Dinuclear Copper Sulfate-Based Square Lattice Topology Network with High Alkyne Selectivity.

Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g., SiF62-, TiF62-, and NbOF52-, although sulfate anions have recently been highlighted as inexpensive and earth-friendly alternatives. Herein, we report the use of a rare copper sulfate dimer molecular building block to generate two square lattice, sql, coordination networks which can be prepared via solvent layering or slurrying, CuSO4(1,4-bib)1.5, 1, (1,4-bib = 1,4-bisimidazole benzene) and CuSO4(1,4-bin)1.5, 2, (1,4-bin = 1,4-bisimidazole naphthalene). Variable-temperature SCXRD and PXRD experiments revealed that both sql networks underwent reversible structural transformations due to linker rotations or internetwork displacements. Gas sorption studies conducted upon the narrow-pore phase of CuSO4(1,4-bin)1.5, 2np, found a high calculated 1:99 selectivity for C2H2 over C2H4 (33.01) and CO2 (15.18), as well as strong breakthrough performance. Across-the-board, C3H4 selectivity vs C3H6, CO2, and C3H8 was also observed. Sulfate-based PCNs, although still understudied, appear increasingly likely to offer utility in gas and vapor separations.

Insight into the Gas-Induced Phase Transformations in a 2D Switching Coordination Network via Coincident Gas Sorption and In Situ PXRD.

Switching coordination networks (CNs) that reversibly transform between narrow or closed pore (cp) and large pore (lp) phases, though fewer than their rigid counterparts, offer opportunities for sorption-related applications. However, their structural transformations and switching mechanisms remain underexplored at the molecular level. In this study, we conducted a systematic investigation into a 2D switching CN, [Ni(bpy)2(NCS)2]n, sql-1-Ni-NCS (1 = bpy = 4,4'-bipyridine), using coincident gas sorption and in situ powder X-ray diffraction (PXRD) under low-temperature conditions. Gas adsorption measurements revealed that C2H4 (169 K) and C2H6 (185 K) exhibited single-step type F-IVs sorption isotherms with sorption uptakes of around 180-185 cm3 g-1, equivalent to four sorbate molecules per formula unit. Furthermore, parallel in situ PXRD experiments provided insight into sorbate-dependent phase switching during the sorption process. Specifically, CO2 sorption induced single-step phase switching (path I) solely between cp and lp phases consistent with the observed single-step type F-IVs sorption isotherm. By contrast, intermediate pore (ip) phases emerged during C2H4 and C2H6 desorption as well as C3H6 adsorption, although they remained undetectable in the sorption isotherms. To our knowledge, such a cp-lp-ip-cp transformation (path II) induced by C2H4/6 and accompanied by single-step type F-IVs sorption isotherms represents a novel type of phase transition mechanism in switching CNs. By virtue of Rietveld refinements and molecular simulations, we elucidated that the phase transformations are governed by cooperative local and global structural changes involving NCS- ligand reorientation, bpy ligand twist and rotation, cavity edge (Ni-bpy-Ni) deformation, and interlayer expansion and sliding.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (C3H8) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are C3H8 selective offer the potential to significantly reduce the energy footprint for capturing C3H8 from natural gas, where C3H8 is typically present as a minor component. Here we report the C3H8 recovery performance of a previously unreported lonsdaleite, lon, topology MOF, a chiral metal-organic material, [Ni(S-IEDC)(bipy)(SCN)]n, CMOM-7. CMOM-7 was prepared from three low-cost precursors: Ni(SCN)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy), and its structure was determined by single crystal X-ray crystallography. Pure gas adsorption isotherms revealed that CMOM-7 exhibited high C3H8 uptake (2.71 mmol g-1) at 0.05 bar, an indication of a higher affinity for C3H8 than both C2H6 and CH4. Dynamic column breakthrough experiments afforded high purity C3H8 capture from a gas mixture comprising C3H8/C2H6/CH4 (v/v/v = 5/10/85). Despite the dilute C3H8 stream, CMOM-7 registered a high dynamic uptake of C3H8 and a breakthrough time difference between C3H8 and C2H6 of 79.5 min g-1, superior to those of previous MOF physisorbents studied under the same flow rate. Analysis of crystallographic data and Grand Canonical Monte Carlo simulations provides insight into the two C3H8 binding sites in CMOM-7, both of which are driven by C-H···π and hydrogen bonding interactions.

