A new intersecting tunnel structure in the AIMIII[PO3(OH)]2 series for AI = Ag,MIII = In: Analysis of structural relationships

A new indium hydroxyphosphate containing silver, AgIn[PO₃(OH)]₂, has been synthesized using hydrothermal method. It crystallizes in the P2₁/c space group with the cell parameters a = 6.6400(2) Å, b = 14.6269(6) Å, c = 6.6616(4) Å, β = 95.681(5)°, V = 643.82(6) Å³, Z = 4. Its three-dimensional framework, built up of corner-sharing PO₃(OH) tetrahedra and InO₆ octahedra, presents intersecting tunnels running along <111> and [100] directions, in which the Ag⁺ cations are located. The presence of hydroxyl groups has been confirmed from IR spectroscopy studies and hydrogen atoms were located from the single crystal X-ray diffraction study. The structural relationships with the other compounds of general formula A^IM^III[PO₃(OH)]₂ are analyzed.     

Synthesis of silver nanoparticles supported on silica aerogel using gamma radiolysis

Silver clusters on SiO₂ support have been synthesized using ⁶⁰Co gamma radiation. The irradiation of Ag⁺ in aqueous suspension of SiO₂ in the presence of 0.2 mol dm⁻³ isopropanol resulted in the formation of yellow suspension. The absorption spectrum showed a band at 408 nm corresponding to typical characteristic surface plasmon resonance of Ag nanoparticles. The effect of Ag⁺ concentration on the formation of Ag cluster indicated that the size of Ag clusters vary with Ag⁺ concentration, which was varied from 4×10⁻⁴ to 5×10⁻³ mol dm⁻³. The results showed that Ag clusters are stable in the pH range of 2–9 and start agglomerating in the alkaline region at pH above 9. The effect of radiation dose rate and ratio of Ag⁺/SiO₂ on the formation of Ag clusters have also been investigated. The prepared clusters have been characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), which showed the particle size of Ag clusters to be in the range of 10–20 nm.     

Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids: Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and α-linolenic) and glycerolipids. Remarkably, the formation of M₂H⁺ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag₂H⁺ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu₂H⁺ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also, Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly, Ag₂H⁺ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag₂H⁺ ion is a significant dissociation channel from the complex ion [Ag₂(L–H)]⁺ where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu₂H⁺ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I).     

Crystal structure and ionic conductivity of AgCr2(PO4)(P2O7)

Single crystals of a new phosphate AgCr₂(PO₄)(P₂O₇) have been prepared by the flux method and its structural and the infrared spectrum have been investigated. This compound crystallizes in the monoclinic system with the space group C2/c and the parameters are, a = 11.493 (3) Å, b = 8.486 (3) Å, c = 8.791 (2) Å, β = 114.56 (2)°, V = 779.8 (3) ųand Z = 4. Its structure consists of CrO₆ octahedra sharing corners with P₂O₇ units to form undulating chains extending infinitely along the [110] direction. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the Ag⁺ ions are located. The infrared spectrum of this compound was interpreted on the basis of P₂O₇^4? and PO₄^3? vibrations. The appearance of ν_sP–O–P in the spectrum suggests a bent P–O–P bridge for the P₂O₇^4? ions in the compound, which is in agreement with the X-ray data. The electrical measurements allow us to obtain the activation energy of (1.36 eV) and the conductivity measurements suggest that the charge carriers through the structure are the silver captions.     

Lithium Intercalation into ATi2(PS4)3 (A = Li,Na, Ag)

Comparison of the electrochemical insertion of lithium into ATi₂(PS₄)₃ with A = Li, Na, Ag and ATi₂(PO₄)₃ with Li, Ag is striking. Whereas only four lithium per formula unit (Li/f.u.) can be inserted reversibly into the phosphates, up to 7 and 10 Li/f.u. can be inserted reversibly in the thiophosphates with A = Li and Ag. Moreover, the Ag⁺ to Ag⁰ reduction in AgTi₂(PO₄)₃ is not reversible, but in AgTi₂(PS₄)₃ it is reversible. Strong hybridization of the Ag-5s and host antibonding bands stabilizes the formal valences Ag⁰, Ti⁺, and (PS₄)⁴⁻ in the discharged state of AgTi₂(PS₄)₃; but only the formal valence Ti²⁺ is accessible in LiTi₂(PS₄)₃. Unfortunately the large volume change associated with the lithium insertion renders the structure progressively more amorphous on cycling, which causes the capacity to fade quite dramatically on further cycling. The thiophosphates transform to the phosphates on heating in air.     

