Pressure-induced structural effects in the square lattice (sql) topology coordination network Sql-1-Co-NCS·4OX

A high-pressure study of a switching coordination network of square lattice topology (sql) loaded with o-xylene (OX), [Co(4,4′-bipyridine)2(NCS)2]n·4nC8H10 (sql-1-Co?NCS·4OX), was conducted up to approximately 1 GPa to investigate pressure-induced structural changes. Previous reports revealed that sql-1-Co-NCS exhibits multiple phases thanks to its ability to switch between closed (nonporous) and several open (porous) phases in the presence of various gases, vapors, and liquids. Networks of such properties are of topical interest because they can offer high working capacity and improved recyclability for gas adsorption. The monoclinic crystal structure of sql-1-Co-NCS·4OX at 100 K was previously reported to show an increase in interlayer separation of more than 100% compared to the corresponding closed phase, sql-1-Co-NCS, when exposed to gases or vapors under ambient conditions. Herein, a tetragonal crystal form of sql-1-Co-NCS·4OX (space group I4/mmm, Phase I) that exists at 0.1 MPa/303 K is reported. Exposure of Phase I to high pressure using penetrable pressure transmitting media (OX and 1:1 vol MeOH/EtOH) did not result in further separation of the sql networks. Rather, compression of the crystals and release of adsorbed OX molecules occurred. These pressure-induced changes are discussed in terms of structural voids, framework conformation, and molecular packing of the sql layers. Although Phase I retained tetragonal symmetry throughout the investigated pressure range, the interlayer voids occupied by OX molecules were significantly reduced between 0.3 and 0.5 GPa; further compression above 0.5 GPa induced structural disorder. Additionally, analysis of the electron count present in the pores of sql-1-Co-NCS confirmed the multistep evacuation of OX molecules from the crystal, and two intermediate phases, Ia and Ib, differing in the OX loading level, are postulated </p

Polymorphism in ionic cocrystals comprising lithium salts and L‑proline

The occurrence of polymorphism in ionic cocrystals formed by two lithium salts, lithium salicylate (LIS) and lithium 4-methoxybenzoate (L4M), and L-proline (PRO) has been investigated. The previously reported monoclinic form of the 1:1 cocrystal of LIS and PRO, LISPRO(α), and a new thermodynamically stable orthorhombic polymorph, LISPRO(β), were prepared and characterized. The two polymorphs form square grid, sql, topology coordination networks and differ mainly in the conformation of the salicylate ions and positioning of the sql nets. LISPRO(α) was observed to transform to LISPRO(β) under slurry conditions. The 1:1 ionic cocrystal of L4M and PRO (L4MPRO) was found to form three polymorphs. Apart from the previously reported orthorhombic crystal form, L4MPRO(α), two new monoclinic crystal forms, L4MPRO(β) and L4MPRO(γ), were obtained by modifying crystallization conditions. The new polymorphs were found to be metastable, undergoing transformations to L4MPRO(α) upon exposure to humidity. Experimental conditions that induce transformations between the polymorphs of LISPRO and L4MPRO are detailed, and the structural differences between the polymorphs are discussed in the broader context of polymorphism.</p

A dynamic and multi-responsive porous flexible metal–organic material

Stimuli responsive materials (SRMs) respond to environmental changes through chemical and/or structural transformations that can be triggered by interactions at solid-gas or solidliquid interfaces, light, pressure or temperature. SRMs span compositions as diverse as organic polymers and porous inorganic solids such as zeolites. Metal–organic materials (MOMs), sustained by metal nodes and organic linker ligands are of special interest as SRMs. SR-MOMs have thus far tended to exhibit only one type of transformation, e.g. breathing, in response to one stimulus, e.g. pressure change. We report [Zn2(4,4′-biphenyldicarboxylate) 2(4,4′-bis(4-pyridyl)biphenyl)]n, an SR-MOM, which exhibits six distinct phases and four types of structural transformation in response to various stimuli. The observed structural transformations, breathing, structural isomerism, shape memory effect, and change in the level of interpenetration, are previously known individually but have not yet been reported to exist collectively in the same compound. The multi-dynamic nature of this SR-MOM is mainly characterised by using in-situ techniques

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

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

Recyclable switching between nonporous and porous phases of a square lattice (sql) topology coordination network

A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits recyclable switching induced by CO2. The sorption isotherms are stepped with moderate hysteresis, temperature controlled and saturation uptake is fixed. Such switching, which has rarely been observed, offers the promise of exceptional working capacity for gas storage

Crystal engineering of a rectangular sql coordination network to enable xylenes selectivity over ethylbenzene†

Separation of the C8 aromatic isomers, p-xylene (PX), m-xylene (MX), o-xylene (OX) and ethylbenzene (EB), is relevant thanks to their widespread application as chemical feedstocks but challenging because of their similar boiling points and close molecular dimensions. Physisorptive separation could offer an energy-efficient solution to this challenge but sorbents which exhibit strong selectivity for one of the isomers remain a largely unmet challenge despite recent reports of OX or PX selective sorbents with high uptake capacity. For example, the square lattice, sql, topology coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits the rare combination of high OX selectivity and high uptake capacity. Herein we report that a crystal engineering approach enabled isolation of the mixed-linker sql coordination network [Co(bipy)(bptz) (NCS)2]n (sql-1,3-Co-NCS, bipy = 4,4′-bipyridine, bptz = 4,4′-bis(4-pyridyl)tetrazine) and study of its C8 vapour and liquid sorption properties. sql-1,3-Co-NCS was found to exhibit high adsorption capacity from liquid xylenes (∼37 wt%) and is to our knowledge the first sorbent to exhibit high selectivity for each of xylene isomer over EB (SOX/EB, SMX/EB, SPX/EB > 5). Insights into the performance of sql-1,3-Co-NCS are gained from structural studies which reveal stacking interactions between electron-deficient bptz linkers and the respective xylenes. sql-1,3-Co-NCS is the first N-donor mixed-linker sql coordination network studied for its gas/vapour sorption properties and represents a large and diverse class of understudied coordination networks

Impact of partial interpenetration in a hybrid ultramicroporous material on C2H2/C2H4 separation performance

Phases of a 2‐fold pcu Hybrid Ultramicroporous Material (HUM), SIFSIX‐14‐Cu‐i, exhibiting 99%, 93%, 89%, and 70% partial interpenetration have been obtained. 1:99 C2H2/C2H4 gas separation studies reveal that as the proportion of interpenetrated component decreases, so does the separation performance