New wheel-shaped Ln6 clusters for conversion of CO2 and magnetic properties

Wang, Wenmin; Qiao, Na; Xin, Xiao-Yan; Yang, Chen; Chen, Ying; Dong, Shanshan; Zhang, Chenxi

doi:10.1016/j.jre.2022.09.012

Cited by 12 publications

(3 citation statements)

References 93 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Catalytic properties. Considering the excellent solvent stability and Lewis acidity of clusters 1 – 3 mentioned above, − the catalytic properties of clusters 1 – 3 as catalysts were explored and studied. After condition exploration, the optimized reaction conditions are 70 °C under 0.1 MPa CO 2 with 3 mol % catalyst 1 and 2.5 mol % co-catalyst tetrabutylammonium bromide (TBAB) under solvent-free condition (Table , entry 6).…”

Section: Resultsmentioning

confidence: 99%

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Wang

Qiao

Xin

et al. 2022

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

A series of new Ln8 clusters [Ln8(acac)4(HL)4(L)2(μ3-O)4(C2H5O)4]·2C2H5OH·2CH2Cl2 (Ln(III) = Gd (1), Dy (2), and Ho (3); Hacac = acetylacetone and H2L = 2-hydroxy-benzoic acid (5-hydroxymethyl-furan-2-ylmethylene)-hydrazide) have been designed and constructed using a multiple coordination site Schiff base ligand (H2L) as  well  as a β-diketonate auxiliary ligand.  The structures, magnetic properties, and catalytic performance of clusters 1–3 have been studied. X-ray crystallography data revealed that clusters 1–3 possess similar structures with two chair-form Ln4 cores bridged by four μ3-O atoms. Clusters 1–3 display extensive and high solvent stability. Magnetic analysis exhibits that cluster 1 possesses a comparably large magnetocaloric effect (−ΔS m = 33.06 J kg–1 K–1 at 2.0 K and 7.0 T). AC susceptibility measurement suggests that cluster 2 exhibits single-molecule magnet behavior under zero-field conditions. What’s more, all clusters can effectively convert CO2 with epoxides. The highest yield is 98% at 70 °C 0.1 MPa catalyzed by 1. In addition, cluster 1 can be reused three times with a negligible loss of catalytic activity.

show abstract

Section: Resultsmentioning

confidence: 99%

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Wang

Qiao

Xin

et al. 2022

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…It is becoming increasingly clear that the excessive emission of CO 2 caused by ocean acidification is becoming a major priority. − Fruitful efforts have turned toward converting nontoxic and renewable CO 2 into value-added fine chemicals. − Given that CO 2 is the kinetic inertness and thermodynamic stability, this way in itself is greatly challenging. CO 2 is an important building block molecule to the synthesis of many important classes of compounds. − The oxazolidinones, five-membered heterocyclic compounds, have been widely studied because of the application in antibiotics with the activity against Gram-positive bacteria.…”

Section: Introductionmentioning

confidence: 99%

Two Series of Tetranuclear Ln(III)-Based Clusters: Structures, Magnetic Behaviors, and Efficient Cycloaddition of CO₂ to Oxazolidinones

Qiao,

Xin,

Yang

et al. 2023

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

Four new and interesting Ln4 clusters formulated as [Ln4(NO3)2(acac)4(HL1)2(CH3OH)2]·2(CH3CN)] (Ln = Gd(1), Dy(2); H4L1 = 2-(hydroxymethyl)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)propane-1,3-diol); acac = acetylacetone) and [Ln4(NO3)2(acac)4(L2)2(CH3CH2OH)2] (Ln = Gd(3), Dy(4); H3L2 = 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)-2-methylpropane-1,3-diol; acac = acetylacetone) were designed and constructed. Single-crystal X-ray studies indicate that all clusters have a defect dicubane topology in which four Ln(III) are on a plane bond with an arrangement of a parallelogram with the μ3-O bridge. The difference between the two series of clusters lies in the change of the ligand substituent and terminal coordinated solvent molecules. All Ln(III)-based clusters 1–4 have exhibited excellent solvent stability. The magnetic investigation suggests that clusters 1 and 3 possess a different magnetothermal effect (−ΔS m = 35.24 J kg–1 K–1 for 1, and −ΔS m = 36.68 J kg–1 K–1 for 3). In addition, the diversity in the environment of the metal center leads to the distinct dynamic behavior of U eff/k B (21.27 K for 2 and 1.96 K for 4) and τ0 (1.43 × 10–7 s for 2 and 2.43 × 10–6 s for 4). More importantly, clusters 1–4 as heterogeneous catalysts can efficiently catalyze the reaction of CO2 with bromopropylene oxide and aromatic amine to synthesize oxazolidinones under mild conditions. By comparison, clusters 1 and 2 show higher catalytic activity than 3 and 4, in which the Brønsted acidic −OH groups working together with Lewis acid metal sites improve the catalytic activity of Ln(III)-based clusters 1 and 2. To the best of our knowledge, it is the first example of Ln(III)-based clusters that show good magnetic property and high catalytic activity simultaneously by regulating the coordination environment of Ln(III) ions. Our work provided a promising direction for regulating properties of multifunctional polynuclear Ln(III)-based clusters via changing the coordinated environment of the metal center. It also helps inspire the development of polynuclear Ln(III)-based multifunctional materials.

