Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Li, Yunlan; Huang, Zhong‐Ming; Wang, Hai‐Ling; Zhu, Zhong‐Hong; Liang, Fu‐Pei; Zou, Hua‐Hong

doi:10.1039/d2ce01506d

Cited by 6 publications

(3 citation statements)

References 56 publications

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“…As shown in Figure b, the Cole–Cole diagrams of complex (1) are relatively semicircular, and the fitted values are basically consistent with the generalized Debye model. The anisotropic energy barrier and magnetic relaxation time of complex (1) was analyzed by the Arrhenius equation (τ = τ 0 exp( U eff / k B T ), where τ 0 is the pre-exponential factor, U eff is the flip energy barrier, and k B is the Boltzmann constant). − The results show that under the optimal external DC fields, the effective energy barrier and magnetic relaxation time of complex (1) are U eff = 6.5 (0.30) K; τ 0 = 4.1 × 10 –5 s (Figure c, blue line). In addition, we also considered the Raman process ( CT n ).…”

Section: Resultsmentioning

confidence: 99%

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Ai,

Li,

Zhu

et al. 2023

Crystal Growth & Design

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The potential docking spots in the structure of lanthanide complexes provide opportunities for subsequent synthetic modification or introduction of other metal centers. Usually, multidentate chelating ligands are used to construct lanthanide complexes, and multiple dense coordination sites tightly wrap the metal center; it is difficult to expose vacant coordination sites in a wide range. Herein, a series of lanthanide complexes with a potential docking spot were obtained by in situ Schiff base reaction via a solvothermal "one-pot" method, and their structures and molecular magnetic properties were explored. Specifically, DyCl 3 •6H 2 O, ovanillin, and 3-methoxysalicylaldehyde were reacted under solvothermal conditions at 100 °C to obtain a mononuclear dysprosium complex [Dy(L 1 ) 2 Cl 3 ] (1) with exposed N 2 O 4 coordination sites, and it is a field-induced single-molecule magnet (SMM). In addition, Ln(NO 3 ) 3 •6H 2 O 4-diethylaminosalicylaldehyde and 2,2-dimethyl-1,3-propanediamine reacted under solvothermal conditions at 80 °C, and five binuclear complexes, [Ln 2 (L 2 ) 3 (NO 3 ) 6 ]•3CH 3 CN (Ln = Dy (2), Tb (3), Ho (4), Er (5), and Gd (6)), with a large number of exposed N 4 O 4 coordination sites were obtained, which were mononuclear as independent units and connected by Schiff base ligands (L 2 ) 2− . It is worth noting that the maximum −ΔS m of complex (6) is 15.92 J kg −1 K −1 , higher than the commercially used magnetic refrigerant GGG (Gd 3 Gd 5 O 12 ; about 14.6 J kg −1 K −1 ), and complex (6) can be considered as a potential molecular-based material for magnetic refrigeration. Schiff base ligands with multidentate chelating coordination are usually used to construct lanthanide complexes. Their abundant and dense coordination sites can quickly capture metal centers to form clusters, but it is difficult to free up exposed coordination sites that can be used for structural modification.

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Section: Resultsmentioning

confidence: 99%

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Ai,

Li,

Zhu

et al. 2023

Crystal Growth & Design

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“…The structural transformation of clusters should follow alternative pathways: in situ distortion–transformation or destruction–reorganization. − Although several advanced techniques, such as high-resolution electrospray ionization mass spectrometry, have been employed to detect intermediates during cluster transformation, clusters with an unambiguous transformation path remain limited. − In recent years, the ligand exchange has become an emerging synthetic method for obtaining coinage metal nanoclusters. − In this work, the introduction of chiral ligands into an {Nd 9 Fe 2 } solution triggers the conversion of {Nd 9 Fe 2 } to {Nd 8 Fe 3 } at low temperatures (Figure a). As shown in Figure a,b(I), there is a characteristic absorption peak at 443 nm in the UV–vis absorption spectrum after the reaction.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis of Homochiral Hierarchical Nd₈Fe₃-Oxo Cluster from Racemic Nd₉Fe₂-Oxo Cluster

Lu,

Ding,

Zhong

et al. 2024

Inorg. Chem.

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Enantioselective synthesis of homochiral rare earth clusters is still a great challenge. In this work, we developed an efficient "cluster to cluster" approach, that is, a pair of enantiomerical R/S-{Nd 8 Fe 3 }-oxo clusters were successfully obtained from the presynthesized racemic {Nd 9 Fe 2 }-oxo cluster. R/S-hydrobenzoin ligands trigger the transformation of the pristine clusters by an SN 2 -like mechanism. Compared to the pristine cluster with an achiral core, the new cluster exhibits hierarchical chirality, from ligand chirality to interface chirality, then to helix chirality, and finally to supramolecular double helix chirality. The spectral experiments monitored the transformation and confirmed distinctly structurerelated optical activity. The enantiomeric pure cluster also exhibits a potential asymmetric catalytic activity.

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“…From this perspective, Ln III -based molecular cluster-aggregates (MCAs) have emerged as a suitable platform for luminescence at the nanoscale. − In addition to a large number of emitting centers within a precise crystalline structure, MCAs offer excellent control over uniformity and composition. − On top of that, the careful choice of a ligand moiety ensures, at the same time, core rigidity (which reduces phonon-assisted deactivation routes) and a suitable way to efficiently sensitize Ln III optical centers. The so-called “antenna effect” is essential to account for the low absorption coefficient of Ln III and accomplish high performance.…”

Section: Introductionmentioning

confidence: 99%

Composition Control in Molecular Cluster-Aggregates: A Toolbox for Optical Output Tunability via Energy Transfer Pathways

Calado,

Gálico,

Murugesu

2023

ACS Appl. Mater. Interfaces

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Composition control is a powerful tool for obtaining high-performance lanthanide (Ln) luminescent materials with adjustable optical outputs. This strategy is well-established for hierarchically structured nanoparticles, but it is rarely applied to molecular compounds due to the limited number of metal centers within a single unit. In this work, we present a series of molecular cluster-aggregates (MCAs) with an icosanuclear core {Ln2Eu2Tb16} (Ln = Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tm, and Yb) in which we explore composition control, akin to nanoparticles, to modulate the optical output. More specifically, we target to understand how the presence of a third LnIII doping ion would impact the well-known TbIII → EuIII energy transfer and the ratiometric optical thermometry performance based on the TbIII/EuIII pair. Photophysical properties at room and at varying temperatures were investigated. Based on experimental data and well-established intrinsic features, such as spin–orbit coupling strength and LnIII 4f energy levels’ structure, we discuss the possible luminescent processes present in each MCA and provide insight into qualitative trends that can be rationally correlated throughout the series.

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Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Abstract: Lanthanide clusters with pleasing structures and excellent molecular magnetic properties have attracted extensive attention, but there are still very few examples to explore and dissect their self-assembly process, which limits...

Cited by 6 publications

References 56 publications

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Enantioselective Synthesis of Homochiral Hierarchical Nd₈Fe₃-Oxo Cluster from Racemic Nd₉Fe₂-Oxo Cluster

Composition Control in Molecular Cluster-Aggregates: A Toolbox for Optical Output Tunability via Energy Transfer Pathways

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Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

Abstract: Lanthanide clusters with pleasing structures and excellent molecular magnetic properties have attracted extensive attention, but there are still very few examples to explore and dissect their self-assembly process, which limits...

Cited by 6 publications

References 56 publications

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Lanthanide Complexes with a Potential Docking Spot: Structure and Magnetism

Enantioselective Synthesis of Homochiral Hierarchical Nd8Fe3-Oxo Cluster from Racemic Nd9Fe2-Oxo Cluster

Composition Control in Molecular Cluster-Aggregates: A Toolbox for Optical Output Tunability via Energy Transfer Pathways

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Enantioselective Synthesis of Homochiral Hierarchical Nd₈Fe₃-Oxo Cluster from Racemic Nd₉Fe₂-Oxo Cluster