Large Heterometallic Dy<sub>12</sub>Na<sub>6</sub> Cage-like Cluster Supported by in Situ Generated Ligand

Wang, Guo‐Ming; Li, Jinhua; Han, Song‐De; Pan, Jie; Wei, Li; Wang, Zonghua; Bao, Zhen‐Zhen

doi:10.1021/acs.cgd.6b00239

Cited by 13 publications

(6 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Direct evidence of the substitution of both NO 3 – and OH – in ZnNd-1 by OAc – could be further ascertained by the IR spectrum (Figure S3). The bridged acetate in ZnNd-2 can be testified by the IR typical peaks at 1633, 1589, and 1548 cm –1 for μ 2 -acetate . These anion exchange behaviors are good reflections of the Lewis basicity of the anions.…”

Section: Resultsmentioning

confidence: 95%

“…The bridged acetate in ZnNd-2 can be testified by the IR typical peaks at 1633, 1589, and 1548 cm −1 for μ 2 -acetate. 15 These anion exchange behaviors are good reflections of the Lewis basicity of the anions. As described above, because of its stronger Lewis basicity, OAc − anios not only replace the monodentate and bidententate nitrates in ZnNd-1 but also remove the coordinated water molecule and μ 2 -OH − with the aid of its strong bridging preference.…”

Section: ■ Experimental Detailsmentioning

confidence: 95%

See 1 more Smart Citation

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

et al. 2018

View full text Add to dashboard Cite

Five heterometallic Zn-Ln macrocycles based on a salicylamide imine multidentate unsymmetrical ligand HL [1-(2-hydroxy-3-methoxy-benzamido)-2-(2-hydroxy-3-methoxy-benzylideneamino)-ethane] have been prepared via a coordination-driven self-assembly strategy. Single-crystal X-ray diffraction analysis reveals that the five metallocycles are isomorphic with a formula of [ZnLnL(OH)(NO)(HO)]·3NO· nCHCN (ZnLn-1, where Ln = Pr, Nd, Eu, Tb, or Yb; for ZnPr-1, n = 4; for ZnNd-1, ZnEu-1, and ZnTb-1, n = 2; for ZnYb-1, n = 3), where six octadentate ligands L and two in situ-formed μ-OH ions bridged the alternating Zn-Ln-Zn subunits into a macrocycle. Along with the structural novelty, ZnNd-1 shows distinctive enhanced emission in the visible and near-infrared range upon addition of OAc. On the basis of ultraviolet-visible spectroscopy, H nuclear magnetic resonance, single-crystal X-ray diffraction, and high-resolution electrospray ionization mass spectrometry, we deduced that this emission enhancement could be attributed to the synergistic effect of TICT and the absent nonradiative transition of μ-OH induced distinctively by OAc bridging. Our results demonstrate that the Nd-containing heterometallic macrocycle can act as a host for anion exchanging and provide a nice example of heterometallic macrocycles with interesting properties and potential applications.

show abstract

Section: Resultsmentioning

confidence: 95%

Section: ■ Experimental Detailsmentioning

confidence: 95%

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The strong absorption peaks at about 1484, 1290, 1030, and 815 cm –1 in ZnGd-1 and ZnGd-2 suggest the existence of bidentate nitrates. The asymmetric and symmetric stretching frequencies at 1631 and 1552 cm –1 confirmed the presence of the acetate group (Δν = 271 cm –1 ) in ZnGd-3 . Thermogravimetric experiments were conducted at 25–800 °C under an N 2 atmosphere to evaluate the thermal stabilities of these compounds.…”

Section: Resultsmentioning

confidence: 91%

“…The asymmetric and symmetric stretching frequencies at 1631 and 1552 cm −1 confirmed the presence of the acetate group (Δν = 271 cm −1 ) in ZnGd-3. 41 Thermogravimetric experiments were conducted at 25−800 °C under an N 2 atmosphere to evaluate the thermal stabilities of these compounds. Due to the structural similarities, the three kinds of compounds showed similar weight loss behaviors, as shown in Figure S5.…”

Section: Resultsmentioning

confidence: 99%

Anion-Dependent Structure and Luminescence Diversity in Zn^II-Ln^III Heterometallic Architectures Supported by a Salicylamide-Imine Ligand

et al. 2021

View full text Add to dashboard Cite

To advance the structural development and fully explore the application potential, it is highly desirable but challenging to elucidate the relationship between the structures and properties of Zn II -Ln III heterometallic species. Herein, three types of Zn II -Ln III heterometallic compounds (Ln III = Gd III , Tb III ) formulated as for Ln = Gd, x = 5; for Ln = Tb, x = 4) were dictated by common inorganic anions, NO 3 − and OAc − , with the aid of the multidentate ligand H 2 L with propane as the central skeleton and 3-methoxysalicylamide and 3-methoxysalicylaldimine as terminal groups. ZnLn-1 features cubic cages with four {Zn 4 L 3 } tetrahedral subunits and four Ln 3+ centers positioned at the eight vertices alternately when NO 3 − was introduced into the reaction system exclusively. An attempt to replace NO 3 − in ZnLn-1 with OAc − partially led to the formation of {Zn 2 Ln 2 L 2 } heterometallic wheels. Meanwhile, ZnLn-3 featuring double-hairpin-like {Zn 4 Ln 2 L 4 } hemicycles that are orthogonal to each other assisted by intermolecular hydrogen bonds was constructed when NO 3 − in ZnLn-1 was completely replaced by OAc − . Their structural integrity in solution were ascertained by both emission and 1 H NMR spectroscopy. Ascribed to the different Zn 2+ -containing antenna, ZnTb-2 possesses a relatively strong emission characteristic of Tb 3+ ; ZnTb-1 has moderate Tb 3+ luminescence, yet an absence of Tb 3+ emission is found in ZnTb-3. Such an emission difference could be mainly attributed to the antenna effect directed by distinct structural characteristics induced by anions. The anion-dictated self-assembly strategy presented herein not only offers a facile approach to regulate the coordination mode of H 2 L to such an extent to obtain diverse structures of Zn II -Ln III heterometallic species but also provides an understanding of how common inorganic anions tune coordination-driven self-assemblies as well as the subsequent luminescence properties.

