Proton ionizable crown compounds. 18. Comparison of alkali metal transport in a H2O-CH2Cl2-H2O liquid membrane system by four proton-ionizable macrocycles containing the dialkylhydrogenphosphate moiety

The macrocycle-mediated fluxes of alkali, alkaline earth, and several transition metal cations have been determined and compared in a H₂O-CH₂Cl₂-H₂O liquid membrane system using four water-insoluble macrocycles containing a dialkylhydrogenphosphate moiety. Transport of alkali metal cations by these ligands was greatest from a source phase pH = 12 or above into an acid receiving phase (pH = 1.5). Very low fluxes were observed for the transport of the alkaline earth cations and all transition metal ions studied except Ag⁺ and Pb²⁺ which were transported reasonably well by these new macrocycles.Deceased: September 5, 1987.     

Acetyl-containing phosphine oxides as extractants for actinides and lanthanides

Extraction capability and selectivity of acetyl-containing phosphine oxides R₂P(O)CMe₂CH₂C(O)Me (R = Pr, Bu, n-C₅H₁₁, n-C₆H₁₃, n-C₈H₁₇, Ph) toward actinides (U^VI, Th^IV) and trivalent lanthanides (La^III, Nd^III, Ho^III, Yb^III) were studied. The new ligands were shown to be more efficient and selective in the extraction of uranium, thorium, and heavy lanthanides from nitric acid solutions into chloroform as compared to the known extractants such as carbamoylphosphine oxide Ph₂P(O)CH₂C(O)NBu₂, trioctylphosphine oxide (n-C₈H₁₇)₃P(O), and tributyl phosphate (n-BuO)₃P(O).     

Transport of Eu2+ in a H2OCHCl3H2O liquid membrane system containing the macrocyclic polyether 18-crown-6

Macrocyclic polyethers transport alkali and alkaline earth, but not trivalent lanthanide cations in H₂OCHCl₃H₂O liquid membrane systems. We report here the use of 18-crown-6 to transport europium after first reducing it to the bivalent oxidation state. In this oxidation state, the Eu(NO₃)₂ flux is comparable to that of Sr(NO₃)₂.     

Untersuchung der Cokristallisation in den Systemen. Mn(OOCCH3)2-Co(OOCCH3)2-H2O,Mn(OOCCH3)2-Ni(OOCCH3)2-H2O,Mn(OOCCH3)2-Zn(OOCCH3)2-H2O bei 60°C

Investigation of Cocrystallization in the Systems Mn(OOCCH₃)₂-Co(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Ni(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O at 60°C The three-component systems Mn(OOCCH₃)₂-Co(OOCCH₃)₂-H₂O, Mn(OOCCH₃)₂-Ni(OOCCH₃)₂-H₂O and Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O at 60°C were investigated by physio-chemical analysis. There is an interruption in the series of mixed crystals formed in the three-component systems. The inclusion of Co²⁺- and Ni²⁺ in Mn(OOCCH₃)₂ · 2 H₂O of Mn²⁺ in Co(OOCCH₃)₂ · 2 H₂O, Zn(OOCCH₃)₂ · 2 H₂O and Ni(OOCCH₃)₂ · 4 H₂O is based on isodimorphic substitution. It was found that in the system Mn(OOCCH₃)₂-Zn(OOCCH₃)₂-H₂O crystallizes Zn(OOCCH₃)₂ · Mn(OOCCH₃)₂ · 2 H₂O. It was identified by the X-ray and differential thermal analysis.     

Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2′,3′-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H₂O)₂][Cd(Dpq)(1,8-NDC)]·2H₂O (1), [Cd(Dpq)(1,4-NDC)(H₂O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2′,3′-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H₂NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H₂NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H₂NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π-π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π-π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.     

The missing hydrate AlF3·6H2O [Al(H2O)6]F3: Ionothermal synthesis,crystal structure and characterization of aluminum fluoride hexahydrate

AlF₃ is a strong Lewis acid and several hydrates of it are known, namely the monohydrate, the trihydrate (of which two polymorphs have been described) and the nonohydrate, which forms in the abundance of water, as well as a more complex fluoride of composition Al_0.82□_0.18F_2.46(H₂O)_0.54 whose structure has been related to the ReO₃ type. The monohydrate features edge connected [AlF₆] octahedra, in the tri- and nonahydrate mixed F/O coordination of aluminum is observed. Here we report on a new aluminium fluoride hydrate, AlF₃·6H₂O, which could be obtained via ionothermal synthesis in the ionic liquid n-hexyl-pyridinium tetrafluoroborate. The ionic liquid serves in the synthesis of AlF₃·6H₂O as the reaction partner (fluoride source) and solvent. Overmore it controls the water activity allowing access to the missing AlF₃·6H₂O. Single-crystal X-ray diffraction analysis of AlF₃·6H₂O shows that it crystallizes in the anti-Li₃Bi-type of structure according to F₃[Al(H₂O)₆] (Fm-3m, a = 893.1(2) pm, Z = 4) featuring hexaaqua aluminium(III) cations and isolated fluoride anions. The compound was further characterized by powder X-ray diffraction, TG/DTA, IR analyses.     

