Synthesis, structure, and properties of [Be(H2O)4][UO2(CH3COO)3]2

Crystals of previously unknown compound [Be(H₂O)₄][UO₂(CH₃COO)₃]₂ were prepared and studied by X-ray diffraction analysis. The compound crystallizes in the tetragonal system, unit cell parameters (at 100 K): a = 10.3647(3), c = 23.4127(8) Å, V = 2515.16(13) ų, space group I4₁/a, Z = 4, R = 0.0194. The structure consists of mononuclear complexes [Be(H₂O)₄]²⁺ and [UO₂(CH₃COO)₃]^? linked with each other by electrostatic interactions and hydrogen bonds formed by water molecules and O atoms of acetate anions. The compound was also studied by methods of thermal analysis and IR spectroscopy.     

On the synthesis and rebinding properties of [Co(C2H3O2)2(z-Histidine)] imprinted polymers prepared by precipitation polymerization

In the present study, the synthesis via free-radical precipitation polymerization of metal-complexing polymer microparticles capable of specific binding to [Co(C₂H₃O₂)₂(z-Histidine)] complex is reported. Initially, the functional monomer (i.e., 4-vinylpyridine, a vinyl monomer with metal chelate properties) is complexed together with the template [Co(C₂H₃O₂)₂(z-Histidine)] molecule via the mediation of cobalt ions. Evidence of the polymerizable complex formation is obtained through the compleximetric titration of the z-Histidine in the prepolymerization reaction mixture. Subsequent polymerization of the polymerizable complex with a bi-functional or tri-functional cross-linker results in the formation of imprinted polymer microparticles in the size range of 1–5 µm. The effects of agitation, cross-linker type, degree of cross-linking and molar ratio of the template to the functional monomer on the rebinding properties of the imprinted polymers are experimentally assessed. The synthesized imprinted polymers can potentially find application in the purification of his-tagged recombinant proteins.     

Vinyl-group alignment along the upper rim of a multi-component resorcin[4]arene

Cocrystallization of C-methylcalix[4]resorcinarene 1 with 4-vinylpyridine obtained from MeNO₂ yields a six-component host–guest complex 1·4(4-vinyl-pyridine)·MeNO₂ 2 in which the upper rim of 1 is extended supramolecularly by way of four O–H⋯N(pyridine) hydrogen bonds and the included solvent serves as a guest. The pyridine moieties of 2 assemble along the upper rim of 1 as two stacked dimers in which the vinyl substituents of the aromatic adopt a parallel orientation. The X-ray crystal structure of resorcinol·2(4-vinylpyridine) 3 has also been determined and reveals that the vinyl groups of 3 are aligned in an antiparallel fashion. These observations allow us to suggest that multi-component resorcin[4]arenes which possess vinyl-pyridines as cavity extenders may provide a route to aligning olefinic bonds in the solid state.     

Chemical vapor deposition copolymerization of 4-carboxyl-[2,2] paracyclophane and 4-amino-[2,2] paracyclophane

Chemical vapor deposition copolymerization (CVDCP) of 4-carboxyl-[2,2] paracyclophane (4-carboxyl-PCP) and 4-amino-[2,2] paracyclophane (4-amino-PCP) is carried out. It is shown in FTIR and ¹³C NMR spectra of the copolymer that an amide or imide bond is formed during the pyrolysis and the transportation of the pyrolysis products. Partial crosslinking, caused by the amidation or imidation of -COOH and -NH₂ among different chains in the copolymer, is possible during the transportation and deposition process. Compared with poly(carboxyl-p-xylylene-co-p-xylylene) (PPX-Carb), the thermal stability of the copolymer is improved. The crystallinity of the copolymer is reduced which is confirmed by transmittance and XRD results of the copolymer.     

Reverse ATRP of 4-vinylpyridine with Diethyl 2,3-Dicyano-2,3-Diphenylsuccinate/CuCl2/5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane

Diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS) was applied to initiate reverse atom transfer radical polymerization of 4-vinylpyridine (VP) in 2-propanol with CuCl₂ and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane (Me₆[14]aneN₄) as catalyst and ligand for the first time. First-order kinetics of the polymerization rate with respect to the monomer concentration, linear increase of the molecular weight with monomer conversion and a polydispersity index in the range of 1.15–1.28 were indicatives of controlled radical polymerization. Use of Me₆[14]aneN₄ as the ligand had many advantages over the use of hexamethyl tris[2-(dimethylamino)ethyl]amine (Me₆-TREN) and 2,2′-bipyridine (bpy). A slower polymerization rate and a broad polydispersity index were observed using CuBr₂ instead of CuCl₂ as catalyst. The block copolymer PVP-b-PAN was obtained via a conventional ATRP process in N, N-dimethylformamide (DMF) using the resulting poly (4-vinylpyridine) as macroinitiator.     