Switching Adsorbent Layered Material that Enables Stepwise Capture of C8 Aromatics via Single-Crystal-to-Single-Crystal Transformations.

Separation of the C8 aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C8 selectivity. Herein, we report the mixed-linker square lattice (sql) coordination network [Zn2(sba)2(bis)]n·mDMF (sql-4,5-Zn, H2sba or 4 = 4,4'-sulfonyldibenzoic acid, bis or 5 = trans-4,4'-bis(1-imidazolyl)stilbene) and its C8 sorption properties. sql-4,5-Zn was found to exhibit high uptake capacity for liquid C8 aromatics (∼20.2 wt %), and to the best of our knowledge, it is the first sorbent to exhibit selectivity for PX, EB, and MX over OX for binary, ternary, and quaternary mixtures from gas chromatography. Single-crystal structures of narrow-pore, intermediate-pore, and large-pore phases provided insight into the phase transformations, which were enabled by flexibility of the linker ligands and changes in the square grid geometry and interlayer distances. This work adds to the library of two-dimensional coordination networks that exhibit high uptake, thanks to clay-like expansion, and strong selectivity, thanks to shape-selective binding sites, for C8 isomers.

Consecutive Single-Crystal-to-Single-Crystal Isomerization of Novel Octamolybdate Anions within a Microporous Hybrid Framework with Robust Water Sorption Properties.

The 3D hybrid framework [{Cu(cyclam)}3 (κ-Mo8 O27 )] ⋅ 14H2 O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-single-crystal transformations upon heating to afford two different anhydrous phases (2 a and 3 a). These transitions modify the framework dimensionality and enable the isomerization of κ-octamolybdate (κ-Mo8 ) anions into λ (2 a) and µ (3 a) forms through metal migration. Hydration of 3 a involves condensation of one water molecule to the cluster to afford the γ-Mo8 isomer in 4, which dehydrates back into 3 a through the 6 a intermediate. In contrast, 2 a reversibly hydrates to form 5, exhibiting the same Mo8 cluster as that of 1. It is remarkable that three of the Mo8 clusters (κ, λ and µ) are new and that up to three different microporous phases can be isolated from 1 (2 a, 3 a, and 6 a). Water vapor sorption analyses show high recyclability and the highest uptake values for POM-based systems. The isotherms display an abrupt step at low humidity level desirable for humidity control devices or water harvesting in drylands.

Water vapour and gas induced phase transformations in an 8-fold interpenetrated diamondoid metal-organic framework.

In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal-organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2], X-dia-2-Cd, HImibz or 2 = 4-((4-(1H-imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC-SC) transformations between four distinct phases: an as-synthesised (from N,N-dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-ß, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2-loaded phase X-dia-2-Cd-δ. While the space group remained constant in the four phases, the cell volumes and calculated void space ranged from 4988.7 Å3 and 47% (X-dia-2-Cd-α), respectively, to 3200.8 Å3 and 9.1% (X-dia-2-Cd-γ), respectively. X-dia-2-Cd-γ also exhibited a water vapour-induced structural transformation to the water-loaded X-dia-2-Cd-ß phase, resulting in an S-shaped sorption isotherm. The inflection point occurred at 18% RH with negligible hysteresis on the desorption profile. Water vapour temperature-humidity swing cycling (60% RH, 300 K to 0% RH, 333 K) indicated hydrolytic stability of X-dia-2-Cd and working capacity was retained after 128 cycles of sorbent regeneration. CO2 (at 195 K) was also observed to induce a structural transformation in X-dia-2-Cd-γ and in situ PXRD studies at 1 bar of CO2, 195 K revealed the formation of X-dia-2-Cd-δ, which exhibited 31% larger unit cell volume than X-dia-2-Cd-γ.

Highly Productive C3H4/C3H6 Trace Separation by a Packing Polymorph of a Layered Hybrid Ultramicroporous Material.

Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql-SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g-1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding "sweet spot" for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.

Structural Phase Transformations Induced by Guest Molecules in a Nickel-Based 2D Square Lattice Coordination Network.

Herein, we report the crystal structure and guest binding properties of a new two-dimensional (2D) square lattice (sql) topology coordination network, sql-(azpy)(pdia)-Ni, which is comprised of two linker ligands with diazene (azo) moieties, (E)-1,2-di(pyridin-4-yl)diazene(azpy) and (E)-5-(phenyldiazenyl)isophthallate(pdia). sql-(azpy)(pdia)-Ni underwent guest-induced switching between a closed (nonporous) ß phase and several open (porous) α phases, but unlike the clay-like layer expansion to distinct phases previously reported in switching sql networks, a continuum of phases was formed. In effect, sql-(azpy)(pdia)-Ni exhibited elastic-like properties induced by adaptive guest binding. Single-crystal X-ray diffraction (SCXRD) studies of the α phases revealed that the structural transformations were enabled by the pendant phenyldiazenyl moiety on the pdia2- ligand. This moiety functioned as a type of hinge to enable parallel slippage of layers and interlayer expansion for the following guests: N,N-dimethylformamide, water, dichloromethane, para-xylene, and ethylbenzene. The slippage angle (interplanar distances) ranged from 54.133° (4.442 Å) in the ß phase to 69.497° (5.492 Å) in the ethylbenzene-included phase. Insight into the accompanying phase transformations was also gained from variable temperature powder XRD studies. Dynamic water vapor sorption studies revealed a stepped isotherm with little hysteresis that was reversible for at least 100 cycles. The isotherm step occurred at ca. 50% relative humidity (RH), the optimal RH value for humidity control.

A Robust Molecular Porous Material for C2 H2 /CO2 Separation.

A molecular porous material, MPM-2, comprised of cationic [Ni2 (AlF6 )(pzH)8 (H2 O)2 ] and anionic [Ni2 Al2 F11 (pzH)8 (H2 O)2 ] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2 H2 over CO2 thanks to a high (ΔQst )AC [Qst (C2 H2 ) - Qst (CO2 )] of 13.7 kJ mol-1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2 H2 from a 1:1 C2 H2 /CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2 H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2 H2 molecules and F atoms of AlF6 3- are found to enable high selectivity toward C2 H2 , as determined by density functional theory simulations.

Adsorbate-dependent phase switching in the square lattice topology coordination network [Ni(4,4'-bipyridine)2(NCS)2]n.

Switching coordination networks (CNs) featuring stepped sorption isotherms that are accompanied by phase changes offer promise for gas storage and separation applications. However, their responsiveness to different adsorbates remains largely understudied. Herein, we report the variable switching behaviour of a previously known square lattice (sql) topology CN, [Ni(4,4'-bipyridine)2(NCS)2] (sql-1-Ni-NCS), with respect to nine gaseous adsorbates.

Acetylene storage performance of [Ni(4,4'-bipyridine)2(NCS)2]n, a switching square lattice coordination network.

We report that the previously reported square lattice coordination network [Ni(4,4'-bipyridine)2(NCS)2]n, sql-1-Ni-NCS, undergoes acetylene induced switching between closed (nonporous) and open (porous) phases. The resulting stepped sorption isotherms exhibit temperature controlled steps, consistent high uptake and benchmark working capacity (185 cm-3 g-1 or 189 cm-3, 1-3.2 bar, 288 K) for acetylene storage.

Toward an Understanding of the Propensity for Crystalline Hydrate Formation by Molecular Compounds. Part 2.

The propensity of molecular organic compounds to form stoichiometric or nonstoichiometric crystalline hydrates remains a challenging aspect of crystal engineering and is of practical relevance to fields such as pharmaceutical science. In this work, we address the propensity for hydrate formation of a library of eight compounds comprised of 5- and 6-membered N-heterocyclic aromatics classified into three subgroups: linear dipyridyls, substituted Schiff bases, and tripodal molecules. Each molecular compound studied possesses strong hydrogen bond acceptors and is devoid of strong hydrogen bond donors. Four methods were used to screen for hydrate propensity using the anhydrate forms of the molecular compounds in our library: water slurry under ambient conditions, exposure to humidity, aqueous solvent drop grinding (SDG), and dynamic water vapor sorption (DVS). In addition, crystallization from mixed solvents was studied. Water slurry, aqueous SDG, and exposure to humidity were found to be the most effective methods for hydrate screening. Our study also involved a structural analysis using the Cambridge Structural Database, electrostatic potential (ESP) maps, full interaction maps (FIMs), and crystal packing motifs. The hydrate propensity of each compound studied was compared to a compound of the same type known to form a hydrate through a previous study of ours. Out of the eight newly studied compounds (herein numbered 4-11), three Schiff bases were observed to form hydrates. Three crystal structures (two hydrates and one anhydrate) were determined. Compound 6 crystallized as an isolated site hydrate in the monoclinic space group P21/a, while 7 and 10 crystallized in the monoclinic space group P21/c as a channel tetrahydrate and an anhydrate, respectively. Whereas we did not find any direct correlation between the number of H-bond acceptors and either hydrate propensity or the stoichiometry of the resulting hydrates, analysis of FIMs suggested that hydrates tend to form when the corresponding anhydrate structure does not facilitate intermolecular interactions.

