Three Giant Lanthanide Clusters Ln37 (Ln = Gd, Tb, and Eu) Featuring A Double-Cage Structure

Yang, Zhou; Zheng, Xiu‐Ying; Cai, Jiwen; Hong, Zi-Feng; Yan, Zhen; Kong, Xiang‐Jian; Ren, Yan‐Ping; Liu, Long; Zheng, Lan‐Sun

doi:10.1021/acs.inorgchem.6b02714

Cited by 71 publications

(35 citation statements)

References 38 publications

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“…2). The compounds with the cubane core are widely described for d and f elements in both isolated molecular clusters [13,14] and structural blocks of the more complicated polynuclear complexes [35,36] and coordination polymers [37,38].…”

Section: Resultsmentioning

confidence: 99%

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

et al. 2022

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Tetranuclear hydroxo complexes [La4(Deta)4(OH)4(Tfa)3(DetadcH)2](HTfa)(H2O)7(Tfa)3 (I) and [Nd4(Deta)4(OH)4(Tfa)3(DetadcH)2](H2O)n(Tfa)3 (II) with diethylene-N,N′-dicarbamate anions (DetadcH–) are synthesized for the first time by the reactions of lanthanum trifluoroacetate and neodymium trifluoroacetate with a solution of diethylenetriamine (Deta) in air under the self-controlled hydrolysis conditions and are characterized by X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and elemental analysis. Compounds I and II contain the same-type complex cationic fragment with the cubane metal–oxygen core stabilized due to four chelate Deta ligands and two bridging DetadcH– ligands. The DFT calculations of the geometry and vibrational spectrum of the [La4(Deta)4(OH)4(Tfa)3(DetadcH)2]3+ complex cation are performed.

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Section: Resultsmentioning

confidence: 99%

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

et al. 2022

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“…Complex 3 possessing two isotropic Gd III ions can be potentially used as a low‐temperature magnetic cooling materials, in which the magnetic entropy change –Δ S m as a crucial parameter for the MCE can be calculated by numerical integration based on the experimental magnetization data and the Maxwell equation Δ S m ( T ) Δ H = ∫[ ∂M ( T,H )/ ∂T ] H dH . As shown in Figure , under the fixed external magnetic field, the resulting –Δ S m of 3 increases slowly with the decreasing temperature.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, three essential factors (a large‐spin ground stare, negligible magnetic anisotropy, and a large magnetic density) have been extensively recognized to be significant for the large magnetic entropy change . Therefore, isotropic Gd III ion with large spin value of 7/2 and short magnetic bridges with a purpose to improve metal/ligand mass ratio (CO 3 2– , OH – , CH 3 COO – , and NO 3 – ) have been the promising candidates for the high‐performing molecular magnetic coolers . Up to date, a very large number of Gd III ‐based complexes, such as [Gd 104 ], [Gd 48 ], and [Gd 24 ] highnuclear clusters as well as [Gd 60 ] nanocage have been reported to exhibit excellent magnetic refrigeration properties .…”

Section: Introductionmentioning

confidence: 99%

Three Phenoxo‐Bridged Dinuclear Lanthanide Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Zhang

Dai

Dong

et al. 2018

Zeitschrift anorg allge chemie

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Three dinuclear lanthanide complexes [Ln2(H2L)2(NO3)4] [Ln = Dy (1), Tb (2), and Gd (3)] [H3L = 2‐hydroxyimino‐N′‐[(2‐hydroxy‐3‐methoxyphenyl)methylidene]‐propanohydrazone] were solvothermally synthesized by varying differently anisotropic rare earth ions. Single‐crystal structural analyses demonstrate that all the three complexes are crystallographically isostructural with two centrosymmetric LnIII ions aggregated by a pair of monodeprotonated H2L– anions. Weak intramolecular antiferromagnetic interactions with different strength were mediated by a pair of phenoxo bridges due to superexchange and/or single‐ion anisotropy. Additionally, the DyIII‐based entity shows the strongest anisotropy exhibits field‐induced single‐molecule magnetic behavior with two thermally activated relaxation processes. In contrast, 3 with isotropic GdIII ion has a significant cryogenic magnetocaloric effect with the maximum entropy change of 25.7 J·kg–1·K–1 at 2.0 K and 70.0 kOe.

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“…Generally, carbonate ions play important roles as anion templates during the formation of polynuclear lanthanide clusters. 31,[41][42][43] In many cases, carbonate ions are generated by decomposition of the precursor and/or uptake of carbon dioxide from the air. Therefore, in the crystal structure of KGF-3, it is likely that the molecules coordinating to five metal ions in a pentagonal pocket (Figure 2d) are carbonate ions.…”

Section: Exploration Of the Optimized Synthetic Conditionsmentioning

confidence: 99%

Failure-experiment-supported optimization of poorly reproducible synthetic conditions for novel lanthanide metal-organic frameworks with two-dimensional secondary building units

Kitamura¹,

Terado²,

Zhang³

et al. 2021

Preprint

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A series of novel metal organic frameworks with lanthanide double-layer-based inorganic subnetworks (KGF-3) was synthesized assisted by machine learning. Pure KGF-3 was difficult to isolate in the initial screening experiments. The synthetic conditions were successfully optimized by extracting the dominant factors for KGF-3 synthesis using two machine-learning techniques. Cluster analysis was used to classify the obtained PXRD patterns of the products and to decide automatically whether the experiments were successful or had failed. Decision tree analysis was used to visualize the experimental results, with the factors that mainly affected the synthetic reproducibility being extracted. The water adsorption isotherm revealed that KGF-3 possesses unique hydrophilic pores, and impedance measurements demonstrated good proton conductivities (σ = 5.2 × 10−4 S cm−1 for KGF-3(Y)) at a high temperature (363 K) and high relative humidity (95%).

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Three Giant Lanthanide Clusters Ln₃₇ (Ln = Gd, Tb, and Eu) Featuring A Double-Cage Structure

Cited by 71 publications

References 38 publications

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Three Phenoxo‐Bridged Dinuclear Lanthanide Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Failure-experiment-supported optimization of poorly reproducible synthetic conditions for novel lanthanide metal-organic frameworks with two-dimensional secondary building units

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