Solubility of some lanthanide sulfates in polycomponent systems containing H2SO4

Summary The paper presents data on the solubility of La, Ce, Pr, Nd sulfates in the polycomponent system La₂(SO₄)₃·8H₂O-Ce₂(SO₄)₃·8H₂O-Pr₂(SO₄)₃·8H₂O-Nd₂(SO₄)₃· 8H₂O-H₂SO₄-H₂O (at 25°C and 64°C) as well as in the same polycomponent system but in the presence of CaSO₄·2H₂O. The solubility of the sulfates — ocathydrates of Pr at 25°C and 64°C and of La and Ce at 64°C in tricomponent systemLn ₂(SO₄)₃·8H₂O-H₂SO₄-H₂O are also reported.

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Löslichkeit einiger Lanthanidsulfate in Mehrkomponenten-Systemen mit H₂SO₄

Zusammenfassung Die Arbeit präsentiert Daten für die Löslichkeit von La-, Ce-, Pr- und Nd-Sulfaten in den Vielkomponenten-Systemen La₂(SO₄)₃·8H₂O-Ce₂(SO₄)₃·8H₂O-Pr₂(SO₄)₃·8H₂O-Nd₂(SO₄)₃· 8H₂O-H₂SO₄-H₂O (bei 25°C und 64°C) sowie in den gleichen Systemen, jedoch in Anwesenheit von CaSO₄·2H₂O. Über die Löslichkeit von Sulfatoctahydraten von Pr bei 25°C und 64°C und von La und Ce bei 64°C in den Dreikomponenten-SystemenLn ₂(SO₄)₃·8H₂O-H₂SO₄-H₂O wird auch berichtet.

     

Isotype 1D polymers of cobalt(II) or zinc(II) constructed with square-planar tetraaqua-metal(2+) units and the bis-zwitterionic form of the μ2-O,O′-trans-1,4-dihydrogen-cyclohexanediaminotetraacetate(2−) ligand

An uncompleted reaction between equimolar amounts of Co₂CO₃(OH)₂·2H₂O and trans-1,4-H₄cyclohexanediaminotetraacetic acid in water affords the ‘acid’ complex {[Co^II(trans-1,4-H₂CDTA)(H₂O)₄]·6H₂O}_n (1). Its IR spectrum does not show the expected ν(CO) band of carboxylic groups. Reactions in aqueous solution between Na(trans-1,4-H₃CDTA) and Zn(AcO)₂·2H₂O or Na₂(trans-1,4-H₂CDTA) and Zn(NO₃)₂·6H₂O yield {[Zn(trans-1,4-H₂CDTA)(H₂O)₄]·6H₂O}_n (2) and {[Zn₂(trans-1,4-CDTA)(H₂O)₂]·H₂O}_n (3) respectively. Crystal structures of compounds 1-3 and that of the trans-1,4-H₄CDTA·2H₂O acid are reported. For steric reasons, in the four reported structures the 1,4-CDTA ligand has the two iminodiacetate moieties as equatorial groups in the 1,4-cyclohexanedi-yl chair. Compounds 1 and 2 are isotype 1D polymers constructed by square planar M^II(H₂O)₄²⁺ knots (M^II = Co^II or Zn^II) linked to bis-zwitterionic trans-1,4-H₂CDTA²⁻ ligands that play a typical μ₂-O,O′-dicarboxylate bridging role. These 1D polymeric structures seem to be favoured by the H-bonded intra-stabilization of the bis-zwitterionic trans-1,4-H₂CDTA²⁻ ligand. In the neutral complex (3), the trans-1,4-CDTA acts as a bridging bis-chelating ligand as well as a syn-anti carboxylate building a polymer where the zinc(II) centres exhibit a rough bipyramidal trigonal coordination.     

Chirality and Polarity in the f‐Block Borates M4[B16O26(OH)4(H2O)3Cl4] (M=Sm,Eu, Gd,Pu, Am,Cm, and Cf)

The reactions of trivalent lanthanides and actinides with molten boric acid in high chloride concentrations result in the formation of M₄[B₁₆O₂₆(OH)₄(H₂O)₃Cl₄] (M=Sm, Eu, Gd, Pu, Am, Cm, Cf). This cubic structure type is remarkably complex and displays both chirality and polarity. The polymeric borate network forms helical features that are linked via two different types of nine‐coordinate f‐element environments. The f–f transitions are unusually intense and result in dark coloration of these compounds with actinides.     

