Complete phase diagrams and physico-chemical properties for the ternary system (CsCl + NaCl + H2O) were determined at T = (298.15, 308.15, and 318.15) K, respectively. The X-ray diffraction method and Schreinemaker’s wet residue method were used to verify the solid phase. The phase diagrams show this ternary system is a complex type. Three crystallization regions were found corresponding to the single salt NaCl, a compound CsCl·2NaCl·2H2O, and a solid solution series [Cs1–x(Na·H2O)x]Cl (x in [Cs1–x(Na·H2O)x]Cl changed from 0 to 0.43 (298.15 K), 0.39 (308.15 K), and 0.36 (318.15 K) at each temperature. With rising temperature, the crystallization area of NaCl increased, but CsCl·2NaCl·2H2O and [Cs1–x(Na·H2O)x]Cl decreased simultaneously. However, density and refractive index increased with increasing CsCl concentration.

•Thermodynamic properties of RbF + Rb2SO4 + H2O and CsF + Cs2SO4 + H2O ternary systems were studied.•The exprimental data were fitted using Harned rule Pitzer model.•The activity coefficients, the osmotic coefficients, and the excess Gibbs free energy were calculated.In this paper, the potentiometric method was carried out to investigate the thermodynamic properties of the RbF + Rb2SO4 + H2O and CsF + Cs2SO4 + H2O ternary systems over total ionic strengths from (0.01–0.70) mol·kg−1 for different ionic strength fractions yB of Rb2SO4/Cs2SO4 with yB = 0.00, 0.30, 0.60 and 0.90, at 298.2 K. The Harned model and the Pitzer model were used to correlate the experimental data. The Harned coefficients and the Pitzer mixing parameters were evaluated by multiple linear regression technique. Moreover, the mean ionic activity coefficients of RbF/CsF and Rb2SO4/Cs2SO4, the osmotic coefficients, and the excess Gibbs energies of the studied systems were calculated, respectively.Thermodynamic properties, such as mean activity coefficients, osmotic coefficients and excess Gibbs free energies, of the RbF + Rb2SO4 + H2O and CsF + Cs2SO4 + H2O ternary systems were investigated by potentiometric method at 298.2 K. The Harned rule and the Pitzer model were used to correlate the experimental data.

The synthetic design of new porous open-framework materials with pre-designed pore properties for desired applications such as gas adsorption and separation remains challenging. We proposed one such class of materials, rod metal–organic frameworks (rod MOFs), which can be tuned by using rod secondary building units (rod SBUs) with different geometrical and chemical features. Our approach takes advantage of the readily accessible metal–triazolate 1-D motifs as rod SBUs to combine with dicarboxylate ligands to prepare target rod MOFs. Herein we report three such metal–triazolate–dicarboxylate frameworks (SNNU-21, -22 and -23). During the formation of these three MOFs, Cd or Zn ions are firstly connected by 1,2,4-triazole through the N1,N2,N4-mode to form 1-D metal–organic ribbon-like rod SBUs, which further joint four adjacent rod SBUs via eight BDC linkers to give 3-D microporous frameworks. However, tuned by the different NH2 groups from metal–triazolate rod SBUs, different space groups, pore sizes and shapes are observed for SNNU-21–23. All of these rod MOFs show not only remarkable CO2 uptake capacity, but also high CO2 over CH4 and C2-hydrocarbons over CH4 selectivity under ambient conditions. Specially, SNNU-23 exhibits a very high isosteric heat of adsorption (Qst) for C2H2 (62.2 kJ mol−1), which outperforms the values of all MOF materials reported to date including the famous MOF-74-Co.

•Thermal decomposition of indium-organic framework.•Ag-loaded mesoporous In2O3 materials.•Fast and high responses to HCHO.Mesoporous Ag/In2O3 composite materials with different concentrations of Ag particles have been prepared by the calcination of Ag+-entrapped indium-organic frameworks (InOFs). The structures and components of these MOF-derived Mesoporous Ag/In2O3 composite materials have been characterized thoroughly. Gas sensing measurements indicated that the incorporation of metallic Ag particles into the mesoporous structure significantly improves the gas-sensing properties of In2O3. Specially, the response of 5% Ag-loaded In2O3 sensor to 50 ppm formaldehyde is 5 times higher than that of pure In2O3 particles at 210 °C, which is among the best formaldehyde sensor materials reported to date. Also, Ag/In2O3 composite sensor exhibit short response time (~22 s) and excellent recovery. These results indicated that the InOF-derived mesoporous Ag/In2O3 materials maybe can be used to fabricate high performance formaldehyde sensors in practice.Mesoporous Ag/In2O3 materials have been produced by calcining indium-organic frameworks showing very fast and extremely high response towards HCHO.Download high-res image (230KB)Download full-size image

Highly connected crystalline porous materials are rare but promising for gas adsorption and separation since varying pore shape and size as well as high framework stability may be achieved by tuning the framework connectivity. We demonstrate herein two highly connected frameworks, namely, {[Cd7(BDC)6(MTAZ)2(DMF)6]·3DMF}n (SNNU-11) and {[Cd5(BDC) (PTAZ)8(DMF)2]·4DMF}n (SNNU-12) (BDC = 1,4-benzenedicarboxylic acid, MTAZ = 5-methyl-tetrazole, and PTAZ = 5-(4-pyridyl)-tetrazole). In SNNU-11, BDC ligands link S-shaped [Cd7(MTAZ)2] motifs to form a novel 10-connected framework, which is related to but different from the reported 10-connected bct and gpu nets. Under the similar synthesis condition, the utilization of 5-(4-pyridyl)-tetrazole produced SNNU-12, which is constructed from zigzag Cd5 clusters and exhibits a 12-connected fcu net. Notably, SNNU-12 decorated with uncoordinated nitrogen sites shows not only high CO2 uptake capacity (87.9 cm3 g–1, 1 atm, and 273 K) but also high CO2 over CH4 and C2 hydrocarbons over CH4 selectivity, which is among the highest values of highly connected MOF materials (connectivity ≥10) including famous UiO-66 and rare-earth fcu-MOFs under the same temperature and pressure.

•Ionothermal synthesis of crystalline inorganic materials•Unprecedented quaternary Ag–I–Pb–OH heterometallic framework•[Pb4(OH)4] cubane and [Ag2I6] dimeric building blocks•Remarkable luminescence and tuneable semiconducting propertiesWe reported herein an unprecedented quaternary heterometallic framework, namely, [AgPb2I3(OH)2] (1), which was successfully produced under ionothermal condition. In the title compound, [Pb4(OH)4] cubane and [Ag2I6] building blocks are jointed together to give a (6,6)-connected pcu topology. Compound 1 shows not only remarkable luminescent emissions, but also semiconducting properties tuned by the corresponding metal halide components.A novel quaternary heterometallic framework based on [Pb4(OH)4] cubane and [Ag2I6] building blocks was successfully produced under ionothermal conditions, which shows tuneable semiconducting and luminescent properties.

