Synthesis and characterization of novel bis-arsenic complexes

p-Phenylenebis[diethyl(iso-propyl)arsonium] tetra-N-thiocyanatocobaltate(II) cationic-anionic complex have been synthesized and studied. The X-ray structure of + [(i-Pr)2(Et)4As2(Ph)]+ [Co(NCS)4] 2- have been determined. Crystals belong to the tetragonal system, space group P-42(1)m) with a = 14.4930(14)Å, b = 14.4930(14)Å, c = 8.7090(19)Å; α = 90°, β = 90°, γ = 90°. The structures were refined to an R value of 0.063 from 4082 observed reflections. The As atom is coordinated tetrahedraly to the substituents as well as the anion has a tetrahedral configuration. The synthesis and IR spectral characterization of the complex compounds are described

Effect of Missing-Linker Defects and Ion Exchange on Stability and Proton Conduction of a Sulfonated Layered Zr-MOF

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.3c03873.Intentionally introduced defects into solid materials create opportunities to control and tune their diverse physicochemical properties. Despite the growing interest in defect-engineered metal-organic frameworks (MOFs), there are still only a handful of studies on defective proton-conducting MOFs, including no reports on two-dimensional ones. Ion-conducting materials are fundamentally of great importance to the development of energy storage and conversion devices, including fuel cells and batteries. In this work, we demonstrate the introduction of missing-linker defects into a sulfonated proton conductive 2D zirconium-based MOF (JUK-14), using a facile post-synthetic approach and compare the stability and performance of the resulting materials, including proton conductivity, as well as adsorption of N2, CO2, and H2O molecules. We also discuss the associated presence of interlayer counterions and their effect on the properties and stability. Our approach to defect engineering can be extended to other layered MOFs and used for tuning their activity.Narodowe Centrum Nauki 2019/35/B/ST5/01067 NC

Structure and Reactivity of (PPh4)3[W(CN)5O] ⋅ 7H2O. Kinetics and Mechanism of the Reaction with Molecular Oxygen

The (PPh4)3[W(CN)5O] ⋅ 7H2O has been synthesised and structurally characterised by X-ray diffraction. In the solid state and in ethanol-acetone mixture, the salt reacts with molecular oxygen giving (PPh4)2[W(CN)4O(O2)]. The progress of the solid state reaction was followed by measuring infrared spectra. The integrated intensities of the W=O, O−O and C≡N bands changed with time according to the pseudo first-order kinetics. In solution, the kinetic measurements indicate that the rate law is of the form -d[complex]/dt = k[complex][O2]. The k value is equal to 5.78 (±0.26) mol-1 dm3 s-1 at 298 K. The activation parameters, ΔH‡(k) and ΔS‡(k), are 55 (±3) kJ mol-1 and -46 (±8) J K-1 mol-1, respectively. A reaction mechanism is proposed

Tetra(n-butyl)ammonium salt of a ferrimagnetic complex based on mixed-valent dinuclear ruthenium pivalate and octacyanidotungstate(V)

International audienceA tetra (n-butyl)ammonium (n-Bu4N+) salt of Ru2–W complex consisting of dinuclear ruthenium (II,III) pivalate, ([RuIIRuIII(piv)4]+) (Hpiv = pivalic acid), and octacyanidotungstate(V), [n-Bu4N][{RuIIRuIII(piv)4}2(H2O){WV(CN)8}] (1), was synthesized and characterized by elemental analysis, infrared spectra, and temperature dependence of magnetic susceptibilities (2–300 K). The crystal structure of 1 revealed a zigzag one-dimensional chain molecule along the c axis with alternating arrangement of [RuIIRuIII(piv)4]+ and [WV(CN)8]3−, where another [RuIIRuIII(piv)4]+ unit is dangled from the [WV(CN)8]3− moiety. The magnetic susceptibilities and zero-field-cooled and field-cooled magnetization data showed that the present complex is ferrimagnetic with a Tc value of 5.5 K. The field dependence of magnetization exhibited a hysteresis with a coercive field of 150 Oe at 2 K

Magnetic material based on mixed-valent dinuclear pivalate and cyanidometalate

Mixed-metal complex consisting of ruthenium(II,III) pivalate, ([Ru₂(piv)₄]⁺) (Hpiv = pivalic acid), tetraethylammonium and octacyanidotungstate(V) ions, (Et₄N)[{Ru₂(piv)₄}₂W(CN)₈]·4H₂O, was synthesized and characterized by elemental analysis, infrared and UV-vis spectra and temperature dependence of magnetic susceptibilities (2-300 K). The magnetic susceptibilities, zero-field-cooled and field-cooled magnetizations, and AC susceptibility data showed that the present complex is ferrimagnetic with T_{c} value of 80 K. The field dependence of magnetization exhibited a hysteresis with a coercive field of 17000 Oe at 5 K

Structure and Reactivity of (PPh4)3[W(CN)5O] ⋅ 7H2O. Kinetics and Mechanism of the Reaction with Molecular Oxygen

The (PPh4)3[W(CN)5O] ⋅ 7H2O has been synthesised and structurally characterised by X-ray diffraction. In the solid state and in ethanol-acetone mixture, the salt reacts with molecular oxygen giving (PPh4)2[W(CN)4O(O2)]. The progress of the solid state reaction was followed by measuring infrared spectra. The integrated intensities of the W=O, O−O and C≡N bands changed with time according to the pseudo first-order kinetics. In solution, the kinetic measurements indicate that the rate law is of the form -d[complex]/dt = k[complex][O2]. The k value is equal to 5.78 (±0.26) mol-1 dm3 s-1 at 298 K. The activation parameters, ΔH‡(k) and ΔS‡(k), are 55 (±3) kJ mol-1 and -46 (±8) J K-1 mol-1, respectively. A reaction mechanism is proposed