NH4F·H2O2, a new peroxyhydrate

Conclusions The new molecular compound NH₄F·H₂O₂ was observed during an investigation of the fusibility of the NH₄F-H₂O₂-H₂O system and has been isolated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1617–1618, July, 1968.     

Structural and luminescent properties of a tetranuclear cage-type cadmium(II) carboxylate cluster containing a V-shaped water trimer

The structural characterization of tetranuclear cage-type cadmium(II) carboxylate [Cd₄(2-cpida)₂(2,2′-bpy)₆]·(2,2-bpy)·(ClO₄)·3H₂O (1) (2-H₃cpida = N-(2-carboxyphenyl)iminodiacetic acid, 2,2′-bpy = 2,2′-bipyridine) is described. H-bonding interactions between three lattice water molecules form a V-shaped trimer (H₂O)₃, which is stabilized by 1. In addition, luminescence investigations revealed that 1 shows enhanced emissions as compared with free 2-H₃cpida in the liquid state.     

Synthesis and structural characterization of metal–organic frameworks with the mellitate linker M2(OH)2[C12O12H2]·2H2O (M = Al,Ga, In) MIL-116

A new series of isostructural MOF-type carboxylates called MIL-116 (M₂(OH)₂[C₁₂O₁₂H₂]·2H₂O), was synthesized from the combination of mellitic acid and trivalent p cations M = Al³⁺, Ga³⁺ or In³⁺. Their structures were analyzed either by single-crystal microdiffraction using the synchrotron radiation beamline (ID13 station at ESRF, Grenoble) or solved from powder X-ray diffraction. The 3D hybrid framework is built up from the connection of infinite straight chains of metal-centered octahedra sharing trans corners linked to each other through the mellitate ligands. Here the ligand acts as octadentate linker with four of the carboxylic groups involved in the M–O–C bondings. The two other carboxylate arms remain non-bonded under their protonated form. This represents a rare case of the occurrence of both non-bonding and bonding organic functionalities in a MOF-type solid. Within the tunnels are located water species that interact with the non-coordinated –COOH groups pointing towards the channel.     

The phase diagrams of the CdCl2-NaCl-H2O system at 298 K

Solid-liquid equilibrium of ternary system Cd²⁺, Na⁺//Cl^?-H₂O at 298 K were studied by an isothermal solution saturation method. Experimental results indicate that there are three univariant curves AE, EF, and FB, two invariant points E, F, and three crystallization fields in the ternary system. The ternary system has one double salt Na₂CdCl₄ · 3H₂O. The crystallization zones of equilibrium solid phases are CdCl₂ · H₂O (AEG field), Na₂CdCl₄ · 3H₂O (EFM field), and NaCl (FBN field), respectively. The composition of the invariant point E is CdCl₂ · H₂O and Na₂CdCl₄ · 3H₂O of which content was 52.70 and 4.11%, respectively. The composition of the invariant point F is Na₂CdCl₄ · 3H₂O and NaCl of which content was 27.92 and 14.95%, respectively. The density of solution in the ternary system show regular changes along with the increased cadmium concentration. The results indicated that CdCl₂ · H₂O possessed the highest solubility among those three salts, which means a strong transfer of Cd ion and a high pollution risk of soil environment. And the solubility of NaCl would be restrained as the three salts existing together.     

Multicomponent heterocyclization of carboxamides with H2S and CH2O

Multicomponent heterocyclization of aliphatic amides with H₂S and CH₂O (1:3:2) in water-organic solvent mixture in the presence of BuONa led to the formation of 1,3,5-dithiazinane in high yield (30–95%) and with high selectivity (100%). Under these conditions benzamide gave 3,5-dibenzoyl-1,3,5-thiadiazinane in 74% yield, whereas due to ortho-effect the acetylsalicylamide with H₂S and CH₂O in a system BuOH-H₂O without BuONa formed N-acetylsalicyloyl-1,3,5-dithiazinane (80%). Heterocyclization of α-aminosuccinic acid monoamide depending on the H₂S and CH₂O concentration occurred either at one or both NH₂ yielding respectively mono-or bisdithiazinanes.     