Scalable Room-Temperature Synthesis of Highly Robust Ethane-Selective Metal-Organic Frameworks for Efficient Ethylene Purification.

The development of new techniques and materials that can separate ethylene from ethane is highly relevant in modern applications. Although adsorption-based separation techniques using metal-organic frameworks (MOFs) have gained increasing attention, the relatively low stability (especially water resistance) and unscalable synthesis of MOFs severely limit their application in real industrial scenarios. Addressing these challenges, we rationally designed and synthesized two new C2H6-selective MOF adsorbents (NKMOF-8-Br and -Me) with ultrahigh chemical and thermal stability, including water resistance. Attributed to the nonpolar/hydrophobic pore environments and appropriate pore apertures, the MOFs can capture C2 hydrocarbon gases at ambient conditions even in high humidity. The single-crystal structures of gas@NKMOF-8 realized the direct visualization of adsorption sites of the gases. Both the single-crystal data and simulated data elucidate the mechanism of selective adsorption. Moreover, the NKMOF-8 possesses high C2H6 adsorption capacity and high selectivity, allowing for efficient C2H6/C2H4 separation, as verified by experimental breakthrough tests. Most importantly, NKMOF-8-Br and -Me can be scalably synthesized through stirring at room temperature in minutes, which confers them with great potential for industrial application. This work offers new adsorbents that can address major chemical industrial challenges and provides an in-depth understanding of the gas binding sites in a visual manner.

High Working Capacity Acetylene Storage at Ambient Temperature Enabled by a Switching Adsorbent Layered Material.

Unlike most gases, acetylene storage is a challenge because of its inherent pressure sensitivity. Herein, a square lattice (sql) coordination network [Cu(4,4'-bipyridine)2(BF4)2]n (sql-1-Cu-BF4) is investigated with respect to its C2H2 sorption behavior from 189 to 298 K. The C2H2 sorption studies revealed that sql-1-Cu-BF4 exhibits multistep isotherms that are temperature-dependent and consistent with the transformation from "closed" (nonporous) to four "open" (porous) phases induced by the C2H2 uptake. The Clausius-Clapeyron equation was used to calculate the performance of sql-1-Cu-BF4 for C2H2 storage at pressures >1 bar, which revealed that its volumetric working capacity at 288 K is slightly superior to acetone (174 vs 170 cm3 cm-3) over a safer pressure range (1-3.5 vs 1-15 bar). Molecular simulations provided insights into the observed switching phenomena, revealing that the layer expansion of sql-1-Cu-BF4 occurs via intercalation and inclusion of C2H2. These results indicate that switching adsorbent layered materials offer promise for utility in the context of C2H2 storage and delivery.

Highly Selective, High-Capacity Separation of o-Xylene from C8 Aromatics by a Switching Adsorbent Layered Material.

Purification of the C8 aromatics (xylenes and ethylbenzene) is particularly challenging because of their similar physical properties. It is also relevant because of their industrial utility. Physisorptive separation of C8 aromatics has long been suggested as an energy efficient solution but no physisorbent has yet combined high selectivity (>5) with high adsorption capacity (>50 wt %). Now a counterintuitive approach to the adsorptive separation of o-xylene from other C8 aromatics involves the study of a known nonporous layered material, [Co(bipy)2 (NCS)2 ]n (sql-1-Co-NCS), which can reversibly switch to C8 aromatics loaded phases with different switching pressures and kinetics, manifesting benchmark o-xylene selectivity (SOX/EB ≈60) and high saturation capacity (>80 wt %). Structural insight into the observed selectivity and capacity is gained by analysis of the crystal structures of C8 aromatics loaded phases.

Artificial neural network modelling of continuous wet granulation using a twin-screw extruder.

Computational modelling of twin-screw granulation was conducted by using an artificial neural network (ANN) approach. Various ANN configurations were considered with changing hidden layers, nodes and activation functions to determine the optimum model for the prediction of the process. The neural networks were trained using experimental data obtained for granulation of pure microcrystalline cellulose using a 12mm twin-screw extruder. The experimental data were obtained for various liquid binder (water) to solid ratios, screw speeds, material throughputs, and screw configurations. The granulate particle size distribution, represented by d-values (d10, d50, d90) were considered the response in the experiments and the ANN model. Linear and non-linear activation functions were taken into account in the simulations and more accurate results were obtained for non-linear function in terms of prediction. Moreover, 2 hidden layers with 2 nodes per layer and 3-Fold cross-validation method gave the most accurate simulation. The results revealed that the developed ANN model is capable of predicting granule size distribution in high-shear twin-screw granulation with a high accuracy in different conditions, and can be used for implementation of model predictive control in continuous pharmaceutical manufacturing.

Time resolved study of three ruthenium(II) complexes at micellar surfaces: A new long excited state lifetime probe for determining critical micelle concentration of surfactant nano-aggregates.

Three different ruthenium complexes have been synthesized and their luminescence properties in different solvent environments are reported. Luminescence intensities and excited state lifetimes of Ru-I, Ru-II and Ru-III vary with solvent viscosity. The excited state lifetime of Ru-I linearly increases in the viscosity range 1.76-12,100cP. Ru-II shows two linear increases: one in the low and another in the high viscosity ranges, whereas Ru-III illustrates a linear enhancement only in the low viscosity range. Interestingly, luminescence intensities and excited state lifetimes of Ru-I, Ru-II and Ru-III are found to be sensitive to nano-aggregation. However, the surfactant head charge and that of the ruthenium center as well as the hydrophobic tail of the ancillary ligand of the complexes have a great role in deciding the nature of the interaction and on the excited state properties at micellar surfaces. It is proposed that the long lifetime of Ru-III in water could be due to the coiling of the carbon chain of the ancillary ligand around the ruthenium center. At micelle surface, this coiling of the carbon chain is lost due to the parallel alignment with surfactants and thus quenching of the excited state lifetime is seen. Furthermore, it is shown that the variation of the excited state lifetime with respect to the change in surfactant concentration is a result of the formation of micelles from the surfactant monomer, thus, a novel technique for the determination of the critical micelle concentration (cmc) based on the long excited state lifetime of Ru-III located at the micellar nano-aggregates is reported.

Effect of curcumin on liposome: curcumin as a molecular probe for monitoring interaction of ionic liquids with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine liposome.

Recent increase and wider use of ionic liquids (ILs) for various applications has drawn attention to their toxicological consequence on human health. The present study explores effects of three different kinds of widely used ILs, such as 1-methyl-3-octylimidazolium chloride, 1-buytl-3-methyl imadazolium tetrafluoroborate and 1-benzyl-3-methyl imidazolium tetrafluoroborate, on liposome properties of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) by applying curcumin as molecular probe. Fluorescence intensity of curcumin is reported as a novel rotor which is sensitive to viscosity and thus the fluidity of the solvent. It follows a linear relationship of log fluorescence vs viscosity as proposed by Förster-Hoffmann equation. Curcumin binds strongly to liposome. At low concentration, the lipophilic drug curcumin does not appreciably influence the phase transition temperature of DPPC but as concentration reaches high levels significantly depresses the phase transition temperature. ILs diminish membrane fluidity. 1-methyl-3-octylimidazolium chloride disorders membrane properties by lowering the phase transition as is observed for higher concentration of curcumin, but 1-buytl-3-methyl imidazolium tetrafluoroborate and 1-benzyl-3-methyl imidazolium tetrafluoroborate do not modify phase transition temperature perceptibly; rather they broaden the phase transition at low molar concentration ratio. The three different kinds of ILs under study behave similarly at a high IL:DPPC ratio (1:2), while they behave differently at lower ratios (1:10-1:5).