show abstract

“…Although these types of catalytic reactions were intensively studied, the cycloaddition reaction of epoxides with CO 2 to produce cyclic carbonates is still considered one of the best classic organic reaction for converting of CO 2 . To date, lots of Ln(III)-based compounds have been reported for this type of transformation due to the strong Lewis acidity of Ln 3+ ions. − In 2016, Zhao’s group reported a novel 3D Eu(III)-based metal–organic framework (MOF) which can be considered as a high-efficiency catalyst for the cycloaddition reaction of epoxides and CO 2 . Subsequently, our group constructed a series of Ln 8 clusters, which can catalyze the coupling reaction of CO 2 with epoxides efficiently under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Bifunctional Lanthanide-Based Coordination Polymers: Conversion of CO₂ and Highly Selective Luminescence Sensing for Acetylacetone

Wang,

Cheng,

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

A series of bifunctional Ln(III)-based coordination polymers (CPs) {Ln(L)(DMA)2(NO3)} n [Ln(III) = Eu (1), Gd (2), and Dy (3); organic ligand H2L = 2,2′-(1,3,5,7-tetrahydroxyoctahydro-4,8-ethanopyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)diacetic acid)] have been successfully synthesized. CPs 1–3 are isostructural and constructed from the dimeric Ln2 unit in which two adjacent LnIII ions are bridged by two μ3-carboxyl oxygens, and the Ln2 dimeric unit is connected by two NO3 – ions, four DMA molecules, and four completely protonated L2– ligands forming a 2D layer structure. The magnetic research reveals that CP 2 shows a significant cryogenic magnetocaloric effect (−ΔS m = 22.9 J kg–1 K–1; T = 2.0 K and ΔH = 7.0 T), whereas CP 3 exhibits slow magnetic relaxation property under H dc = 0 Oe field. Additionally, the luminescence explorations revealed that CP 1 can act as a recyclable luminescent probe for pollutant acetylacetone among various small organic solvent molecules, and the corresponding detection limit is 10–7 mol/L. More importantly, CP 1 also exhibits good catalytic performance in the cycloaddition reaction of CO2 and epoxides or cyanamides under mild conditions. As far as we know, CP 1 represents the first bifunctional lanthanide homogeneous catalyst that can efficiently catalyze the reaction of cyanamides/epoxides with CO2 simultaneously.

show abstract

New wheel-shaped Ln6 clusters for conversion of CO2 and magnetic properties

Cited by 12 publications

References 93 publications

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Two Series of Tetranuclear Ln(III)-Based Clusters: Structures, Magnetic Behaviors, and Efficient Cycloaddition of CO₂ to Oxazolidinones

Bifunctional Lanthanide-Based Coordination Polymers: Conversion of CO₂ and Highly Selective Luminescence Sensing for Acetylacetone

Contact Info

Product

Resources

About

New wheel-shaped Ln6 clusters for conversion of CO2 and magnetic properties

Cited by 12 publications

References 93 publications

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO2 to Cyclic Carbonates and Large Magnetocaloric Effect

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO2 to Cyclic Carbonates and Large Magnetocaloric Effect

Two Series of Tetranuclear Ln(III)-Based Clusters: Structures, Magnetic Behaviors, and Efficient Cycloaddition of CO2 to Oxazolidinones

Bifunctional Lanthanide-Based Coordination Polymers: Conversion of CO2 and Highly Selective Luminescence Sensing for Acetylacetone

Contact Info

Product

Resources

About

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Octanuclear Ln(III)-Based Clusters Assembled by a Polydentate Schiff Base Ligand and a β-Diketone Co-Ligand: Efficient Conversion of CO₂ to Cyclic Carbonates and Large Magnetocaloric Effect

Two Series of Tetranuclear Ln(III)-Based Clusters: Structures, Magnetic Behaviors, and Efficient Cycloaddition of CO₂ to Oxazolidinones

Bifunctional Lanthanide-Based Coordination Polymers: Conversion of CO₂ and Highly Selective Luminescence Sensing for Acetylacetone