Synthesis and crystal structure of K3[NpO4(OH)2]

Attempts were made to isolate anhydrous compounds of [NpO₄(OH)₂]^3? anions with heavy alkali metal cations (K, Rb, Cs) by crystallization at elevated temperatures, and the salt K₃[NpO₄(OH)₂] was isolated and studied. Crystals of K₃[NpO₄(OH)₂] consist of tetragonal bipyramidal [NpO₄(OH)₂]^3? anions and K⁺ cations. The [NpO₄(OH)₂]^3? anion occupies the position in the symmetry center. The Np-O distances in this anion are 1.8992(7) and 1.9100(7) Å in the equatorial plane of the bipyramid and 2.3231(8) Å with OH groups. The OH hydrogen atoms participate in weak H bonds [O?O 3.0250(11) Å] linking the anions in layers [NpO₄(OH)₂] _n ^3n? parallel to the (010) plane. In the interlayer space, there are two crystallographically different K atoms. Their coordination number (CN) can be considered to be equal to 7 and 8. Comparison with the structures of the known compounds Na₃[NpO₄(OH)₂] and K₃[NpO₄(OH)₂]·2H₂O was made. The structure of the latter compound was redetermined with higher accuracy. The failure of attempts to prepare the anhydrous rubidium and cesium compounds is probably due to large ionic radius of these cations, requiring high coordination number.     

Phase diagrams of the ternary liquid systems [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2] and [Ce(NO3)3(TBP)3]-C10H22-[Th(NO3)4(TBP)2] and of the quaternary liquid system [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2]-[Th(NO3)4(TBP)2]

The phase diagrams of the ternary liquid systems [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂] and [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] and of the quaternary liquid system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂]-[Th(NO₃)₄(TBP)₂] at T = 298.15 K are constructed. The phase diagrams are characterized by areas of homogeneous solutions and of two-phase liquid systems (systems with phase separation), with one phase (I) enriched in [Ce(NO₃)₃(TBP)₃], [Th(NO₃)₄(TBP)₂], and [UO₂(NO₃)₂(TBP)₂], and the other phase (II), in C₁₀H₂₂. Using the data on the mutual solubility of the components in the systems under consideration and equations of the NRTL model, the parameters of intermolecular interactions and the excess Gibbs energies (G ^ex) were calculated for the binary, ternary, and quaternary systems. Passing from the ternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] to the quaternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂ (TBP)₂]-[Th(NO₃)₄(TBP)₂] does not appreciably affect the distribution of C₁₀H₂₂ between phases I and II, but leads to the redistribution of [Ce(NO₃)₃(TBP)₃] into phase II and of [Th(NO₃)₄(TBP)₂] into phase I.     

Physicochemcial analysis of the phase diagram of the ternary liquid system [Y(NO3)3(TBP)3]-tetradecane-[UO2(NO3)2(TBP)2]

The phase diagram of the ternary liquid system (TLS) [Y(NO₃)₃(TBP)₃]-tetradecane-[UO₂ · (NO₃)₂(TBP)₂] (TBP is tri-n-butyl phosphate) at 298.15 K is constructed. The TLS is characterized by an area of homogeneous solutions and an area of two-phase liquid systems with one of the phases (I) enriched in [Y(NO₃)₃(TBP)₃] and [UO₂(NO₃)₂(TBP)₂] and the other phase (II), in tetradecane. The inter-molecular interaction parameters and excess Gibbs energies (g ^E ) for the binary systems and TLS along the binodal curve were calculated from data on the mutual solubility in the binary system [Y(NO₃)₃(TBP)₃]-tetradecane and the ternary liquid system, using equations of the NRTL theory. For the binary system [Y(NO₃)₃(TBP)₃]-[UO₂(NO₃)₂(TBP)₂], g ^E < 0, and for the other binary systems, g ^E > 0. An algorithm is given for computer calculation of the binodal curve and nodes for the TLS within the framework of NRTL equations using the intermolecular interaction parameters.     