show abstract

“…Making use of the in situ ligand transformation from GlcNAc to Chromogen I, a kind of {Ln 9 } cluster that can be further self-organized into nanocage-like {Ln 54 } aggregates was built . The original o -vanillin ligand transformed into 6,6′-(oxybis(methylene))bis (2-methoxyphenol) by a two-step in situ reaction, resulting in the formation of a {Dy 12 Na 6 } cage cluster . But beyond these cases, in situ ligand transformation-assisted assembly was still scarcely observed in the Ln cluster family, especially in polynuclear Dy III -SMMs …”

Section: Introductionmentioning

confidence: 99%

Dysprosium Clusters from 3-Ethoxysalicylidene Terminal-Decorated Acylhydrazone Ligands: In Situ Ligand Transformation-Assisted Assembly and Zero-Field Single-Molecule Magnet Behaviors

Chen

Peng

Pan

et al. 2023

Crystal Growth & Design

View full text Add to dashboard Cite

High-performance polynuclear lanthanide single-molecule magnets (Ln-SMMs) are still scarce now. Herein, we report the assembly of three novel Dy III clusters, where in situ ligand transformation-assisted assembly offered a system with high SMM performance successfully. These clusters, [Dy 6 (bepho) 3 (NO 3 ) 6 (CH 3 OH) 3 (H 2 O) 3 ]•5CH 3 OH•CH 3 CN•2H 2 O (1), [Dy 4 (bepho) 2 (H 3 epho) 2 (CH 3 OH) 2 ]•2CH 3 OH (2), and [Dy 5 (eehz) 3 (eqzl)(μ-CH 3 O)(μ 3 -CH 3 O) 2 (μ 4 -O)(CH 3 OH)]•2CH 3 OH (3), were all assembled from 3-ethoxysalicylidene terminal-decorated acylhydrazones. H 4 bepho, H 5 epho, H 3 eehz, and Heqzl represent N,N′-bis(3-ethoxysalicylicdene)pyridine-2,6-dicarbohydrazide N-oxide, N-(3-ethoxysalicylidene)pyridine-2,6-dicarbohydrazide N-oxide, N-(3-ethoxysalicylicdene)-2-(3-ethoxysalicylideneamino)benzohydrazide, and 3-(3-ethoxysalicylicdeneamino)quinazolinone, respectively. Cluster 1 is built by H 4 bepho directly, showing a hexanuclear zig-zag chain structure, while for 2 and 3, their original ligands all undergo unprecedented in situ transformations during the assembly. H 5 epho featuring asymmetric chelating arms and Heqzl bearing the quinazolinone parent are formed in 2 and 3, respectively, and participate in the assembly of clusters along with original ligands. In 2, H 4 bepho and H 5 epho construct a quasi-linear {Dy 4 } topology. A unique pentanuclear core of 3 is assembled by H 3 eehz and Heqzl. It consists of a [Dy 4 ] tetrahedron and a [Dy 3 ] triangle unit sharing an edge. Clusters 1−3 all show zero-field SMM behaviors, and 2 displays two distinct relaxation processes. Strikingly, the quantum tunneling of magnetization (QTM) effect in 3 might be suppressed by intramolecular magnetic interactions associated with its unique cluster topology. The zero-field energy barrier (U eff ) of 3 reaches up to 211.3 K, which is among the high values for all polynuclear Ln-SMM species and also the second largest one in the {Ln 5 }-SMM family.

show abstract

Large Heterometallic Dy₁₂Na₆ Cage-like Cluster Supported by in Situ Generated Ligand

Cited by 13 publications

References 25 publications

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

Anion-Dependent Structure and Luminescence Diversity in Zn^II-Ln^III Heterometallic Architectures Supported by a Salicylamide-Imine Ligand

Dysprosium Clusters from 3-Ethoxysalicylidene Terminal-Decorated Acylhydrazone Ligands: In Situ Ligand Transformation-Assisted Assembly and Zero-Field Single-Molecule Magnet Behaviors

Contact Info

Product

Resources

About

Large Heterometallic Dy12Na6 Cage-like Cluster Supported by in Situ Generated Ligand

Cited by 13 publications

References 25 publications

Coordination-Driven Self-Assembled ZnII6-LnIII3 Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc–

Coordination-Driven Self-Assembled ZnII6-LnIII3 Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc–

Anion-Dependent Structure and Luminescence Diversity in ZnII-LnIII Heterometallic Architectures Supported by a Salicylamide-Imine Ligand

Dysprosium Clusters from 3-Ethoxysalicylidene Terminal-Decorated Acylhydrazone Ligands: In Situ Ligand Transformation-Assisted Assembly and Zero-Field Single-Molecule Magnet Behaviors

Contact Info

Product

Resources

About

Large Heterometallic Dy₁₂Na₆ Cage-like Cluster Supported by in Situ Generated Ligand

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

Coordination-Driven Self-Assembled Zn^II₆-Ln^III₃ Metallocycles Based on a Salicylamide Imine Ligand: Synthesis, Structure, and Selective Luminescence Enhancement Induced by OAc^–

Anion-Dependent Structure and Luminescence Diversity in Zn^II-Ln^III Heterometallic Architectures Supported by a Salicylamide-Imine Ligand