Solubility of CO2 in 1-(2-hydroxyethyl)-3-methylimidazolium ionic liquids with different anions

The solubility of carbon dioxide in a series of 1-(2-hydroxyethyl)-3-methylimidazolium ([hemim]⁺) based ionic liquids (ILs) with different anions, viz. hexafluorophosphate ([PF₆]^?), trifluoromethanesulfonate ([OTf]^?), and bis-(trifluoromethyl)sulfonylimide ([Tf₂N]^?) at temperatures ranging from 303.15 K to 353.15 K and pressures up to 1.3 MPa were determined. The solubility data were correlated using the Krichevsky–Kasarnovsky equation and Henry’s law constants were obtained at different temperatures. Using the solubility data, the partial molar thermodynamic functions of solution such as Gibbs free energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of CO₂ in the ILs studied follows the same behaviour as the corresponding conventional 1-ethyl-3-methylimidazolium ([emim]⁺) based ILs with the same anions, i.e. [hemim][NTf₂] > [hemim][OTf] > [hemim][PF₆] > [hemim][BF₄].     

Long-distance electronic interaction in a molecular wire consisting of a ferrocenyl–ethynyl unit bridging two [(η5-C5H5)(dppe)M] metal centers

Several multinuclear ferrocenyl–ethynyl complexes of formula [(η⁵-C₅H₅)(dppe)M^II?CC–(fc)_n–CC–M^II(dppe)(η⁵-C₅H₅)] (fc = ferrocenyl; dppe = Ph₂PCH₂CH₂PPh₂; 1: M^II = Ru²⁺, n = 1; 2: M^II = Ru²⁺, n = 2; 3: M^II = Ru²⁺, n = 3; 4: M^II = Fe²⁺, n = 2; 5: M^II = Fe²⁺, n = 3) were studied. Structural determinations of 2 and 4 confirm the ferrocenyl group directly linked to the ethynyl linkage which is linked to the pseudo-octahedral [(η⁵-C₅H₅)(dppe)M] metal center. Complexes of 1–5 undergo sequential reversible oxidation events from 0.0 V to 1.0 V referred to the Ag/AgCl electrode in anhydrous CH₂Cl₂ solution and the low-potential waves have been assigned to the end-capped metallic centers. The solid-state and solution-state electronic configurations in the resulting oxidation products of [1]⁺ and [2]²⁺ were characterized by IR, X-band EPR spectroscopy, and UV–Vis at room temperature and 77 K. In [1]⁺ and [2]²⁺, broad intervalence transition band near 1600 nm is assigned to the intervalence transition involving photo-induced electron transfer between the Ru³⁺ and Fe²⁺ metal centers, indicating the existence of strong metal-to-metal interaction. Application of Hush’s theoretical analysis of intervalence transition band to determine the nature and magnitude of the electronic coupling between the metal sites in complexes [1]⁺ and [2]²⁺ is also reported. Computational calculations reveal that the ferrocenyl–ethynyl-based orbitals do mix significantly with the (η⁵-C₅H₅)(dppe)Ru metallic orbitals. It clearly appears from this work that the ferrocenyl–ethynyl spacers strongly contribute in propagating electron delocalization.     

Volumetric properties of ternary (IL + 2-propanol or 1-butanol or 2-butanol + ethyl acetate) systems and binary (IL + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate) systems

The experimental densities for the binary or ternary systems were determined at T = (298.15, 303.15, and 313.15) K. The ionic liquid methyl trioctylammonium bis(trifluoromethylsulfonyl)imide ([MOA]⁺[Tf₂N]⁻) was used for three of the five binary systems studied. The binary systems were ([MOA]⁺[Tf₂N]⁻ + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate). The ternary systems were {methyl trioctylammonium bis(trifluoromethylsulfonyl)imide + 2-propanol or 1-butanol or 2-butanol + ethyl acetate}. The binary and ternary excess molar volumes for the above systems were calculated from the experimental density values for each temperature. The Redlich–Kister smoothing polynomial was fitted to the binary excess molar volume data. Virial-Based Mixing Rules were used to correlate the binary excess molar volume data. The binary excess molar volume results showed both negative and positive values over the entire composition range for all the temperatures.The ternary excess molar volume data were successfully correlated with the Cibulka equation using the Redlich–Kister binary parameters.     

Ethanol extraction from its azeotropic mixture with hexane employing different ionic liquids as solvents

In this work, the ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMim][NTf₂], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMim][NTf₂], 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, [BMpy][NTf₂], 1-butyl-3-methylpyridinium trifluoromethanesulfonate, [BMpy][TfO], have been investigated for their use as solvents in extraction processes for the ethanol removal from its azeotropic mixture with hexane. Therefore, the experimental determination of the liquid + liquid equilibrium for the ternary systems {hexane (1) + ethanol (2) + [EMim][NTf₂] (3)}, {hexane (1) + ethanol (2) + [BMim][NTf₂] (3)}, {hexane (1) + ethanol (2) + [BMpy][NTf₂] (3)} and {hexane (1) + ethanol (2) + [BMpy][TfO] (3)} was carried out at T = 298.15 K and atmospheric pressure. Classical parameters such as selectivity and solute distribution ratio, derived from the tie-line data, were calculated and afterwards, the structural influence of the ionic liquids on the extraction process was analyzed. Finally, the experimental LLE data were correlated by means of the NRTL and UNIQUAC models.     

