3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

Zhang, Sheng; Liu, Xiangyu; Liu, Bin; Xia, Zhengqiang; Wang, Weitao; Yang, Qi; Ke, Hongshan; Wei, Qing; Xie, Gang; Chen, Sanping; Gao, Shengli

doi:10.1007/s11426-015-5318-9

Cited by 8 publications

(6 citation statements)

References 67 publications

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“…Notably, MOFs made exclusively from Co(III) SBUs are themselves unprecedented. Indeed, the only previous examples of MOFs containing Co(III) in the nodes are cases of mixed-valent Co(II)/Co(III) materials − or examples where the presence of dilute Co(III) within a native Co(II) MOF has been inferred from its catalytic activity. , …”

Section: Resultsmentioning

confidence: 99%

Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework

et al. 2017

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Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal−organic framework (MOF) to produce stable and safe-tohandle Co(III) materials featuring terminal Co(III)−halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)−halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

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Section: Resultsmentioning

confidence: 99%

Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework

et al. 2017

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“…Metal–organic frameworks (MOFs) have several unique properties such as uniform and tunable pore sizes, diverse structural topologies, and tunable functionalities . These features endow MOFs with excellent abilities in a wide range of applications, including gas storage/separation, guest‐dependent luminescence, catalysis, and so on . Furthermore, combining the functions of MOFs with metal cores to create multifunctional core@shell nanocomposites has been extensively investigated .…”

Section: Methodsmentioning

confidence: 99%

Surfactant‐Free Palladium Nanoparticles Encapsulated in ZIF‐8 Hollow Nanospheres for Size‐Selective Catalysis in Liquid‐Phase Solution

Wang

Cao

et al. 2016

ChemCatChem

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Encapsulation of surfactant‐free Pd nanoparticles (NPs) in the metal–organic framework material ZIF‐8 hollow nanospheres was achieved. Pd@ZIF‐8 hollow nanospheres showed excellent size‐selective catalytic properties in the liquid‐phase hydrogenation of olefins. As a result of the uniform pore size of the ZIF‐8 shell (apertures of 3.4 Å), the catalyst showed high activity for the hydrogenation of 1‐hexene (1.9×8.2 Å) but very low activity for larger molecules such as cis‐cyclooctene (5.3×5.5 Å), trans‐stilbene (4.2×11.3 Å), and triphenylethylene (9.1×9.2 Å). Other surfactant‐free noble‐metal nanoparticles could also be employed to produce NPs@MOFs for catalysis.

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“…The 2D coordination polymer, [Co(L) 2 (SCN) 2 ·2CH 3 CN·2DMF] n (where L = 4′-(4-methoxyphenyl)-4,2′:6′,4″-terpyridine]) represents a particularly interesting example where the extended ligand-spacer prevents any magnetic interaction among the metal nodes thereby leading to isolated single-ion magnetic centers . Similar field-induced SIM behavior has been also explored by other research groups in 1D, − 2D, − and 3D − Co(II) based coordination polymers where the metal centers remain magnetically isolated.…”

Section: Introductionmentioning

confidence: 68%

Field-Induced Slow Magnetic Relaxation and Anion/Solvent Dependent Proton Conduction in Cobalt(II) Coordination Polymers

Mondal

Dey

Roy

et al. 2018

Crystal Growth & Design

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Three new coordination polymers (CPs), namely, 2D {[Co(L)2(H2O)2](ClO4)2·3DMA·0.4H2O} n (1), 3D {[Co(L)2(H2O)2]·(Cl)2} n (2), and 2D {[Co(L)2(NCS)2]} n (3) were obtained by the self-assembly of corresponding cobalt(II) salts and a linear semirigid linker bis(4-imidazol-1-yl-phenyl)diazene (L) designed with two terminal imidazole groups and an azo moiety in the middle. CPs 1 and 2 are composed of a cationic framework which leads to incorporation of anion in the framework along with solvent molecules (only in 1), whereas CP 3 possesses a neutral framework. The cationic core adopts a cis and trans configuration in 1 and 2, respectively. The structures consist of 2D net with sql topology in 1, eightfold interpenetrating 3-periodic network with dia topology in 2 and threefold interpenetrating 2-periodic network with sql (2,4L2) topology in 3. The structural diversity of CPs 1–3 is governed by several factors, including the different coordination ability of the anions, reaction conditions and intermolecular interactions. Using the method of molecular Voronoi polyhedral, all intermolecular interactions in CPs 1–3 have been analyzed. Magnetic susceptibility measurements in the range 2–300 K reveal that in these CPs Co(II) ions behave as magnetically isolated centers with a significant orbital contribution to the magnetic moment. Alternating current (ac) measurements show signature of slow magnetic relaxation in these CPs. Ab initio investigations on simplified model structures indicate that CoII nodes in the CPs exhibit easy-plane magnetic anisotropy. Furthermore, CP 1 displays significant value of proton conductivity which reaches up to 3.96 × 10–4 S cm–1 at 80 °C and 95% relative humidity (RH).

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3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

Cited by 8 publications

References 67 publications

Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework

Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework

Surfactant‐Free Palladium Nanoparticles Encapsulated in ZIF‐8 Hollow Nanospheres for Size‐Selective Catalysis in Liquid‐Phase Solution

Field-Induced Slow Magnetic Relaxation and Anion/Solvent Dependent Proton Conduction in Cobalt(II) Coordination Polymers

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3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

Cited by 8 publications

References 67 publications

Reversible Capture and Release of Cl2 and Br2 with a Redox-Active Metal–Organic Framework

Reversible Capture and Release of Cl2 and Br2 with a Redox-Active Metal–Organic Framework

Surfactant‐Free Palladium Nanoparticles Encapsulated in ZIF‐8 Hollow Nanospheres for Size‐Selective Catalysis in Liquid‐Phase Solution

Field-Induced Slow Magnetic Relaxation and Anion/Solvent Dependent Proton Conduction in Cobalt(II) Coordination Polymers

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Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework

Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework