Synthesis, structure and magnetic properties of a novel ferromagnetic cluster [FeV6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2

Khan, M. Ishaque; Tabussum, Saadia; Doedens, Robert J.; Golub, Vladimir; O’Connor, Charles J.

doi:10.1016/j.inoche.2003.10.003

Cited by 17 publications

(15 citation statements)

References 21 publications

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“…This may be attributed to monomethylamine cations in 1 hindering the polymerization of 1a . Previously, the heterometals in FeV complexes were usually bridged by the alkoxy group of alcohol, such as methyl alcohol, alkamine. − In our cases, α-hydroxycarboxylic acid with α-alkoxy and carboxy groups serve as a good candidate to build O-bridged heterometal clusters. However, only malic acid has been used for the preparation of 1 , while use of its homologue citric or homocitric acid was unsuccessful.…”

Section: Resultsmentioning

confidence: 76%

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

et al. 2020

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Isolated octanuclear iron–vanadium malate (NH4)3(CH3NH3)3[FeIII 2VIV 2VV 4O11(mal)6]·7.5H2O (1; H3mal = malic acid) and its family of metal hydrates M′3n [MII(H2O)2]1.5n [FeIII 2VIV 2VV 4O11(mal)6] n ·xnH2O (2 or 2-Fe, M′ = NH4 +, M = Fe, x = 7.5; 3 or 3-Cu, M′ = K+, M = Cu, x = 10; 4 or 4-Zn, M′ = K+, M = Zn, x = 6.5) have been obtained by self-assembly in water. The cluster anion [Fe2V6O11(mal)6]6– (1a) shows an interesting iron bicapped-triangular-prismatic structure, which is bridged by M2+ hydrates (M = Fe, Cu, Zn) to construct isostructural metal organic frameworks (MOFs) 2–4. The mixed-valence vanadium systems in 1–4 were determined by theoretical bond valence calculations (BVS) and charge balance. The magnetic susceptibilities are further elucidated as high spin for Fe3+ in 1a and bridging Fe2+ in 2-Fe, respectively. A strong ferromagnetic interaction was also observed for 2-Fe at 3 K. 2-Fe, 3-Cu, and 4-Zn have similar hydrophilic channels with diameters of 6.8, 6.5, and 6.6 Å, respectively, which show obvious affinity for O2 in comparison with no adsorption of N2, H2, CO2, and CH4 at room temperature under different pressures. Moreover, 2-Fe and 4-Zn exhibit irreversible O2 absorptions, which may be attributed to charge transfer between O2 and open metal sites (OMSs) formed during vacuum heating pretreatment. UV–vis and EPR spectra show a change in electronic structure of 2-Fe after O2 adsorption. The reversible adsorption observed in 3-Cu suggests a weak interaction between O2 and Cu2+ due to the Jahn–Teller effect. The properties of gas adsorption provide an insight into the performances of small molecules in the channels constructed by synthetic octanuclear model compounds, which are related to the interactions between the gas substrate and the heterometal cluster in biology.

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Section: Resultsmentioning

confidence: 76%

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

et al. 2020

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“…21 In a reduced oxidation state of vanadium, cyclic heteropolyoxovanadium complexes, [MV 6 O 6 {(OCH 2 CH 2 ) 2 N(CH 2 CH 2 OH)} 6 ]X (M = Li, Na, Mg, Mn, Fe, Co, Ni; X = Cl − , Br − ), have been reported. 22 An Anderson-type crown-shaped polyoxovanadate with organic ligands, [V 6 O 12 (OH) 3 (O 2 CCH 2 CH 2 NH 3 ) 3 (SO 4 )] + , can bind an anion at the center. 23 The metavanadate-based macrocyclic ligand,…”

Section: ■ Introductionmentioning

confidence: 99%

Lanthanide Complexes of Macrocyclic Polyoxovanadates by VO₄ Units: Synthesis, Characterization, and Structure Elucidation by X-ray Crystallography and EXAFS Spectroscopy

et al. 2011

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Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

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“…We are currently exploring the design and development of open framework composites by the amalgamation of vanadium oxide based structures with metal−organic compounds and their coordination polymers. − Unlike aluminosilicates, vanadium-based frameworks exhibit a variety of metal oxidation states, variable coordination numbers, and diverse geometries around the vanadium. These features could provide a basis for new types of catalytic behavior.…”