•Mesoporous In2O3 materials prepared by thermal decomposition of InOFs;•Tunable surface areas of porous In2O3 controlled by the calcination temperature;•Mesoporous In2O3 materials showed the highest responses to HCHO.Mesoporous In2O3 materials were synthesized by calcining indium-organic frameworks (InOFs, CPM-5 and MIL-68), which were further successfully utilized to detect toxic HCHO vapor. By taking the intrinsic structural features of two InOF precursors into account, the surface areas of produced indium oxides were well investigated via controlling the calcination temperature. The influence of surface area on the gas sensing performance was studied in detail. Porous In2O3 prepared by heat treatment at 650 °C showed the highest responses to 50 ppm HCHO (Rg/Ra = 31.8 and 38.0, respectively; Rg, resistance in gas; Ra, resistance in air) at 210 °C, which surpass the values of all the reported In2O3 materials to date under the similar conditions. The promising HCHO-sensing properties enable these InOF-templated mesoporous In2O3 materials to be competitive candidates for detecting poisonous formaldehyde in practice.Mesoporous In2O3 materials successfully produced by calcining indium-organic frameworks showing tunable porosity and high responses to HCHO, which surpass the values of all the reported In2O3 materials under the similar conditions.

•Activity coefficients of RbCl/CsCl in EC + H2O were determined.•Pitzer, modified Pitzer, and extended Debye–Hückel models were used.•The SLE and LLE of RbCl/CsCl + EC + H2O systems were studied.The (solid + liquid) equilibrium (SLE) and (liquid + liquid) equilibrium (LLE) of RbCl/CsCl + ethylene carbonate (EC) + H2O ternary systems were carefully investigated at 298.15 K. The SLE and LLE data were correlated by the corresponding equations respectively. Furthermore, the thermodynamic properties of RbCl/CsCl in the EC–water systems were determined by potentiometric method at T = 298.15 K. The experiment data were correlated by the Pitzer, modified Pitzer and the extended Debye–Hückel equations. The mean activity coefficients, osmotic coefficients and excess Gibbs free energies, standard Gibbs free energy of transfer and the standard solubility product of systems were calculated. The mean activity coefficient γ± decreases with the increase of the molality of electrolyte at the fixed mass fraction of EC. But γ± vary abnormally with the increase of the EC content. The result of ΔGt0 reflects the spontaneously transfer of the electrolytes from water to the mixed solvents.Thermodynamic properties, such as mean activity coefficients, osmotic coefficients and excess Gibbs free energies, of the ternary systems RbCl/CsCl + EC + H2O were determined at 298.15 K. Moreover, the (solid + liquid) equilibrium (SLE) and (liquid + liquid) equilibrium (LLE) of RbCl/CsCl + EC + H2O systems were studied at 298.15 K to maintain the homogeneity of the mixtures for potentiometric measurement.

In the present work, the density, ρ, refractive index, nD, and dynamic viscosity, η, for four binary solutions containing ionic liquids [Cnmim]X (Cnmim = 1-alkyl-3-methylimidazolium; n = 6, 8; X = Cl, Br) and ethylene glycol (EG) were investigated at temperatures of 288.15–333.15 K and at ambient pressure. In addition, the excess molar volume, VmE, was calculated and correlated using the Redlich-Kister polynomial equation. The temperature effect on the density of the binary systems studied was expressed by a linear two-parameter equation. The variation in density, refractive index, and viscosity with the composition was described by polynomial equations. The influence of carbon chain-length and the anion of the ionic liquids, and the influence of the temperature on the physicochemical properties of the binary systems can be explained by comparison of the experimental results.

•Thermodynamic properties of RbF + RbCl + H2O and CsF + CsCl + H2O ternary systems were determined.•The Pitzer model and the Harned rule were used to correlate the experimental data.•The mean activity coefficients, osmotic coefficients, and the excess Gibbs free energy were also obtained.Thermodynamic properties of (RbF + RbCl + H2O) and (CsF + CsCl + H2O) systems were determined by the potentiometric method for different ionic strength fractions yB of RbCl/CsCl at 298.2 K. The Pitzer model and the Harned rule were used to fit the experimental values. The Pitzer mixing parameters and the Harned coefficients were evaluated. In addition, the mean ionic activity coefficients of RbF/CsF and RbCl/CsCl, the osmotic coefficients, and the excess Gibbs energies of the systems studied were calculated.Thermodynamic properties, such as mean activity coefficients, osmotic coefficients and excess Gibbs free energies, of the RbF + RbCl + H2O and CsF + CsCl + H2O ternary systems were determined from potentiometric measurement at 298.2 K. The Pitzer model and the Harned rule were used to fit the experimental data.

Thermodynamic properties of the RbF + RbBr + H2O and RbF + RbNO3 + H2O systems were determined by the potentiometric method at the total ionic strengths ranging from 0.0017 to 0.7005 mol·kg–1 for different ionic strength fractions yB of RbBr/RbNO3 with yB = 0.00, 0.30, 0.60, and 0.90, at 298.2 K. Combining the Nernst equation and Pitzer equation, the mean ionic activity coefficients of RbF and RbBr/RbNO3, the osmotic coefficients, and the excess Gibbs energies of the studied systems were calculated.

The (solid + liquid) equilibrium (SLE) of N,N-diethylformamide (DEF) + MCl (M = Na, K, Rb) + H2O ternary systems were investigated from 288.15 to 338.15 K under atmospheric pressure. The isothermal solubility, density, and refraction index of the ternary solution, as well as the solubility at multiple temperature were reported. The (liquid + liquid) equilibrium (LLE) of (DEF + CsCl + H2O) ternary system was further studied at 298.15 and 308.15 K. The Jouyban–Arcee model was utilized to correlate the solubility, density, and refractive index data. The LLE was correlated by the Othmer–Tobias and the Bancroft equations. The complete phase diagrams of the (DEF + CsCl + H2O) system were further presented.

The potentiometric method was used to obtain mean activity coefficients of RbF in urea/formamide–water mixed solvents at 298.2 K. The weight fractions of amide were varied from 0 to 40 %. The Pitzer, modified Pitzer and extended Debye–Hückel equations were used for representing the mean activity coefficients and other related thermodynamic properties of the systems. Furthermore, corresponding parameters of the thermodynamic models mentioned herein before were also obtained.

Reported herein is a novel porous metal–organic framework (MOF) exhibiting unique nanoscale cages derived from the 3-fold self-interpenetration of chiral eta networks based on trifurcate {Zn2(CO2)3} building blocks and 1,3,5-tris(4-carboxyphenyl)benzene ligands. The attractive self-interpenetrated structural features contribute to the highest CO2 uptake capacity and CO2 binding ability among the interpenetrated MOFs.

Thermodynamic properties of LiCl in mixed solvents composed of polyhydric alcohols and water are measured by using the potentiometric technique at 298.15 K. The polyhydric alcohols are 1,2-propanediol (PG), 1,2-ethanediol (EG), and 1,2,3-propanetriol (GL). Pitzer and extended Debye–Hückel equations are applied to correlate the experimental data. The mean activity coefficients, the osmotic coefficients, and the excess Gibbs free energies were calculated. Meanwhile, the standard free energy of transference from water to the mixtures, the standard solubility product, and the primary LiCl hydration number are also obtained.

Nine members of the novel Ln–pyridine-3,5-dicarboxylate coordination polymer family, namely, [Ln(PDC)(GA)]n (Ln = Gd (1), Tb (2), Dy (3), Er (4)), [Ln(PDC)(OAc)(H2O)]n·nH2O (Ln = Sm (5), Eu (6), Gd (7)), [Gd(PDC)(OAc)(H2O)2]n·nH2O (8), and [Tb(PDC)1.5(H2O)]n (9) (PDC = pyridine-3,5-dicarboxylate, GA = glycolate, OAc = acetate), have been successfully obtained by carefully regulating the ancillary ligand or reaction temperatures. Complexes 1–4 are isomorphous two-dimensional networks generated by Ln–glycolate chains and bridging PDC ligands. When the HOAc was utilized instead of glycolic acid, isomorphic three-dimensional compounds 5–7 were isolated. The Ln3+ atoms are first bridged by acetate anions to give dinuclear clusters, which are extended by nearby six PDC ligands forming a 3D (3,6)-connected flu-topological framework. Notably, the increase of reaction temperature from 160 to 180 °C during the synthesis of compound 7 led to compound 8, the other 3D (3,6)-connected structure on the base of dinuclear subunits with rtl topology. Furthermore, the absence of HOAc introduced the formation of compound 9, in which each binuclear cluster links adjacent eight PDC anions to give a 3D (3,8)-connected tfz-d topological structure. The elemental analyses, XRPD, FT-IR, and TGA were also investigated to characterize compounds 1–9. Furthermore, solid-state photoluminescence measurements show that these Ln–pyridine-3,5-dicarboxylate coordination polymers produce strong emissions at room temperature.

•Rare sulfonate and imidazole co-ligand system•Unique 3D interpenetrated framework triggered by ligand configuration•Good degradation efficiency of organic dye under visible light irradiationThe combination of 1,4-bis(imidazol-1-ylmethyl)benzene (BIYB) and anthraquinone-2,7-disulfonic acid (H2AQDA) ligands leads to a copper coordination polymer, namely, {[Cu(BIYB)2(AQDA)]·H2O}n (1). The cis-BIYB ligands link one unique Cu(II) atoms to give 1D double chains, but trans-BIYB connects the other Cu(II) centers to generate 2D (4,4)-layers. Each H2AQDA ligand acts as a μ2-bridging linking the double chains and (4,4)-layers to generate the 3D framework of 1. Cu(1) and Cu(2) can be viewed as 6- and 4-connected nodes, which lead to a (4,6)-connected self-penetrated network. Notably, complex 1 represents the rare example of coordination polymer-based visible-light-driven photocatalyst, and shows good degradation efficiency of organic dye.A unique 3D interpenetrated Cu coordination polymer framework triggered by the cis- and trans-configurations of organic ligand exhibits remarkable visible-light-driven photocatalytic activity.

•Thermodynamics of LiCl + amides (urea, NMF, DMF, DMA) + water system were reported.•The Pitzer, modified Pitzer and extended Debye–Hückel models were used.•The mean activity coefficients, excess Gibbs free energy were calculated.•The standard solubility product and the primary hydration number were obtained.This article deals with the mean activity coefficients of LiCl in amide–water mixtures with both ɛ-increasing co-solvent (urea–water, N-methylformamide–water), and ɛ-decreasing co-solvent (N,N-dimethylformamide–water, N,N-dimethylacetamide–water) systems at 298.15 K by potentiometric method. Meanwhile, thermodynamic properties including the osmotic coefficients, the excess Gibbs free energy, the standard solubility product, the primary LiCl hydration number and the standard free energy of transference from water to the mixtures were also calculated. The nonideal behavior of these systems has been discussed in terms of the Pitzer, the Modified Pitzer and the extended Debye–Hückel equations parameters.The thermodynamic properties of LiCl in amide–water mixtures with both ɛ-increasing co-solvent (urea–water, N-methylformamide–water), and ɛ-decreasing co-solvent (N,N-dimethylformamide–water, N,N-dimethylacetamide–water) systems at 298.15 K were determined by potentiometric method.

Density ρ, refractive index nD, and viscosity η for ionic liquids [Cnmim]Cl (Cnmim = 1-alkyl-3-methylimidazolium; n = 2, 4, 6, 8 for ethyl, butyl, hetyl, and octyl) + N,N-dimethylformamide (DMF) binary systems have been investigated at atmospheric pressure from 288.15 K to 318.15 K. The molar excess Gibbs energy ΔG*E, volumetric properties including excess molar volume VE, and apparent molar volume Vφ,i have been calculated from the experimental data. Furthermore, the refractive index and viscosity deviations (ΔnD, Δη) from the ideal behavior have been obtained and well fitted to the Redlich–Kister equation. Our results show that DMF can effectively adjust the physicochemical properties of 1-alkyl-3-methylimidazolium ionic liquids.

We report herein the solid–liquid equilibria (SLE) of N,N-dimethylacetamide (DMA) + MCl (M = Na, K, Rb, and Cs) + H2O ternary systems for the first time. At the three given temperatures (T = 298.15 K, 308.15 K, and 318.15 K), the solubilities, densities, and refractive indices for these ternary systems are determined with the mass fraction of DMA in salt-free solvent system ranging from 0.0 to 1.0. The solubility of salts decreases significantly with the addition of DMA, and the salting-out ratios are calculated accordingly. The nonrandom two-liquid (NRTL) model can effectively fit the experimental solubility. Furthermore, to investigate the temperature effect on the SLE, the dynamic solubility measurement system is selected to determine the solubility of the salts in the mixed solvent (wDMA = 0.3, 0.5, and 0.7) with the temperature continuously increased. The solubility data at multiple temperatures are well fitted by the modified Apelblat equation and the λh equation.

The solubility, density and refractive index of RbCl/CsCl + [Cnmim]Cl (n = 2, 4, 6, 8) + H2O saturated systems have been studied at T = (288.15, 298.15 and 308.15) K. The solubility data were correlated by the nonrandom two-liquid (NRTL) model and an empirical equation. Both models can qualitatively represent the equilibrium behavior. In addition, the results denote that all the ionic liquids trigger salting-out effects with the order: [C2mim]Cl > [C4mim]Cl > [C6mim]Cl > [C8mim]Cl. The density and refractive index of the saturated solutions were determined for describing the relationship between the physical property and composition of the solution.

