Fluorinated mixed valence Fe(<scp>ii</scp>)–Fe(<scp>iii</scp>) phosphites with channels templated by linear tetramine chains. Structural and magnetic implications of partial replacement of Fe(<scp>ii</scp>) by Co(<scp>ii</scp>)

Orive, Joseba; Luis, Roberto Fernández de; Fernández, J. Rodrı́guez; Legarra, E.; Plazaola, F.; Arriortua, Marı́a I.

doi:10.1039/c4ce00264d

Cited by 3 publications

(2 citation statements)

References 88 publications

(72 reference statements)

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“…In these figures are also included the temperature dependences of C mag under applied magnetic fields up to 90 kOe. In both compounds, at zero field, the most significant features are (i) the jump in C mag at the order temperature has a small value, suggesting the existence of a complex magnetic order, , and (ii) in addition to the low-temperature peak, appears a broad maximum centered around 11 K, which usually is attributed to the existence of two-dimensional magnetic order, crystalline electrical field or the presence of short-range magnetic interactions. , …”

Section: Results and Discussionmentioning

confidence: 96%

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

et al. 2016

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The present work provides two new examples of supramolecular metal-organic frameworks consisting of three-dimensional extended noncovalent assemblies of wheel-shaped heptanuclear [Cu7(μ-H2O)6(μ3-OH)6(μ-adeninato-κN3:κN9)6](2+) entities. The heptanuclear entity consists of a central [Cu(OH)6](4-) core connected to six additional copper(II) metal centers in a radial and planar arrangement through the hydroxides. It generates a wheel-shaped entity in which water molecules and μ-κN3:κN9 adeninato ligands bridge the peripheral copper atoms. The magnetic characterization indicates the central copper(II) center is anti-ferromagnetically coupled to external copper(II) centers, which are ferromagnetically coupled among them leading to an S = 5/2 ground state. The packing of these entities is sustained by π-π stacking interactions between the adenine nucleobases and by hydrogen bonds established among the hydroxide ligands, sulfate anions, and adenine nucleobases. The sum of both types of supramolecular interactions creates a rigid synthon that in combination with the rigidity of the heptameric entity generates an open supramolecular structure (40-50% of available space) in which additional sulfate and triethylammonium ions are located altogether with solvent molecules. These compounds represent an interesting example of materials combining both porosity and magnetic relevant features.

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Section: Results and Discussionmentioning

confidence: 96%

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

et al. 2016

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“…The binding energies around 133 eV are significantly lower than those observed for P(V) species, 22 which is consistent with phosphite groups. 23…”

Section: Scanning Electron Microscopymentioning

confidence: 99%

A_x(H₃O)_2−xMn₅(HPO₃)₆ (A = Li, Na, K and NH₄): open-framework manganese(ii) phosphites templated by mixed cationic species

et al. 2016

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Ax(H3O)2-xMn5(HPO3)6 (A = Li, x = 0.55 (1-Li); A = Na, x = 0.72 (2-Na); A = K, x = 0.30 (3-K); A = NH4, x = 0.59 (4-NH4)) phases were synthesized by employing mild hydrothermal conditions. 1-Li was studied by single crystal X-ray diffraction, while sodium, potassium and ammonium containing analogues were obtained as polycrystalline samples and characterized by powder X-ray diffraction. The four compounds were characterized by ICP-Q-MS, thermal analysis and XPS, IR, UV/Vis and EPR spectroscopy. Single crystal data indicate that 1-Li crystallizes in the P3[combining macron]c1 space group with lattice parameters a = 10.3764(1) Å and c = 9.4017(1) Å with Z = 2. The crystal structure of these phases is constituted by a three-dimensional [Mn(ii)5(HPO3)6](2-) anionic skeleton templated by alkali metal and ammonium cations together with protonated water molecules. Such an inorganic framework is formed by layers of edge-sharing MnO6 octahedra placed in the ab plane and joined along the c direction through phosphite pseudotetrahedra. The sheets display 12-membered ring channels parallel to the c-axis, ca. 5 Å in diameter, where the extraframework species display a strong disorder. EPR measurements point to the existence of short range ferromagnetic interactions around 12 K. Magnetic susceptibility and heat capacity measurements show that all the compounds exhibit long range antiferromagnetic order below circa 4 K, with a significant magnetocaloric effect around the Neel temperature.

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An open-framework manganese(ii) phosphite and its composite membranes with polyvinylidene fluoride exhibiting intrinsic water-assisted proton conductance

et al. 2017

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Proton conducting materials have important technological applications as key components in electrochemical devices, including fuel cells, electrochemical sensors, electrochemical reactors and electrochromic displays. And the exploration of novel proton conducting materials is significant for the development of efficient electrochemical devices. In this study, we have investigated the proton conductance of an open-framework manganese(ii) phosphite, (NH)(HO)Mn(HPO) (1). The open-framework manganese(ii) phosphate shows superior water-stability and excellent thermal stability. There was intrinsic water-assisted proton conductivity with σ = 3.94 × 10 S cm at 328 K and 98% RH. Furthermore, composite membranes have further been fabricated using polyvinylidene fluoride (PVDF) and 1, labeled as 1@PVDF-X, where the symbol X represents the mass percentage of 1 (as X%) in the composite membrane and X = 10-55%. The composite membranes display good mechanical performance and durability for practical applications, and the proton conductivity of 1@PVDF-55 reaches 3.32 × 10 S cm in deionized water at 336 K.

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Fluorinated mixed valence Fe(ii)–Fe(iii) phosphites with channels templated by linear tetramine chains. Structural and magnetic implications of partial replacement of Fe(ii) by Co(ii)

Abstract: Three novel 3D open-framework fluorinated mixed valence Fe(ii)–Fe(iii) phosphites with channels templated by protonated tetramine chains were synthesized.

Cited by 3 publications

References 88 publications

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

A_x(H₃O)_2−xMn₅(HPO₃)₆ (A = Li, Na, K and NH₄): open-framework manganese(ii) phosphites templated by mixed cationic species

An open-framework manganese(ii) phosphite and its composite membranes with polyvinylidene fluoride exhibiting intrinsic water-assisted proton conductance

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Fluorinated mixed valence Fe(ii)–Fe(iii) phosphites with channels templated by linear tetramine chains. Structural and magnetic implications of partial replacement of Fe(ii) by Co(ii)

Abstract: Three novel 3D open-framework fluorinated mixed valence Fe(ii)–Fe(iii) phosphites with channels templated by protonated tetramine chains were synthesized.

Cited by 3 publications

References 88 publications

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

3D Magnetically Ordered Open Supramolecular Architectures Based on Ferrimagnetic Cu/Adenine/Hydroxide Heptameric Wheels

Ax(H3O)2−xMn5(HPO3)6 (A = Li, Na, K and NH4): open-framework manganese(ii) phosphites templated by mixed cationic species

An open-framework manganese(ii) phosphite and its composite membranes with polyvinylidene fluoride exhibiting intrinsic water-assisted proton conductance

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A_x(H₃O)_2−xMn₅(HPO₃)₆ (A = Li, Na, K and NH₄): open-framework manganese(ii) phosphites templated by mixed cationic species