Conglomerate crystallization behavior of racemic [Co(N4)(aminoacidato)]2+ complexes

Crystal structures, absolute configurations, and crystalline packing features of nine complexes, namely, cis-α-Λ-(RR)(δλδ)-[Co(trien)(D-histidinato)](ClO₄)₂·2H₂O 1, cis-β₁-Δ-(RR)(λδδ)- [Co(trien)(L-asparaginato)](ClO₄)₂ 2, cis-β₂-Λ(SS)(λλδ)-[Co(trien)(L-valinato)](ClO₄)₂·H₂O 3, cis-β₂-Δ-(RR)(δδλ)[Co(trien)(D-methioninato)](ClO₄)₂ and its enantiomer 4, trans(N,t-N)-[Co(tren)(DL-leucinato)]X₂, (X=ClO₄⁻ 5, BF₄⁻ 6, PF₆⁻ 7), and trans(N,t-N)-[Co(tren)(DL- methioninato)]X₂ (X=Br⁻ 8, Cl⁻(BF₄⁻) 9) (trien=triethylenetetramine, tren=tris(2-aminoethyl)amine), have been determined. All compounds were prepared from racemic DL-amino acid. 1–3 crystallize as conglomerates. 5–7 are isomorphous and crystallize as the so-called conglomeratic solids. While 4, 8 and 9 undergo racemic crystallization. In 1–7, the carboxylic oxygen of the amino acid forms double hydrogen bonds with the amino hydrogen atoms of N4 and/or amino acidato of an adjacent cation. By these hydrogen bonds, cations having the same chirality are linked together into helical string. In the isomorphous 8 and 9, the cation containing L-methionine interacts with a cation containing D-methioninine, through hydrogen bonds, to form a racemic pair, and no spiral string arrangements are observed.     

Synthesis and structure determination of new open-framework chromium carboxylate MIL-105 or CrIII(OH)·{O2C–C6(CH3)4–CO2}·nH2O

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr^III(OH)·{O₂C-C₆(CH₃)₄-CO₂}·nH₂O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO₄(OH)₂ octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally give MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) Å, b = 9.984(1) Å, c = 6.970(1) Å, β = 110.67(1)° and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) Å, b = 11.165(1) Å, c = 6.916(1) Å and Z = 4.     

A zinc phosphate, [NH3(CH2)3NH3][Zn4(PO4)2(HPO4)2], possessing alternate inorganic and organic layers

A new zinc phosphate of the formula, [NH₃(CH₂)₃NH₃][Zn₄(PO₄)₂(HPO₄)₂], has been synthesized hydrothermally starting from a zinc amine complex. It crystallizes in the monoclinic space group C2/c; a=17.279(1), b=5.193(1), c=20.115(1) Å, β=92.6(1)°; V=1803.1(2) ų; Z=4; D_calc=2.05 g cm⁻³; μ (MoKα)=5.62 mm⁻¹. The final R, and wR₂=0.037, 0.093 obtained for 136 observed data [I>2σ(I)]. The structure consists of macroanionic sheets of interconnected ZnO₄ and PO₄ tetrahedra in the ab plane. The sheets are held together by hydrogen bond interactions with the organic structure-directing amine, forming alternate inorganic–organic layers in this material. Hydrogen bond interactions between the inorganic layers, via the terminal –OH group, leads to the formation of pseudo one-dimensional channels.     

Influence of temperature on phase separation in the ternary systems [Th(NO3)4(TBP)2]-isooctane-third organic component

The phase diagrams of ternary liquid systems (TLSs) [Th(NO₃)₄(TBP)₂]-isooctane-third organic component [n-butanol, isobutanol, n-octanol, n-decanol, cyclohexanol, toluene, o-xylene, CCl₄, CHCl₃, o-dichlorobenzene, TBP, and higher isomeric carboxylic acids (HICAs)] were studied in the temperature range 298.15–333.15 K. These diagrams contain the fields of homogeneous solutions and the field of separation into two liquid phases (I, II). Phases I is enriched in [Th(NO₃)₄(TBP)₂] and third component, and phase II is enriched in isooctane. With increasing temperature, the field of separation into two liquid phases contracts and the content of the third component in the critical points decreases. The compositions of ternary systems in the critical point depend on the kind of the third component. In phase separation, the third component is predominantly concentrated in phase I, in spite of the fact that the third component and isooctane have infinite mutual solubility at all the temperatures.     

Synthesis and electroluminescent property of tris{2-(naphtha [3,4]imidazol-2-yl) pyridinato} Aluminum

An emission material, tris{2-(naphtha [3,4]imidazol-2-yl) pyridinato} Aluminum (AlNIP) used for organic light emitting devices, has been synthesized. The decomposition temperature was observed at 510 °C and no melting transition (T_m) of AlNIP was observed up to 400 °C. The emission spectrum of organic emitting device using AlNIP as emitted layer exhibits a broad maximum at 536 nm. The color of the emitted light is in the orange region in the CIE coordinate of x = 0.41 y = 0.53.     

A new three-dimensional open-framework iron(III) phosphate, [C2N2H10][Fe2(HPO4)4]

A new open-framework iron(III) phosphate, I, [C₂N₂H₁₀][Fe₂(HPO₄)₄] has been hydrothermally synthesized in the presence of ethylenediamine (en). The structure is built up from the vertex linkages between the FeO₆ octahedra and the PO₄ tetrahedra, strictly alternating, forming the three-dimensional architecture. The linkages between the FeO₆ and PO₄ polyhedra gives rise to ladder-like edge-shared chains, which are connected variously forming two types of channels. The di-protonated en molecules occupy these channels. Crystal data for I, [C₂N₂H₁₀][Fe₂P₄O₁₆]: a=9.341(1), b=8.892(1), c=9.480(1) Å, β=117.6(1)°, V=698.1(1) ų, space group P2/n (No. 13), Z=2, M=557.7, D_calc=2.65 g cm⁻³, MoKα (λ=0.71073 Å), R₁=0.03, wR₂=0.08 and S=1.10. Magnetic susceptibility studies indicate a predominantly antiferromagnetic interaction with T_N=30 K.     

Synthesis,Structure, and Physicochemical Properties of AI 4[UO2(CO3)3]·nH2O (AI = Li,Na, K,NH4)

Procedures for the synthesis of Li₄[UO₂(CO₃)₃]·1.5H₂O, Na₄[UO₂(CO₃)₃], K₄[UO₂(CO₃)₃], (NH₄)₄[UO₂(CO₃)₃], and K₃Na[UO₂(CO₃)₃] were optimized. The structures of these compounds and their thermolysis were studied by X-ray diffraction, precision IR spectroscopy, and thermal analysis. The standard enthalpies of formation of these compounds at 298.15 K were determined by reaction calorimetry.     

Investigation of Cs(H2PO4)1 − x (HSO4) x (x = 0.15–0.3) superprotonic phase stability

A detailed investigation of the highly conductive Cs(H₂PO₄)_1?x (HSO₄) _x (x = 0.15–0.3) proton electrolyte, its structural properties, and ageing behavior was carried out using X-ray diffraction, DSC, and impedance and NMR spectroscopy. The high conductivity of electrolytes (～2 × 10^?2 S/cm) remains stable during long-term ageing at 180–200°C due to stabilization of the high temperature phase to lower temperatures. The room temperature ¹H MAS NMR spectrum of (CsH₂PO₄)_1?x (CsHSO₄) _x demonstrates the predominantly highly mobile protons present in these materials with the residual low-mobile protons, which agrees with the XRD data. According to XRD and ¹H NMR data, the cubic phase of Cs(H₂PO₄)_{1 ? x} (HSO₄) _x (x = 0.15–0.3) that stabilizes at room temperature gradually transforms to a low-temperature monoclinic one. The kinetics of the phase transformation for mixed salt depends markedly on the relative air humidity. A possible stabilization mechanism of the Cs(H₂PO₄)_{1 ? x} (HSO₄) _x superionic phase with high proton mobility at low temperatures is discussed.     

Synthesis and structural study of new potassium uranyl selenates K2(H5O2)(H3O)[(UO2)2(SeO4)4(H2O)2](H2O)4 and K3(H3O)[(UO2)2(SeO4)4(H2O)2](H2O)5

Single crystals of new uranyl selenates K₂(H₅O₂)(H₃O)[(UO₂)₂(SeO₄)₄(H₂O)₂](H₂O)₄ (1) and K₃(H₃O)[(UO₂)₂(SeO₄)₄(H₂O)₂](H₂O)₅ (2) were prepared by isothermal evaporation at room temperature. The crystal structure of 1 was solved by the direct method [C2/c, a = 17.879(5), b = 8.152(5), c = 17.872(5) Å, β = 96.943(5)°, V = 2585.7(19) ų, Z = 4] and refined to R ₁ = 0.0449 (wR ₂ = 0.0952) for 2600 reflections with |F _o| ≥ 4σ _F . The structure of 2 was solved by the direct method [P2₁/c, a = 17.8377(5), b = 8.1478(5), c = 23.696(1) Å, β = 131.622(2)°, V = 2574.5(2) ų, Z = 4] and refined to R ₁ = 0.0516 (wR ₂ = 0.1233) for 4075 reflections with |F _o| ≥ 4σ _F . The structures of 1 and 2 are based on [(UO₂)₂(SeO₄)₄(H₂O)₂]^4? layers. The charge of the inorganic layer is compensated by potassium and oxonium ions arranged in the interlayer space. Each K ion is surrounded by seven O atoms belonging to uranyl selenate layers and water molecules, so that it binds with each other the adjacent uranyl selenate structural elements.     