The solubilities, densities and refractive indices for the four ternary systems ethylene glycol/glycerin+RbNO3/CsNO3+H2O were measured with mass fractions of ethylene glycol or glycerin in a range of 0 to 1.0 at 288.15 and 298.15 K. In all the cases, the presence of either ethylene glycol or glycerin significantly reduces the solubilities of the rubidium nitrate and cesium nitrate in aqueous solution, but the refractive indices increase with the increase of mass fraction of either ethylene glycol or glycerin. The density, refractive index and solubility of the saturated ternary systems were correlated with each other via polynomial equations. In addition, the refractive indices and densities of unsaturated solutions were also determined for the four ternary systems with different salt concentrations, which were correlated with the salt concentration and proportion of ethylene glycol or glycerin in the solution.

Seven novel d10-metal–imidazole-4,5-dicarboxylate compounds namely [Zn(H2EIMDC)2(H2O)2]·2.25H2O (1), [Ag2(HPIMDC)(HPIM)2] (2), [Zn(HPIMDC)(H2O)]n (3), {[Cd(H2PIMDC)2]}n (4), {(H3O)[Cd(MIMDC)]}n (5), {(H3O)[Cd(EIMDC)]}n (6) and {(H3O)[Cd2(PIMDC)(HPIMDC)]}n (7), (H3MIMDC = 2-methyl-1H-imidazole-4,5-dicarboxylic acid, H3EIMDC = 2-ethyl-1H-imidazole-4,5-dicarboxylic acid, and H3PIMDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, HPIM = 2-propyl-1H-imidazole), have been synthesized by careful control of the synthetic conditions such as the solvent, pH value and the metal-to-ligand molar ratios. X-ray single-crystal structural analyses reveal that the change of alkyl groups on the 2-position of the ligand leads to the diversity of their structures, which range from discrete compounds (1 and 2), one-dimensional chain (3), two-dimensional layer (4) to three-dimensional frameworks (5, 6 and 7). Specially, under the same reaction conditions, the extending of the 2-position alkyl substitutents gradually reduces the symmetry of the ultimate 3D frameworks, which vary from tetragonal I4/mmm (5), tetragonal P42/nmc (6) to orthorhombic Pbam (7) space groups. Alkyl-substituted imidazole-4,5-dicarboxylate ligands exhibit either singly, doubly, or triply deprotonated fashion, and coordinate to Zn(II), Cd(II) or Ag(I) ions in terminal μ2-, μ3- or μ4-modes. Compounds 1–7 have also been characterized by means of elemental analyses, X-ray powder diffractions, FT-IR, TGA and gas-adsorption. Furthermore, solid-state photoluminescence measurements show that all these d10-metal compounds produce strong blue emissions at room temperature.

This article reports mean activity coefficients determined by the potentiometric method for RbF and CsF in alanine/proline/serine + water mixtures at 298.15 K. The experimental results were modeled by the Pitzer, modified Pitzer, and extended Debye–Hückel equations. The results showed that the three models fit the experimental data well and gave satisfactory results. The osmotic coefficients, excess Gibbs free energy, and corresponding parameters were also obtained.

A 3D metal–organic framework, namely, {[EMIM][In3(μ3-OH)2(1,2,4,5-BTC)2∙2H2O]}n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized by using 1-ethyl-3- methylimidazolium bromide ([EMIM]Br) ionic liquid as solvent. The 7-coordinated pentagonal bipyramidal In(1) and octahedral In(2) atoms are connected by the μ3-OH groups to form an infinite [In3(μ3-OH)2]n inorganic chain along the a-axis, which are further extended by 1,2,4,5-BTC ligands to generate the 3D anionic microporous framework of 1. The [EMIM]+ cations occupy the 1D channels acting as template and charge-balancing species. Compound 1 shows strong blue luminescence and remarkable photocatalytic degradation of methylthionine chloride.An anionic porous indium MOF constrcuted from [In3(μ3-OH)2]n inorganic chains exhibiting blue luminescence and remarkable photocatalytic activity.Highlights► Ionothermal synthesis ► Anionic In-MOFs based on [In3(μ3-OH)2]n inorganic chain ► Rod-packing topological net ► Blue photoluminescence and remarkable photocatalytic activity

•ATPS of ionic liquids + Rb2CO3/Cs2CO3 + H2O.•The binodal curves were fitted using a three-parameter equation.•The tie-lines were correlated by the Othmer–Tobias and Bancroft equations.•The different effecting factors on the ATPS were investigated.This work was devoted to propose a series of novel aqueous two-phase systems (ATPSs) composed of 1-alkyl-3-methylimidazolium bromide + Rb2CO3/Cs2CO3 + water ([C2mim]Br = 1-ethyl-3-methylimidazolium bromide, [C3mim]Br = 1-propyl-3-methylimidazolium bromide, [C4mim]Br = 1-butyl-3-methylimidazolium bromide, [Amim]Br = 1-allyl-3-methylimidazolium bromide). The phase behavior of these ATPSs had been experimentally determined at T = 288.15 K < T < 308.15 K. In particular, the effects of the ionic liquid structure, temperature and the types of inorganic salts on the phase equilibrium of ATPSs have been discussed in detail. The binodal curves were fitted by a three-parameter equation. The tie-lines were correlated by the Othmer–Tobias and Bancroft equations.The phase behavior for a series of aqueous two-phase systems composed of 1-alkyl-3-methylimidazolium bromide + Rb2CO3/Cs2CO3 + water had been experimentally determined in the temperature range of 288.15–308.15 K.

The mean activity coefficients for CsCl in N-methylformamide or urea (w) + H2O (1 − w) systems were determined in this work by potentiometry, using ion-selective electrodes at 298.15 K. The value of mass fraction w was varied between 0.00 and 0.40 in five unit-steps and the molality of CsCl was between 0.0020 and 1.4009 mol·kg−1. The experimental data have been correlated with the Pitzer, modified Pitzer and the extended Debye–Hückel equations. The resulting values of the mean activity coefficients, the osmotic coefficients and the standard Gibbs energy of transfer, together with the Pitzer ion-interaction parameters (β(0), β(1) and Cφ), extended Debye–Hückel parameters (a, c and d), and modified Pitzer parameters (b, BMX, CMX) are reported for the investigated systems.

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

Activity coefficients of RbCl or CsCl in methanol + ethanol + water were determined at 298.15 K by the cells containing ion-selective electrodes (ISEs). The molalities of RbCl and CsCl are up to approximately 1 mol·kg–1 in the mixed solvents, and the mass fractions of five aqueous MeOH/EtOH mixtures studied were (5/5, 10/5, 5/10, 10/10, and 15/15) %. The experimental data were optimized using the extended Debye–Hückel, the Pitzer, and the modified Pitzer equations. The results of the apparent standard electromotive force E0* of the three equations are in good agreement. The mean activity coefficients and the standard Gibbs energy of transfer of RbCl or CsCl from pure water to mixed solvents (MeOH + EtOH + water) were also calculated.