Kristallstruktur von (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2

Crystal Structure of (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ . (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ crystallizes from hydrobromic acid solution of Re₃Br₉ · 2 H₂O and NMe₄Br at 0 – 5°C. The crystal structure (monoclinic; P2₁/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; R_w = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re₃Br₁₁(H₂O)]^2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re₃Br₉(H₂O)₃](H₂O)₂}.     

Investigation of peroxyhydrates and hydrates of rubidium and cesium carbonates Communication 2. Physicochemical study of the ternary system Rb2CO2-H2O2-H2O

Conclusions A physicochemical investigation of the system Rb₂CO₃-H₂O₂-H₂O in the region of high hydrogen peroxide concentrations at low temperatures revealed for the first time the formation of a peroxyhydrate with a high hydrogen peroxide content, of the composition Rb₂CO₃ · 6H₂O₂.     

Phase formation in the ZrO(NO3)2-H3PO4-CsF(HF)-H2O system

The phase formation in the system ZrO(NO₃)₂-H₃PO₄-CsF(HF)-H₂O was studied at the molar ratio CsF/Zr = 1 along the sections PO ₄ ^3? /Zr = 0.5 and 1.5 at a ZrO₂ concentration in the initial solution of 2?C14 wt %. The following compounds were isolated: Cs₅Zr₄F₂₁ · 3H₂O, CsZr₂(PO₄)₃ · 2HF · 2H₂O, CsZrF₂PO₄ · H₂O, CsZr₂F₆PO₄ · 4H₂O (for the first time), CsHZrF₃PO₄ (for the first time), Cs_0.70ZrF(PO₄)_1.23 · nH₂O, and CsHZr₂F₂(P_O4)_2.66 · nH₂O. The compositions of CsZrF₂PO₄ · H₂O, Cs_0.70ZrF(PO₄)_1.23 · nH₂O, and CsHZr₂F₂(PO₄)_2.66 · nH₂O are conditional. All the compounds were characterized by crystal-optical, X-ray powder diffraction, thermal analyses, and IR spectroscopy. The formula CsHZrF₃PO₄ was established by energy-dispersive analysis with a LEO-1450 scanning electron microscope and an MS-46 CAMECA X-ray microanalyzer.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Phase formation and transition in a xanthan gum/H2O/H3PO4 tertiary system

Phase formation and transition in a xanthan gum (XG)/H₂O/H₃PO₄ tertiary system were characterized by polarized optical microscopy, light transmission detection and rheological methods. Three distinct phases and a transition region—the completely separated (S) phase, the liquid crystalline (LC) miscible phase, the isotropically (I) miscible phase and the S plus LC region—were identified. The presence of H₃PO₄ in the XG/H₂O system inhibited the evolution of both the S and LC phases. The S and LC phases contained less than 73 and 62 wt% of H₃PO₄, respectively. As the temperature increased over 65 °C, the LC phase in the H₃PO₄-rich and H₂O-poor region seriously shrunk owing to the breakup of hydrogen bonds among the XG helical structure. At the same XG loading, the viscosity of the XG solutions in LC phase was found to be much higher than that in I phase. It indicated the existence of numerous XG intermolecular interactions in the LC phase that suppress the movement of liquid. A study of the kinetics demonstrated that the shrinkage relaxation time (τ) depended strongly on temperature and was fitted by the Volgel-Fulcher-Tammann (VFT) expression. The potential energy barrier of this liquid was quite low at approximately 3.0 kJ mol^?1, falling in the range of hydrogen-bond disassociation. The light absorbance test in heating mode revealed a biphasic transitional region between the LC phase and I phase. The contour of this region depended on the heating rate, and this fact was explained again by the relaxation behavior of XG helices at temperatures higher than 65 °C.     

LC-DAD-ESI-MS Characterization of Carbohydrates Using a New Labeling Reagent

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupling to liquid chromatography with electrospray ionization mass spectrometry for the detection of carbohydrates from the derivatized rape bee pollen samples is reported. Carbohydrates are derivatized to their bis-NMP-labeled derivatives. Derivatives showed an intense protonated molecular ion at m/z [M+H]⁺ in positive-ion detection mode. The mass-to-charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative analysis of carbohydrates. This characteristic fragment ion is from the cleavage of C2–C3 bond in carbohydrate chain giving the specific fragment ions at m/z [MH-C _m H_2m+1O _m -H₂O]⁺ for pentose, hexose and glyceraldehydes and at m/z [MH-C _m H_2m-1O _m+1-H₂O]⁺ for alduronic acids such as galacturonic acid and glucuronic acid (m = n ? 2, n is carbon number of carbohydrate). No interferences for all aliphatic and aromatic aldehydes presented in natural environmental samples were observed due to the highly specific parent mass-to-charge ratio and the characteristic fragment ions. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed-phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected.