Mixed-anion templated cage-like lanthanide clusters: Gd<sub>27</sub> and Dy<sub>27</sub>

Zheng, Xiu‐Ying; Peng, Jun-Bo; Kong, Xiang‐Jian; Liu, Long; Zheng, Lan‐Sun

doi:10.1039/c5qi00249d

Cited by 87 publications

(50 citation statements)

References 51 publications

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“…The synthesis and characterization of single‐molecule magnets (SMMs) and single‐ion magnets (SIMs) is a rapidly developing field that began with the discovery of SMM behavior in [Mn IV 4 Mn III 8 (µ 3 ‐O) 12 (OAc) 16 (OH 2 ) 4 ] · 2HOAc · 4H 2 O . Among the many reasons for the widespread interest in this family of compounds are the challenges in assembling such molecules and their potential futuristic applications in areas such as quantum computation, spintronics, high‐density magnetic data storage devices, and magnetic refrigeration . SMMs are discrete molecules that display a slow relaxation of magnetization below a certain temperature (blocking temperature).…”

Section: Introductionmentioning

confidence: 99%

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

et al. 2016

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A series of dinuclear lanthanide complexes, [Dy2(LH)2(µ2‐Piv‐κ2O,O′)2(NO3‐κ2O,O′)2] (1), [Tb2(LH)2(µ2‐Piv‐κ2O,O′)2(NO3‐κ2O,O′)2] (2), [Gd2(LH)2(µ2‐Piv‐κ2O,O′)2(NO3‐κ2O,O′)2] (3), and [Ho2(LH)2(µ2‐Piv‐κ2O,O′)2(NO3‐κ2O,O′)2] (4) have been synthesized by the reaction of Ln(NO3)3·nH2O with the multidentate hydrazone‐based Schiff‐base ligand, N′‐(2‐hydroxy‐3‐methoxybenzylidene)acetohydrazide (LH2) in the presence of pivalic acid. X‐ray crystallography data reveals that 1–4 are isostructural, neutral, and contain two mono‐deprotonated ligands, two pivalates, and two chelated nitrates. Within the dinuclear assembly, the two lanthanides are bridged by two phenolate and two pivalate oxygens. Each of the two lanthanide ions is nine‐coordinated and possesses a distorted monocapped square‐antiprism geometry. Detailed magnetochemical analysis revealed the presence of weak antiferromagnetic coupling at low temperature for all complexes. The DyIII analogue displayed SMM behavior in the absence of a dc field with two relaxation domains in which the thermally activated domain exhibits an energy barrier of 40 K and relaxation time of 6.5 × 10–5 s.

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Section: Introductionmentioning

confidence: 99%

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

et al. 2016

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“…However, the formation of cage-shaped clusters is rare, in which the high nuclear caged lanthanide cluster Er 60 is a sodalite caged structure composed of 24 [Er 4 (μ 3 -OH) 4 ] 8+ cubanes by vertex sharing 10 . Cage-shaped dysprosium highnuclearity clusters, such as Dy 17 , Dy 24 , Dy 26 , Dy 27 , and Dy 104 , have been reported [54][55][56][57] . Dy 104 is composed of four single cageshaped Dy 26 bridged by ligands.…”

Section: Resultsmentioning

confidence: 99%

“…The Dy/O/N core of Dy 30 exhibited a spherical cage shape and differed from the octagonalprismatic Dy 17 , capsule-shaped Dy 24 , ball-and-stick-shaped Dy 27 , and vertex angle cage-shaped Dy 26 (or Dy 104 ) ( Fig. 2e) [54][55][56][57] . In the core of Dy 30 , the bond distances of Dy···Dy were within the limits of 3.895-3.925 Å in the triangular lattice Dy 3 .…”

Section: Resultsmentioning

confidence: 99%

Assembly of Dy60 and Dy30 cage-shaped nanoclusters

et al. 2020

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Rapid kinetics, complex and diverse reaction intermediates, and difficult screening make the study of assembly mechanisms of high-nuclearity lanthanide clusters challenging. Here, we synthesize a double-cage dysprosium cluster [Dy 60 (H 2 L 1 ) 24 (OAc) 71 (O) 5 (OH) 3 (H 2 O) 27 ]·6-H 2 O·6CH 3 OH·7CH 3 CN (Dy 60 ) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy 30 cages are included in the Dy 60 structure, which are connected via an OAc − moiety. The core of Dy 60 is composed of 8 triangular Dy 3 and 12-fold linear Dy 3 units. We further change the alkali added in the reaction system and successfully obtain a single cageshaped cluster [Dy 30 (H 2 L 1 ) 12 (OAc) 36 (OH) 4 (H 2 O) 12 ]·2OH·10H 2 O·12CH 3 OH·13CH 3 CN (Dy 30 ) with a perfect spherical cavity, which could be considered an intermediate in Dy 60 formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy 60 . A possible self-assembly mechanism is proposed. We track the formation of Dy 30 and the six intermediate fragments are screened.

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“…It should be nevertheless mentioned that the isothermal entropy change of molecular nanomagnets composed exclusively from transition-metal ions other than Mn 2+ and/or Fe 3+ [50,58] just rarely exceeds the value ∆S M = 10 J•K −1 •kg −1 , which may be regarded as a benchmark for the enhanced MCE. Although the molecular nanomagnets based on transition-metal ions cannot be competitive with the high-nuclear Gd 3+ clusters affording much larger isothermal entropy change [59][60][61][62], they may be of practical relevance for high-temperature applications due to much stronger exchange couplings.…”

Section: Introductionmentioning

confidence: 99%

Insights into Nature of Magnetization Plateaus of a Nickel Complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 from a Spin-1 Heisenberg Diamond Cluster

et al. 2020

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Magnetic and magnetocaloric properties of a spin-1 Heisenberg diamond cluster with two different coupling constants are investigated with the help of an exact diagonalization based on the Kambe’s method, which employs a local conservation of composite spins formed by spin-1 entities located in opposite corners of a diamond spin cluster. It is shown that the spin-1 Heisenberg diamond cluster exhibits several intriguing quantum ground states, which are manifested in low-temperature magnetization curves as intermediate plateaus at 1/4, 1/2, and 3/4 of the saturation magnetization. In addition, the spin-1 Heisenberg diamond cluster may also exhibit an enhanced magnetocaloric effect, which may be relevant for a low-temperature refrigeration achieved through the adiabatic demagnetization. It is evidenced that the spin-1 Heisenberg diamond cluster with the antiferromagnetic coupling constants J1/kB = 41.4 K and J2/kB = 9.2 K satisfactorily reproduces a low-temperature magnetization curve recorded for the tetranuclear nickel complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 (aetpy = 2-aminoethyl-pyridine) including a size and position of intermediate plateaus detected at 1/2 and 3/4 of the saturation magnetization. A microscopic nature of fractional magnetization plateaus observed experimentally is clarified and interpreted in terms of valence-bond crystal with either a single or double valence bond. It is suggested that this frustrated magnetic molecule can provide a prospective cryogenic coolant with the maximal isothermal entropy change −ΔSM=10.6 J·K−1·kg−1 in a temperature range below 2.3 K.

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Mixed-anion templated cage-like lanthanide clusters: Gd₂₇ and Dy₂₇

Abstract: Two record-large odd-numbered Ln27 lanthanide clusters, each one featuring one CO32− and eight ClO4− groups as mixed anion templates, were obtained by controlling the hydrolysis of the Ln3+ ions in the presence of simple propionate ligands.

Cited by 87 publications

References 51 publications

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

Assembly of Dy60 and Dy30 cage-shaped nanoclusters

Insights into Nature of Magnetization Plateaus of a Nickel Complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 from a Spin-1 Heisenberg Diamond Cluster

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Mixed-anion templated cage-like lanthanide clusters: Gd27 and Dy27

Abstract: Two record-large odd-numbered Ln27 lanthanide clusters, each one featuring one CO32− and eight ClO4− groups as mixed anion templates, were obtained by controlling the hydrolysis of the Ln3+ ions in the presence of simple propionate ligands.

Cited by 87 publications

References 51 publications

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

Hydrazone‐Ligand‐Based Homodinuclear Lanthanide Complexes: Synthesis, Structure, and Magnetism

Assembly of Dy60 and Dy30 cage-shaped nanoclusters

Insights into Nature of Magnetization Plateaus of a Nickel Complex [Ni4(μ-CO3)2(aetpy)8](ClO4)4 from a Spin-1 Heisenberg Diamond Cluster

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Mixed-anion templated cage-like lanthanide clusters: Gd₂₇ and Dy₂₇