canaj, Angelos B.; Tzimopoulos, Demetrios I.; Philippidis, Aggelos; Kostakis, George E.; Milios, Constantinos J.

doi:10.1021/ic301038q

Cited by 60 publications

(27 citation statements)

References 18 publications

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“…Upon cooling, the χ M T product decreases slightly in the range 300-60 K, followed by a rapid decrease on lowering the temperarure from 60 to 5.0 K to reach a final value of 17.5 cm 3 K mol -1 . This thermal behavior is associated with the depopulation of the Dy III Stark sublevels and possibly with the presence of weak antiferromagnetic Dy III •••Dy III exchange interactions within the molecule [2,9,19]. The latter was further established by a Curie-Weiss analysis of the "high-temperature" (30-300 K) magnetic susceptibility data (Fig.…”

Section: Accepted Manuscriptmentioning

confidence: 79%

“…S3) with θ= -4.5 K, suggesting the presence of weak antiferromagnetic interactions, even though one may not exclude the effect of the Stark sublevels depopulation on the θ value [19]. Alternating-current (ac) magnetic susceptibility measurements were performed on a polycrystalline sample of 3 in the 1.8-10 K range in a zero applied dc field and under a 3.5 G ac field oscillating at 100-1500 Hz; no frequency-dependent out-of-phase (χ'' M ) signals were observed, indicating that the complex is not SMM [1,9,19]. Preliminary data for the Tb III 2 complex indicate a similar behaviour.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

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Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Anastasiadis

Mylonas-Margaritis

Psycharis

et al. 2015

Inorganic Chemistry Communications

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Section: Accepted Manuscriptmentioning

confidence: 79%

Section: Accepted Manuscriptmentioning

confidence: 99%

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Anastasiadis

Mylonas-Margaritis

Psycharis

et al. 2015

Inorganic Chemistry Communications

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“…14c,14e The latter were further established by a Curie-Weiss analysis of the 40-300 K magnetic susceptibility data with θ = -22.9 K for 2, θ = -7.3 Κ for 70 7 and θ = -11.9 Κ for 8, suggesting the presence of weak antiferromagnetic interactions within the molecules, even though one may not exclude the effect of the Stark sublevels' depopulation on the θ value. 51 No out-of-phase ac susceptibility signals have been detected for 2, 7 and 8 that would be indicative of SMM behaviour. Magnetization measurements for 2, 6, 7 and 8 (Fig.…”

Section: (F 2 )[V D (Clo)] and V 4 (F 2 )[δ D (οClo)] Modes Respectimentioning

confidence: 97%

Employment of methyl 2-pyridyl ketone oxime in 3d/4f-metal chemistry: dinuclear nickel(ii)/lanthanide(iii) species and complexes containing the metals in separate ions

Polyzou¹,

Nikolaou²,

Papatriantafyllopoulou³

et al. 2012

Dalton Trans.

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The use of methyl 2-pyridyl ketone oxime (mpkoH) for the synthesis of Ni(II)/Ln(III) (Ln = lanthanide) complexes, using "one-pot" reactions in the absence of an external base, is described. Depending on the reaction and crystallization conditions employed, two families of complexes have been obtained. The first family consists of true heterometallic species and involves complexes [NiLn(mpko)(3)(mpkoH)(3)](ClO(4))(2), where Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er. The second family contains the pseudo heterometallic complexes [Ni(mpkoH)(3)](2)[Ln(NO(3))(6)](ClO(4)), where Ln = La, Ce, Pr, Nd and Sm. The crystal structures of [NiCe(mpko)(3)(mpkoH)(3)](ClO(4))(2) (1), [NiDy(mpko)(3)(mpkoH)(3)](ClO(4))(2) (8) and [Ni(mpkoH)(3)](2)[La(NO(3))(6)](ClO(4)) (11) have been determined by single-crystal, X-ray crystallography. Complexes 1·1.2MeOH·0.6H(2)O and 8·1.2MeOH·0.6H(2)O crystallise in the monoclinic space group P2(1)/a and are isomorphous; there are two crystallographically independent cations in the unit cell, but their interatomic distances and angles differ little. The Ni(II) and Ln(III) ions are bridged by three oximate groups belonging to the η(1):η(1):η(1):μ mpko(-) ligands. The Ni(II) centre is octahedrally coordinated by the six nitrogen atoms of the mpko(-) ligands in a facial arrangement. The Ln(III) centre is bound to an (O(oximate))(3)N(6) set of donor atoms, the nitrogen atoms belonging to the three N,N'-bidentate chelating mpkoH ligands. The stereochemistry of the Ln(III) atoms has been evaluated by means of continuous shape measures (CShM). The two crystallographically independent Ce(III) atoms in 1 have tricapped trigonal prismatic and capped square antiprismatic coordination geometries, while the polyhedra of the Dy(III) atoms in 8 are both close to a tricapped trigonal prism. The octahedral Ni(II) atoms in 11 are both facially bound to a N(6) set of donor atoms from three N,N'-bidentate chelating mpkoH ligands, while the 12-coordinate La(III) centre in [La(NO(3))(6)](3-) is coordinated by six bidentate chelating nitrato groups. Variable-temperature, solid state dc magnetic susceptibility studies were carried out on complexes 2, 6, 7 and 8. The dc susceptibility data for 6 in the 2.0-300 K range have been fit to a model with one J value, revealing an antiferromagnetic Ni(II)···Gd(III) exchange interaction [J = -1.1 cm(-1) based on H = -J (Ŝ(Ni)·Ŝ(Gd))]. Antiferromagnetic Ni(II)···Pr(III), Ni(II)···Tb(III) and Ni(II)···Dy(III) exchange interactions have also been suggested for 2, 7 and 8, respectively. The combined work demonstrates the usefulness of mpko(-) in the preparation of interesting Ni(II)/Ln(III) compounds, without requiring the presence of external base and ancillary organic ligands.

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“…[8][9][10][11][12][13] In particular, lanthanide containing compounds are being studied in considerable detail for their singlemolecule [8][9][10][11][12][13] and single-ion magnetism behavior. [14][15][16][17] This is because of the large ground-state spin and high magnetic anisotropy that many lanthanide ions provide.…”

Section: Introductionmentioning

confidence: 99%

P–C Bond Cleavage-Assisted Lanthanide Phosphate Coordination Polymers

Goura

Walsh

Tuna

et al. 2015

Crystal Growth & Design

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The reaction of lanthanide(III) salts with an organodiphosphonic acid under hydrothermal conditions resulted in a P–C bond cleavage affording [{Eu4(PO4)(PO4)0.5×4(PO4)0.25×4(H2O)2}·6H2O] n (1), [{Dy4(PO4)(PO4)0.5×4(PO4)0.25×4(H2O)2}·6H2O] n (2), and [{Gd(PO4)0.5(PO4)0.5(H2O)3}·2H2O] n (3). 1 and 2 are porous 3D coordination polymers whose repeating units possess a dimeric motif. While one lanthanide ion in the dimer is eight-coordinate in a distorted square-antiprismatic geometry, the other is nine-coordinate and present in a distorted monocapped square-antiprismatic geometry. In contrast to 1 and 2, 3 possesses a 2D architecture; the asymmetric unit contains a monomeric GdIII center which is nine-coordinate in a distorted monocapped square-antiprismatic geometry.

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A Strongly Blue-Emitting Heptametallic [Dy^III₇] Centered-Octahedral Single-Molecule Magnet

Abstract: The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol and 2-aminoisobutyric acid in dysprosium chemistry has led to the isolation of a novel heptanuclear [Dy(III)(7)] cluster displaying single-molecule-magnetism behavior and blue-emitting properties.

Cited by 60 publications

References 18 publications

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Employment of methyl 2-pyridyl ketone oxime in 3d/4f-metal chemistry: dinuclear nickel(ii)/lanthanide(iii) species and complexes containing the metals in separate ions

P–C Bond Cleavage-Assisted Lanthanide Phosphate Coordination Polymers

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A Strongly Blue-Emitting Heptametallic [DyIII7] Centered-Octahedral Single-Molecule Magnet

Abstract: The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol and 2-aminoisobutyric acid in dysprosium chemistry has led to the isolation of a novel heptanuclear [Dy(III)(7)] cluster displaying single-molecule-magnetism behavior and blue-emitting properties.

Cited by 60 publications

References 18 publications

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone

Employment of methyl 2-pyridyl ketone oxime in 3d/4f-metal chemistry: dinuclear nickel(ii)/lanthanide(iii) species and complexes containing the metals in separate ions

P–C Bond Cleavage-Assisted Lanthanide Phosphate Coordination Polymers

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A Strongly Blue-Emitting Heptametallic [Dy^III₇] Centered-Octahedral Single-Molecule Magnet