Synthesis,characterization and antibacterial activity studies of poly-{styrene-acrylic acid} with silver nanoparticles

This work reports the preparation and characterization of copolymer poly-{styrene-acrylic acid} with monomeric ratio of styrene/acrylic acid of 9:1 using benzoyl peroxide as initiator and furthermore filled with nanosilver (25 ppm and 50 ppm) in water/acetone (1:40 v/v). The nanosilver emulsion was obtained from chemical reduction using NaBH₄ as reducing agent and sodium citrate as the stabilizer. The preparation of nanosilver emulsion was monitored by the appearance of a Plasmon Resonant Absorption band in a UV–visible spectrophotometer and the particles sizes were observed through TEM. Microbiological studies were performed to investigate the antimicrobial activity of this new material against the microorganisms Escherichia coli (ATCC-25922) and Staphylococcus aureus (ATCC-6538), used as reference strains. The antimicrobial activity of the poly-{styrene-acrylic acid} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not found with the poly(styrene-acrylic acid) alone. The present work suggests that silver ions are released from the polymeric matrix to the culture media and have the ability to tune the Ag⁺ ions released by controlling the amount of Ag nanoparticles embedded in the composite.     

Synthesis and characterization of the open-framework cobalt borophosphate: (C4N2H12)Co[B2P3O12(OH)]

A high yield hydrothermal synthesis of the open-framework cobalt borophosphate (C₄N₂H₁₂)Co[B₂P₃O₁₂(OH)], has been developed. The compound was characterized by single crystal X-ray diffraction methods, thermogravimetric analysis, vibrational (IR and Raman) spectroscopy and magnetic measurements. In the structure Co(II)O₆ octahedra, BO₄ and PO₄ tetrahedra form nine-member rings which in turn are linked to form CoBPO layers parallel to the bc plane. The layers are joined together by another set of PO₄ tetrahedra and the (piperazinium)²⁺ cations occupy the channels running along [1 0 0]. The structure is compared with that of (C₂N₂H₁₀)Co[B₂P₃O₁₂(OH)].     

Thioether crown complexes as templates for the assembly of extended polyiodide networks: synthesis and structures of {[M([16]aneS4)]2I}I11 (M = Pd,Pt), [Pd(cis-HO)2[14]aneS4)](I3)2, [Pd([9]aneS3)2](Ix)2 (x = 3, 5)

Pd(II) and Pt(II) complexes of [16]aneS₄ and Pd(II) complexes of cis-(HO)₂[14]aneS₄ and [9]aneS₃ have been used as templates for the self-assembly of polyiodide ions. The complexes {[M([16]aneS₄)]₂I}I₁₁ (M = Pd, Pt), [Pd(cis-(HO)₂[14]aneS₄)](I₃)₂, [Pd([9]aneS₃)₂](I_x)₂ (x = 3, 5) have been synthesized and structurally characterized. In {[M([16]aneS₄)]₂I}I₁₁, the polyiodide network consists of fused 14-member polyanion rings made up of interacting “L”-shaped I₅⁻ and I⁻ units; binuclear [([16]aneS₄)M–I–M([16]aneS₄)]³⁺ complex cations featuring a highly unusual linear and symmetric M–I–M moiety are each surrounded by one of these 14-member polyiodide rings in a belt-like fashion. The structures of [Pd(cis-(HO)₂[14]aneS₄)](I₃)₂ and [Pd([9]aneS₃)₂](I₃)₂ both feature tri-iodides as counter-anions. In [Pd(cis-(HO)₂[14]aneS₄)](I₃)₂, quite asymmetric I₃⁻ ions form sinusoidal infinite chains via head-to-tail I₃⁻⋯I₃⁻ interactions; these chains run along the (001) direction and are stacked along the (100) direction to form highly puckered anionic layers via I⋯I weak interactions that cross-link the chains. In [Pd([9]aneS₃)₂](I₃)₂, [Pd([9]aneS₃)₂]²⁺ cations are bridged on each side by pairs of symmetric I₃⁻ ions through long-range S⋯I contacts to form discrete infinite ribbons that run parallel to the a axis. By contrast, the structure of [Pd([9]aneS₃)₂](I₅)₂ consists of highly puckered polyanionic layers featuring fused 18-member polyiodide rings made up of I₅⁻ ions. Two of these layers related by an inversion center are stacked along the b axis and interact with each other to form large cavities within which the complex cations sit. In these complex arrays the cation can be regarded as a template around which polyanion networks can be structured. The solid state FT-Raman spectra of the reported polyiodides are discussed on the basis of their crystal structures.