Mixing and decomposition behavior of {[4bmpy][Tf2N] + [emim][EtSO4]} and {[4bmpy][Tf2N] + [emim][TFES]} ionic liquid mixtures

Mixing ionic liquids (ILs) has been revealed as a useful way to finely tune the properties of IL-based solvents. The scarce available studies on IL mixtures have shown a quasi-ideal behavior of their physical properties. In this work, we have performed a thermophysical characterization of two binary IL mixtures, namely {4-methyl-N-butylpyridinium bis(trifluoromethylsulfonyl)imide ([4bmpy][Tf₂N]) + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO₄])} and {[4bmpy][Tf₂N] + 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [emim][TFES]}. Both binary IL mixtures have been recently proposed as promising solvents in the (liquid + liquid) extraction of aromatic hydrocarbons from mixtures with alkanes. Densities, viscosities, refractive indices, thermal stability, and specific heats of the {[4bmpy][Tf₂N] + [emim][EtSO₄]} and {[4bmpy][Tf₂N] + [emim][TFES]} IL mixtures have been measured as a function of both temperature and composition. Dynamic viscosities, refractive indices, and thermal stability of the {[4bmpy][Tf₂N] + [emim][EtSO₄]} mixture have exhibited strong deviations from the ideality, in contrast with the quasi-ideal properties of the {[4bmpy][Tf₂N] + [emim][TFES]} mixture and the behavior of the imidazolium and pyridinium-based IL mixtures studied hitherto. The reliability of predictive methods of the thermophysical properties of the mixtures has also been evaluated.     

A kinetic and mechanistic study on the silver (I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid medium

The kinetics and mechanism of Ag(I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid media have been investigated by titrimetric technique of redox in the temperature range of 298–313 K. It is found that the reaction is of first order with respect to Ce(IV) and l-alanine, and it is of a positive fractional order with respect to Ag(I). It is found that the pseudo first order ([l-alanine] ? [Ce(IV)] ? [Ag(I)]) rate constant k′ increases with the increase of[H⁺]. The major oxidation product of alanine has been identified as acetaldehyde by an ¹H NMR and IR spectroscopy. Under the experimental conditions, the kinetically active species has been found to be Ce⁴⁺. Under nitrogen atmosphere, the reaction system can initiate the polymerization of acrylonitrile, indicating generation of free radicals. On the basis of the experimental results, a suitable mechanism has been proposed. The rate constants of the rate-determining step together with the activation parameters were evaluated.     

Controlling the dimensionality of oxalate-based bimetallic complexes: The ferromagnetic chain {[K(18-crown-6)][Mn(bpy)Cr(ox)3]}∞(18-crown-6 = C12H24O6, ox=C2O42-, bpy = C10H8N2)

The bimetallic ferromagnetic chain {[K(18-crown-6)][Mn(bpy)Cr(ox)₃]}_∞ (1) has been synthesized and characterized. It crystallizes in the orthorhombic chiral space group P2₁2₁2₁ [a = 9.0510(2) Å, b = 14.4710(3) Å, c = 26.8660(8) Å, V = 3510.97(1) Å³, Z = 2]. Compound 1 is made up by anionic [Mn(bpy)Cr(ox)₃]⁻ 1D chains and cationic [K(18-crown-6)]⁺ complexes. The magnetic exchange within the chain is ferromagnetic [J = +7.8(7) cm⁻¹]. In the solid state, the ferromagnetic chains are well isolated magnetically and no long range magnetic ordering has been observed above 2 K.     

Separation of toluene from alkanes using 1-ethyl-3-methylpyridinium ethylsulfate ionic liquid at T = 298.15 K and atmospheric pressure

In this paper, the separation of toluene from aliphatic hydrocarbons (heptane, or octane, or nonane) was analyzed by solvent extraction with 1-ethyl-3-methylpyridinium ethylsulfate ionic liquid, [EMpy][ESO₄]. Liquid?liquid equilibrium (LLE) data for the ternary systems {heptane (1) + toluene (2) + [EMpy][ESO₄] (3)}, {octane (1) + toluene (2) + [EMpy][ESO₄] (3)}, and {nonane (1) + toluene (2) + [EMpy][ESO₄] (3)} were obtained by measurements at T = 298.15 K and atmospheric pressure. The selectivity, % removal of aromatic, and solute distribution ratio, obtained from experimental equilibrium results, were used to determine the ability of [EMpy][ESO₄] as a solvent. The degree of consistency of the experimental LLE values was ascertained using the Othmer–Tobias and Hand equations. The experimental results for the ternary systems were correlated with the NRTL model. Finally, the results obtained were compared with other ionic liquids and other solvents.     