In this work, it was found that some monosaccharides normally used to stabilize enzymes at high temperatures, however, actually caused a deactivation of chloroperoxidase (CPO). The red native CPO was converted to a stable pale species that lost enzymatic activity. This deactivation was irreversible and was sensitive to temperature. It was different from the general peroxide-mediated deactivation of CPO.Data from measurement of chlorination activity as well as UV–vis, fluorescent, and CD spectral analysis indicated that monosaccharide-induced deactivation can be attributed to precipitation of protein in the presence of monosaccharide and the interaction of the aldehyde group of sugar with amino groups, especially the terminal amino group, on proteins to form Schiff bases which then rearrange to the stable amino ketone.It is further noted that the deactivation efficiency depends on the stereostructure of monosaccharides. d-Glucose was the most efficient inactivating agents due to its aptitude for both of the interactions mentioned in the above paragraphs. The deactivation was specific to aldose. No deprivation of the heme iron was involved in this deactivation.Graphical abstractHighlights► Monosaccharides could cause a suicide inactivation of chloroperoxidase (CPO). ► The sixth axial ligand position of heme iron was occupied by monosaccharides. ► Absorption of Soret band decreased due to occurrence of precipitation of protein. ► Fluorescent and CD spectral analysis indicated a minor uncoiling of α-helix occurred. ► The stereostructure of monosaccharide is related with this enzymatic inactivation.

Imidazolium-based ionic liquids are firstly utilized as the solvent, structure-directing agent, charge compensating agent, as well as reaction sources to give two novel crystalline 3D open-framework halogeno(cyano)cuprates showing strong luminescence.

A novel 3D indium metal–organic framework, namely, {[EMIM]2[InK(1,2,4,5-BTC)1.5(H2O)2]}n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), has been synthesized under ionothermal conditions by using the ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent. Two In and two K atoms were linked by two μ3-H2O to give a [In2K2(μ3-H2O)2] tetranuclear cluster, which are connected by 1,2,4,5-BTC ligands to form the 3D anionic framework of compound 1. Furthermore, the [EMIM]+ cations acting as extra framework charge-balancing species occupy the channels of the 3D anionic framework. Notably, compound 1 shows strong blue luminescence and remarkable photocatalytic degradation of methylthionine chloride.Ionothermal synthesis of a novel 3D indium MOFs based on tetranuclear clusters showing strong blue luminescence and remarkable photocatalytic degradation of methylthionine chloride.Highlights► Ionothermal synthesis of novel In-MOFs. ► 3D framework based on tetranuclear [In2K2(μ3-H2O)2] clusters. ► Strong blue photoluminescence attributed to the intra-ligand emission. ► Remarkable photocatalytic degradation of the methylthionine chloride.

In this paper, the mean activity coefficients for CsBr, as well as the osmotic coefficients, the excess Gibbs free energies, the Gibbs energies of transference, and the primary hydration in different MeOH–water and EtOH–water mixtures at 298.15 K are calculated by potentiometric measurements. The cell used in this work contains two ion selective electrodes (ISEs): Cs-ISE|CsBr(m), ROH(w), H2O(1 – w)|Br-ISE (R = Me and Et), and the mass fraction of ROH in the mixture (w) was varied between 0 and 0.3 in 0.1 unit steps. The experimental data were correlated very well by the thermodynamics equations of Pitzer, modified Pitzer, and Debye–Hückel models.

This article deals with the mean activity coefficients of RbF or CsF in the glycine + water mixed systems. The Pitzer, the modified Pitzer, and the extended Debye–Hückel equations are used to describe the nonideal behavior of the electrolyte. The osmotic coefficients, the excess Gibbs free energy, and the standard Gibbs energies of transfer were calculated with the corresponding parameters.

A novel 3D (4,6)-connected topological architecture, obtained under ionothermal conditions by using 1-ethyl-3-methyl imidazolium bromide ([EMI]Br) as solvent and structure-directing agent, presents a non-centrosymmetric polar packing arrangement showing an interesting ferroelectric property.

A novel 3D microporous metal–organic framework based on tetrahedral Zn4 clusters has been synthesized and characterized, which presents an unprecedented (3,6)-connected (4·62)3(43·66·86) topology, and the capability of selective adsorption of CO2.

The unusual 10-connected self-penetrating metal–organic framework based on sixteen-nuclear hybrid cadmium clusters has been constructed using 1,2,4-triazole, SCN− and F− as coligands, which represents the highest-connected uninodal network topology presently known for self-penetrating systems.

Seven organic-inorganic hybrid solids, namely, [(CdI2)2(L1)2] (1), [(CdBr2)3(L1)2]n (2), [(CdCl2)5(L1)2]n (3), [(CdI2)(L2)]n (4), [(CdBr2)(L3)]n (5), [(CdBr2)2(L4)2]n (6), and [(CdI2)4(L4)4]n (7), have been obtained via the self-assembly of CdX2 (X = Cl, Br or I) with the four structurally related flexible organic ligands 1,2-bis(benzotriazole)ethane (L1), 1,3-bis(benzotriazole)propane (L2), 1,4-bis(benzotriazole)butane (L3) and 1,6-bis(benzotriazole)hexane (L4) under solvothermal conditions. Compound 1 presents a binuclear structure with a [Cd2N12C4] 18-membered cycle. In 2, the L1 ligands locate alternately on the two sides of the 1-D inorganic chain formed by papilionaceous [Cd2Br2] subunits. The 1-D hexagonal [CdCl2]n grid inorganic chains in 3 are generated by vertex-loss cubane-like [Cd3Cl4] motifs through sharing faces, which are further connected by L1 ligands to give a 2-D hybrid layer. For compound 4, the L2 ligands and 4-connected Cd centres link each other to give a 1-D single chain. In 5 and 6, [Cd2Br4] units are connected by L3 and L4 to generate a 2-D (4, 4) net and 1-D double chain structure, respectively. Four independent [CdI2] centres and four L4 ligands in 7 generate an extraordinarily large [Cd4N24C24] 52-membered cycle. The varying structures of 1–7 indicate that the spacer length of the bis(benzotriazole)alkane ligands and counter-anions play an essential role in the formation of the framework of the Cd(II) hybrid materials. Strong π–π stacking interactions between the benzotriazole ligands pack these low-dimensional hybrid chains or layers into high-dimensional supramolecular frameworks. The UV-vis diffuse reflectance spectra and solid state luminescence measurements show that compounds 1–7 are potential semiconductor and photoluminescence materials.

Self-assembly of CdCl2 and 1,2,4-triazole under hydrothermal condition yields a novel three-dimensional coordination polymer, namely {[Cd8Cl4(Trz)12(H2O)]·2H2O}n (1) (Trz = 1,2,4-triazole). Single-crystal X-ray diffraction reveals that four of the five independent Cd centers are linked by two μ2-Cl and two μ3-Cl atoms to form novel heptanuclear [Cd7Cl4] clusters, which are connected by the bridging water molecules to generate an unprecedented 1D castellated inorganic chain. Furthermore, the fifth unique Cd center and the castellated Cd–Cl–O chain are joint to each other via six different μ3-Trz ligands to give a 3D organic–inorganic hybrid framework of 1.A novel 3D hybrid coordination polymer was obtained via the self-assembly of CdCl2 and 1,2,4-triazole under hydrothermal condition, which is constructed from unprecedented 1D castellated Cd–Cl–O inorganic chains and μ3-triazole ligands.Highlights► 1D castellated inorganic chain based on heptanuclear [Cd7Cl4] clusters. ► 3D organic–inorganic hybrid framework with rod-packing topology. ► Strong blue photoluminescence attributed to LMCT.