Section: Introductionmentioning

confidence: 99%

Inorganic−Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V₂O₆] and [{Co₂(4,4‘-Bipy)₃(H₂O)₂}V₄O₁₂]·2H₂O

et al. 2004

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Synthesis of two novel porous framework hybrid materials, [Co(4,4′-bipy)V 2 O 6 ] (1) and [{Co 2 (4,4′-bipy) 3 (H 2 O) 2 }V 4 O 12 ]‚2H 2 O (2), and their characterization by infrared spectroscopy, thermogravimetry, elemental analysis, manganometric titration, surface area measurement, bond valence sum calculations, temperature-dependent magnetic susceptibility measurement, and single-crystal X-ray structure analyses is described. Both compounds exhibit remarkable thermal stability. The three-dimensional structures of 1 and 2 are composed of fused {VO 4 } motifs linked by {Co(4,4′-bipy)} coordination polymers. The structure of 1 is comprised of {CoO 3 N 2 } trigonal bipyramids, linked in two dimensions by corner-sharing {VO 4 } tetrahedra and in the third dimension by the 4,4′-bipyridine ligands. In the bimetallic layers, the cobalt centers are bridged alternately by {VO 4 } and {V 2 O 7 } units, generating alternating eightmembered {Co 2 V 2 O 4 } and twelve-membered {Co 2 V 4 O 6 } rings. The crystal structure of 2 consists of a novel three-dimensional network containing two types of octahedral Co 2+ ions linked by a {V 2 O 7 } group. The cobalt centers in 2 are linked in three dimensions by bridging 4,4′-bipyridine ligands. The structure contains rather large channels parallel to the c-axis. A disordered water molecule of crystallization is present in the channels. Crystal data for C 10 H 8 N 2 O 6 CoV 2 , 1: triclinic space group P1 h (No. 2), a ) 8.1517(4) Å, b ) 8.5794(4) Å, c ) 10.1233(5) Å, R ) 87.0170(10)°, ) 75.9610(10)°, γ ) 75.1740(10)°, V ) 663.94(6) Å 3 , Z ) 2, D calcd ) 2.066 Mg‚m -3 , R1 ) 0.0252 (all data), wR2 ) 0.0669. Crystal data for C 15 H 16 N 3 O 8 -CoV 2 , 2: monoclinic space group C2/c (No. 15), a ) 30.4457(13) Å, b ) 11.3540(5) Å, c ) 11.5836(5) Å, ) 106.5390(10)°, V ) 3838.6(3) Å 3 , Z ) 8, D calcd ) 1.824 Mg‚m -3 , final R1 ) 0.0447 (all data), wR2 ) 0.1259.

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Synthesis, structure and magnetic properties of a novel ferromagnetic cluster [FeV6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2

Cited by 17 publications

References 21 publications

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

Lanthanide Complexes of Macrocyclic Polyoxovanadates by VO₄ Units: Synthesis, Characterization, and Structure Elucidation by X-ray Crystallography and EXAFS Spectroscopy

Inorganic−Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V₂O₆] and [{Co₂(4,4‘-Bipy)₃(H₂O)₂}V₄O₁₂]·2H₂O

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Synthesis, structure and magnetic properties of a novel ferromagnetic cluster [FeV6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2

Cited by 17 publications

References 21 publications

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe2+, Cu2+, Zn2+) with Reversible and Irreversible Adsorptions for Oxygen

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe2+, Cu2+, Zn2+) with Reversible and Irreversible Adsorptions for Oxygen

Lanthanide Complexes of Macrocyclic Polyoxovanadates by VO4 Units: Synthesis, Characterization, and Structure Elucidation by X-ray Crystallography and EXAFS Spectroscopy

Inorganic−Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V2O6] and [{Co2(4,4‘-Bipy)3(H2O)2}V4O12]·2H2O

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Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

Isolated Mixed-Valence Iron Vanadium Malate and Its Metal Hydrates (M = Fe²⁺, Cu²⁺, Zn²⁺) with Reversible and Irreversible Adsorptions for Oxygen

Lanthanide Complexes of Macrocyclic Polyoxovanadates by VO₄ Units: Synthesis, Characterization, and Structure Elucidation by X-ray Crystallography and EXAFS Spectroscopy

Inorganic−Organic Hybrid Materials Containing Porous Frameworks: Synthesis, Characterization, and Magnetic Properties of the Open Framework Solids [{Co(4,4‘-Bipy)}V₂O₆] and [{Co₂(4,4‘-Bipy)₃(H₂O)₂}V₄O₁₂]·2H₂O