Synthesis and characterization of the bimetallic polymers [MS4Ag2(Hmimt)2]n (where M = Mo or W,Hmimt = 1-methylimidazoline-2(3H)-thione): crystal structures of [WS4Ag2(Hmimt)2]n and [Ag2I2(Hmimt)]n

The title compounds were synthesized by the reactions of [NH₄]₂[MS₄] (M = Mo, W), AgI and Hmimt in acetone and characterized by IR, ¹H NMR and UV–Vis spectroscopy. The polymeric structure of [WS₄Ag₂(Hmimt)₂]_n was determined by X-ray crystallography. In this compound, there are two distinctly different coordination modes for the silver atoms. One Ag atom has a pseudo-tetrahedral geometry with one terminal monodentate-S Hmimt, two μ₂-S bridging Hmimt and one S atom of a monodentate WS₄ unit. The other is surrounded by four sulfur atoms belonging in pairs to two WS₄ fragments; the coordination geometry is distorted tetrahedral. The [WS₄Ag₂(Hmimt)₂]_n polymer represents the first example of tetrathiometalate anions [MS₄]²⁻ (M = Mo, W, or V) coordinated to another metal atom in a monodentate fashion. In both crystal structures determined the Hmimt ligands are present in the thione form, with coordination taking place via the sulfur atom only.     

Stability of underpotentially deposited Ag layers on a Au(1 1 1) surface studied by surface X-ray scattering

Stability of underpotentially deposited (upd) Ag layers on Au(1 1 1) surface was investigated by surface X-ray scattering (SXS). While the complete pseudomorphic Ag bilayer on Au(1 1 1) surface obtained by upd at 10 mV (vs. Ag/Ag⁺) was maintained its structure even after the circuit was disconnected and the surface was exposed to ambient atmosphere, the pseudomorphic Ag monolayer obtained by upd at 50 mV was converted to a partial bilayer with the coverage of 0.66 and 0.46 ML for the 1st and 2nd layer, respectively. These results show that Ag bilayer is structurally more stable than Ag monolayer on Au(1 1 1) and Ag atoms of the upd monolayer move around on the Au(1 1 1) surface without potential control.     

Bonding aspects of P-heterocyclic carbene transition metal complexes. A computational assessment

Gradient-corrected (BP86) density-functional calculations were used to study the chemical bond between transition-metal complexes and N- and P-heterocyclic carbenes EHC (EHC = imidazolin-2-ylidene; 1,3-dimethylimidazolin-2-ylidene; 1,3-dihydro-1,3-diphosphol-2-ylidene; 1,3-dimethyl-1,3-diphosphol-2-ylidene). Forty two complexes of the type [M] ← EHC, [M] = CuCl, AgCl, AuCl, BeCl⁺, Cu⁺, Ag⁺, Au⁺, have been studied. Both electrostatic contributions as well as π-back-donation are of special importance for the [M] ← EHC bond. The metal–ligand bond strengths are comparable for NHC and PHC complexes. Whereas the former undergo stronger electrostatic interactions, the latter show a higher degree of π-bonding. When considering NHC and PHC as ligands for transition-metal-based catalysts, the results of the present study suggest that PHC both compete with NHC – in terms of metal-to-ligand bond strength – as well as complement NHC – in terms of the nature of the metal–ligand bond.     

The reduction process of phytic acid–silver ion system: A pulse radiolysis study

Reduction of silver ion in a silver–phytic acid (1:1 ratio) system has been studied using pulse radiolysis technique. Time-resolved transformation of the intermediates, Ag⁺→Ag⁰→Ag₂⁺→Ag₃²⁺, has been clearly observed in the reduction of silver–phytic acid (1:1) system. The effect of phytic acid on the formation and decay of initial silver clusters has been also studied. The surface plasmon absorption band of stable silver nanoparticle (410 nm) and dynamic light scattering technique has been used to characterize the nanoparticles and measure the average size (R_av=100 nm).     

Synthesis,crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa = hexafluoroacetylacetonate,Phen = o-phenanthroline)

The mixed ligand complex [La(hfa)₃(Phen)₂] (I) was obtained by the interaction of La(hfa)₃ and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P2₁/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)₃(Phen)₂]_(s) = [La(hfa)₃(Phen)]_(g) + Phen_(g), Δ_rH⁰(T) = 316.2 ± 1.8 kJ/mol.