Activity coefficients for RbCl in different ethylene glycol + water and glycerol + water mixed solvents were determined at 298.15 K using potentiometric measurements. The Pitzer and extended Debye−Hückel equations were applied to describe the nonideal behavior of the electrolyte, and the corresponding coefficients were determined for each mixed solvent system.

The mean activity coefficients of the CsCl + propylene glycol + water system were determined at 298.15 K using potentiometric measurements. The range of CsCl molality (m) is (0.01 to 1.20) mol·kg−1, and the mass fraction of propylene glycol (w) in mixed solvent is 0.10 to 0.40. The Pitzer, the modified Pitzer, and the extended Debye−Hückel equations are used to describe the nonideal behavior of the electrolyte. The activity coefficients and the osmotic coefficients of CsCl were calculated by the Pitzer equation. We also obtained the Gibbs energy of transfer of CsCl from water to propylene glycol + water mixtures.

Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {(HETA)[(Cu6I7)(ETA)2]}n(1) and {K(Cu6Br7)(BBTH)}n(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu3I4] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu6I7] cluster, which further form novel 1D [Cu6I7]nn− anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu5Br4] clusters and rhomboid [Cu2Br2] dimers link each other to generate a [Cu6Br7]nn− 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV–vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials.Two unprecedented anionic [CuI6X7]nn− (X=Br and I) chain-based organic–inorganic hybrid solids, namely, {(HETA)[(Cu6I7)(ETA)2]}n (1) and {K(Cu6Br7)(BBTH)}n(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)- hexane) have been synthesized under solvothermal reactions and characterized.

Using 1,2,4-triazole and adipic acid as coligands, a novel three-dimensional metal–organic framework, namely {[Cd4Cl(trz)5(adi)]·H2O}n (1) (trz = 1,2,4-triazole, adi = adipic acid) was hydrothermally synthesized and characterized. The crystal structure reveals that three independent Cd(II) centers are linked via one μ3-Cl and two μ3-COO− groups to form a unique [Cd4Cl(CO2)2] tetranuclear cluster, which acts as a 10-connected node joining adjacent four tetranuclear subunits and six 3-connected trz nodes to give a novel (3,10)-connected topological net with the Schläfli symbol (43)(41862562).A novel 3D metal–organic framework, namely {[Cd4Cl(trz)5(adi)]·H2O}n (1) (trz = 1,2,4-triazole, adi = adipic acid) was prepared under hydrothermal condition and characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, Raman spectrum, TG/DTA and photoluminescence measurements.

The self-assembly of CuCN and 1H-TAZ ligand under hydrothermal conditions generated a novel three-dimensional hybrid supramolecular framework, namely, [Cu6(TAZ)4(CN)2]n (1) (TAZ = tetrazole). Single-crystal X-ray diffraction show that [Cu2(TAZ)2] binuclear subunits are linked by μ2- and μ3-CN groups to give a 2D double-wave-shaped network, which possesses 1D channels with four open-windows. The 2D bilayers interpenetrated each other to form the 3D supramolecular framework of 1.A novel 3D organic–inorganic hybrid supramolecular solid constructed from interpenetrating (3,4,5)-connected 2D porous nets, namely, [Cu6(TAZ)4(CN)2]n (1) (TAZ = tetrazole) was successfully synthesized under hydrothermal conditions and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR, Raman spectrum, DT/TGA and solid state photoluminescence measurements.

Solubilities, densities, and refractive indices have been measured for the four ternary systems, ethylene glycol + NaCl + H2O, ethylene glycol + KCl + H2O, ethylene glycol + RbCl + H2O, and ethylene glycol + CsCl + H2O, at T = 298.15 K, with mass fractions of ethylene glycol ranging from 0 to 1.0. Polynomial equations of fit are proposed for the solubility of the saturated solutions as a function of the mass fraction of ethylene glycol. The equations proposed also account for the density and refractive index for the saturated solutions. On the other hand, the density and refractive index of unsaturated solutions were also determined for the same ternary systems with varied undersaturated salt concentrations. Values for both the properties were also correlated with the salt concentrations and proportions of ethylene glycol in the undersaturated solutions. In all the cases, the presence of ethylene glycol significantly reduces the solubility of the salts in the aqueous solution.

The mean activity coefficient of RbCl or CsCl in N,N-dimethylformamide (DMF) + water mixtures was determined by potentiometric measurements at 298.15 K in the range w = 0.10 to 0.40 DMF. The Pitzer model was adopted to describe the behavior of the electrolytes. We also obtained the osmotic coefficients and the Gibbs energies of transfer of rubidium or cesium chloride from water to DMF + water mixtures.

The mean activity coefficients of KCl were determined in ethylene glycol−water mixed solvents, in the range of (10, 20, 30, and 40) % ethylene glycol, from the electromotive force (EMF) data at (278.15, 288.15, 298.15, and 308.15) K. The Pitzer and extended Debye−Hückel equations were used to describe the nonideal behavior of the electrolyte, and the corresponding activity and osmotic coefficients were determined. Moreover, the standard Gibbs energy of transference of KCl−ethylene glycol−water was evaluated.

A novel 3D coordination polymer [Ag(dmtrz)] (dmtrz = 3,5-dimethyl-1,2,4-triazole) (1) was prepared under solvothermal condition and structurally characterized. The crystal structure reveals that Ag(I) centers are firstly linked via dmtrz anions to form an infinite 21 helix, which is further interconnected to four neighboring anti-parallel helices to form a 3D framework with rare non-interpenetrating 8210-a topology.A new 3D coordination polymer [Ag(dmtrz)] (dmtrz = 3,5-dimethyl-1,2,4-triazole) (1) with a non-interpenetrating 8210-a topology was prepared and characterized via X-ray single-crystal diffraction, elemental analysis, XRPD, FT-IR, Raman spectra, TGA and photoluminescence measurements.

Reaction of the N-tosyl-ethylenediamine and salicylaldehyde forms a new sulfonamide Schiff base N-[2-(2-hydroxybenzylideneamino)ethyl]-4-methyl-benzene-sulfonamide (H2L). Three novel complexes constructed from H2L, namely, [M(HL)2] · xH2O (M = Cu, x = 0 for 1, M = Ni, x = 0 for 2 and M = Zn, x = 1 for 3) have been prepared and characterized via X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, UV–Vis, TGA and photoluminescence measurements. Complex hydrogen bonds, C–H···π and π–π stacking interactions lead 1–3 to present 1-D, 2-D and 3-D supramolecular architectures, respectively.Three novel complexes [M(HL)2] · xH2O (M = Cu, x = 0 for 1, M = Ni, x = 0 for 2 and M = Zn, x = 1 for 3; H2L = N-[2-(2-hydroxybenzylideneamino)ethyl]-4-methyl-benzene-sulfonamide) have been prepared and characterized via X-ray single-crystal diffraction, elemental analysis, XRPD, FT-IR, UV–Vis, TGA and photoluminescence measurements.

The solvothermal reaction of the flexible ligand 1,2-bis(benzotriazole)ethane (bbta) with CuI produced a novel two-dimensional organic-inorganic hybrid solid, namely, [(Cu6I4)2(bbta)2(bta)4]n (bta = benzotriazole) (1). Novel 1D inorganic chains [Cu6I4]n2n- constructing from unprecedented flower-basket-shaped [Cu4II4] clusters are observed, which are further linked by the bbta and bta ligands using rare μ3-bidging mode to generate the 2D organic–inorganic hybrid structure of 1.A novel 2D organic–inorganic hybrid solid [(Cu6I4)2(bbta)2(bta)4]n (1) (bta = benzotriazole, bbta = 1,2-bis(benzotriazole)ethane) constructed from unprecedented flower-basket-shaped [Cu4II4] clusters was prepared under solvothermal condition and characterized.

Liquid−liquid equilibria for the two ternary systems of CH3OH + Rb2CO3 + H2O and CH3CH2OH + Rb2CO3 + H2O were measured at T = (298.15, 308.15, and 318.15) K. Binodal curves, tie-lines, and integrated phase diagrams for the two ternary systems are given. The experimental binodal curve data are correlated using a three- parameter equation, and the tie-line data are corrected by the Othmer−Tobias and Bancroft equations. The salting-out effect of ethanol is greater than that for methanol, but the effect of temperature on the equilibrium was not significant.

This work reports the results of a thermodynamic investigation of the ternary CsCl−MgCl2−H2O mixed electrolyte system. The activity coefficients of this mixed aqueous electrolyte system have been studied with the electromotive force (EMF) measurement of the cell: Cs ion-selective electrode (ISE)|CsCl (mA), MgCl2 (mB), H2O|Ag/AgCl at 298.15 K and over total ionic strengths from (0.01 to 1.50) mol·kg−1 for different ionic strength fractions yB of MgCl2 with yB = 0, 0.25, 0.50, and 0.75. The cesium ion-selective electrode (Cs-ISE) and the Ag/AgCl electrode used in this work were made in this laboratory and had a good Nernstian response. The experimental results obey the Harned rule, and the Pitzer model can be used to describe this aqueous system satisfactorily. The osmotic coefficients, excess Gibbs energies, and activities of water of the mixtures were also calculated.

In this paper, we present the results of our study of the phase equilibria for two quaternary systems: water + 1-propanol/2-propanol + potassium chloride (KCl) + cesium chloride (CsCl) at 298.1 ± 0.1 K. We also produced the binodal curves and tie-lines at different KCl/CsCl mass-fraction ratios, and produced integrated phase diagrams for the quaternary systems. We also discuss the solvation abilities of KCl and CsCl, and the effect of the polarity of the organic solvent on the liquid–liquid equilibrium. We compared the experimental tie-lines derived for the quaternary systems with values predicated by modifying the Eisen–Joffe equation. The model produced satisfactory results.

A new supramolecular complex [Cs(DB24C8)][CuBr2] (1) (DB24C8 = Dibenzo-24-Crown-8) has been prepared, characterized and structurally investigated. The structure of complex 1 features a two-dimensional (2D) (4,4) network in the ac plane based on C–H⋯π interactions and the dimensionality is further increased to 3D by Cs⋯Br weak interactions.This is a novel 0D supramolecular complex whose dimensionality is increased to 3D by C–H⋯π and Cs⋯Br weak interactions. In the pictogram, the ligands were omitted for clarity and the cesium cations were linked by dashed lines according to the connectivity defined by C–H⋯π bonds.

A novel three-dimensional organic–inorganic hybrid solid [Zn3(3atrz)2(H2O)2(MoO4)2]n (1) (3atrz = 3-amino-1,2,4-triazole) constructed from two-dimensional Mo–O–Zn bimetallic oxide networks was prepared under hydrothermal condition and characterized. Unprecedented {Zn6Mo6} 12 metal central-membered inorganic rings together with novel {Zn6(3atrz)6} metal–organic coordination rings exist in this structure.A novel three-dimensional organic–inorganic hybrid solid [Zn3(3atrz)2(H2O)2(MoO4)2]n (1) (3atrz = 3-amino-1,2,4-triazole) was prepared under hydrothermal condition and characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, Raman spectrum, TGA and photoluminescence measurements.

A novel metal–organic coordination polymer, namely, {[K2(H2O)6][Cd3(1,2,4,5-BTC)2]}n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent. Complex 1 features a novel 3-D (4, 8)-connected porous anionic architecture constructed by linking trinuclear Cd subunits with 1,2,4,5-BTC4− ligands, which are further filled with 1-D [K2(H2O)6] cationic chains.A novel metal–organic coordination polymer, namely, {[K2(H2O)6][Cd3(1,2,4,5-BTC)2]}n (1) (1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent.

The methodology for the study of the liquid−liquid equilibrium of quaternary systems including two inorganic salts, water, and an organic solvent has been reviewed and applied to the water + 1-propanol + potassium chloride (KCl) + cesium chloride (CsCl) system. Mutual solubility, tie-line, and binodal curve data for the quaternary system at (35 and 45) °C were measured, and it was found that the effect of temperature on the phase equilibrium was insignificant within the investigated temperature range. Furthermore, the binodal curve data were satisfactorily correlated using a five-parameter equation, and the experimental tie-line data were compared with values predicated by a modification of the Eisen−Joffe equation.

The liquid–liquid–solid equilibria of the two quaternary systems sodium chloride + rubidium chloride + (1-propanol or 2-propanol) + water were investigated at 25 °C. The binodal curves and tie lines together with the integrated phase diagrams for the two quaternary systems have been determined to investigate salting effects. The different equilibrium regions are discussed in detail. The results of the fitting for experimental tie line data by the Eisen−Joffe equation are reasonable.

The mean activity coefficients of LiCl in ROH/water mixed solvents (where R = Me and Et) were determined using the electromotive force (EMF) method at 298.15 K. The Pitzer equation and Pitzer−Simonson−Clegg equation were applied to the experimental data.

In an attempt to probe a potential template role of the large alkali-metal cation cesium in organization of biorelevant ligands, 5-sulfosalicylate, 3,5-dinitrosalicylate and 2,4-dinitrophenol complexes of cesium were prepared and structurally investigated. The structures of cesium 5-sulfosalicylate, cesium 3,5-dinitrosalicylate and cesium 2,4-dinitrophenoxide monohydrate have been determined through X-ray diffraction analysis. The 5-sulfosalicylate anion has lost the proton at the −SO3H group while the 3,5-dinitrosalicylate anion at −COOH group but both retains the usual intermolecular hydrogen bond between phenolic and carboxylic oxygen. In cesium 2,4-dinitrophenoxide monohydrate, the Cs+ cation is 12-coordinate by O atoms in anions and water molecules while the metal atoms in cesium 5-sulfosalicylate and cesium 3,5-dinitrosalicylate have coordination numbers 10 and 11, respectively, with an irregular coordination sphere made up exclusively of oxygen atoms. Even more in cesium 2,4-dinitrophenoxide monohydrate, the water molecules are in rare triply bridging positions between these cations. Both complexes have layer structures containing the cations and polar groups of the ligands in core domains sandwiched by the aromatic rings above and below. The organization of all layer structures appears to be governed mainly by steric effects and electrostatic forces with very little directional influence of the cations.The structures of cesium 5-sulfosalicylate, cesium 3,5-dinitrosalicylate and cesium 2,4-dinitrophenoxide monohydrate have been determined through X-ray diffraction analysis. Both complexes have layer structures containing the cations and polar groups of the ligands in core domains sandwiched by the aromatic rings above and below. The organization of all layer structures appears to be governed mainly by steric effects and electrostatic forces with very little directional influence of the cations.

•The ternary system (NaCl + RbCl + H2O) at T = (288.15, 298.15 and 308.15) K.•The stable (solid + liquid) phase equilibrium was achieved.•The solid phases were determined by Schreinemaker’s wet residue and X-ray diffraction method.The (solid + liquid) phase equilibrium of the ternary system (NaCl + RbCl + H2O) at T = (288.15, 298.15 and 308.15) K was studied by the method of isothermal solution saturation. Moreover, the density and refractive index of the solution was also determined. The solid phase was studied by the Schreinemaker’s wet residue method and verified by X-ray diffraction. The results show that each of the phase diagrams contains one invariant point, two univariant curves, and three crystallization regions. The crystallization region of NaCl increased obviously with the temperature increasing, while the crystallization regions of RbCl and the mixed crystallization region of (NaCl + RbCl) decreased a little. Furthermore, there are break points at the invariant points for density and refractive index curves.

Biotransformation of cyclohexene catalyzed by chloroperoxidase (CPO) from Caldariomyces fumago was employed to prepare value-added oxygenated derivative: trans-1,2-cyclohexanediol (CHD) using H2O2 as oxidants. The conversion of substrate was enhanced to 89.2% in the presence of small quantities of quaternary ammonium salts (QAS) compared to that of only 48.1% in aqueous phosphate buffer after 150 min. The enhancement was dependent on the concentration and alkyl group length of QAS. QAS were found playing multiple functions in reaction media: phase transfer catalysis and tuning the composition of product. UV–vis, fluorescence and circular dichroism (CD) spectral assay were employed to investigate the effect of QAS on micro-environment around active center and structure of protein. The strengthening of α-helix structure of CPO and more exposure heme for easily access of substrate was found responsible for the improvement of catalytic performance of CPO. Moreover, the determined kinetic parameters indicated the affinity and selectivity of CPO to substrate was improved according to the observation of a decrease of Michaelis constant Km while an increase of the second order rate constants kcat/Km.The strategy reported in this work is environment-friendly, straightforward and applicable to large scale preparation.Graphical abstractDownload high-res image (192KB)Download full-size imageHighlights► Cyclohexene was turned to value-added derivative by CPO-catalyzed biotransformation. ► Small quantity of introduced quaternary ammonium salts played multiple functions. ► The strategy is environment-friendly, straightforward and applicable to large scale.

This work focused on a systematic investigation of the influences of the spacer length of the flexible α,ω-bis(benzotriazole)alkane ligands and counteranions on the overall molecular architectures of hybrid structures that include Cu(I). Using the self-assembly of CuX (X = Cl, Br, I, or CN) with the five structurally related flexible organic ligands (L1−L5) under hydro(solvo)thermal conditions, we have synthesized and characterized 10 structurally unique materials of the Cu(I)/X/α,ω-bis(benzotriazole)alkane organic−inorganic hybrid family, {[CuCl]2(L1)}n (1), {[CuBr](L2)}n (2), {[CuCl]2(L3)}n (3), {[CuI]2(L4)}n (4), {[CuBr]2(L4)}n (5), {[CuBr]3(L5)}n (6), {[CuCN]2(L1)}n (7), {[CuCl]4(L2)}n (8), {[CuBr]4(L2)}n (9), and {[CuCl]2(L4)}n (10), by means of elemental analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and photoluminescence measurements. Single-crystal X-ray analyses showed that the inorganic subunits in these compounds were {Cu2X2} binuclear clusters (1 and 2), {Cu4X4} cubane clusters (4, 5, and 10), {CuX}n single chains (3 and 7), a {Cu3X3}n ladderlike chain (6), and unprecedented {Cu8X8}n ribbons (8 and 9). The increasing dimensionality from 1-D (1−4) to 2-D (5 and 6) to 3-D (7−10) indicates that the spacer length and isomerism of the bis(benzotriazole)alkane ligands play an essential role in the formation of the framework of the Cu(I) hybrid materials. The influence of counteranions and π−π stacking interactions on the formation and dimensionality of these hybrid coordination polymers has also been explored. In addition, all the complexes exhibit high thermal stability and strong fluorescence properties in the solid state at ambient temperature.

A novel 3D (4,6)-connected topological architecture, obtained under ionothermal conditions by using 1-ethyl-3-methyl imidazolium bromide ([EMI]Br) as solvent and structure-directing agent, presents a non-centrosymmetric polar packing arrangement showing an interesting ferroelectric property.

The synthetic design of new porous open-framework materials with pre-designed pore properties for desired applications such as gas adsorption and separation remains challenging. We proposed one such class of materials, rod metal–organic frameworks (rod MOFs), which can be tuned by using rod secondary building units (rod SBUs) with different geometrical and chemical features. Our approach takes advantage of the readily accessible metal–triazolate 1-D motifs as rod SBUs to combine with dicarboxylate ligands to prepare target rod MOFs. Herein we report three such metal–triazolate–dicarboxylate frameworks (SNNU-21, -22 and -23). During the formation of these three MOFs, Cd or Zn ions are firstly connected by 1,2,4-triazole through the N1,N2,N4-mode to form 1-D metal–organic ribbon-like rod SBUs, which further joint four adjacent rod SBUs via eight BDC linkers to give 3-D microporous frameworks. However, tuned by the different NH2 groups from metal–triazolate rod SBUs, different space groups, pore sizes and shapes are observed for SNNU-21–23. All of these rod MOFs show not only remarkable CO2 uptake capacity, but also high CO2 over CH4 and C2-hydrocarbons over CH4 selectivity under ambient conditions. Specially, SNNU-23 exhibits a very high isosteric heat of adsorption (Qst) for C2H2 (62.2 kJ mol−1), which outperforms the values of all MOF materials reported to date including the famous MOF-74-Co.