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.

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.

Stimuli responsive materials (SRMs) respond to environmental changes through chemical and/or structural transformations that can be triggered by interactions at solid-gas or solid-liquid 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.

[Co(bipy)(bptz)(NCS)2]n, a new mixed-linker sql coordination network, exhibits high xylene adsorption capacity and high xylene selectivity over ethylbenzene (>5).

A very exceptional effect of pressure-induced dissolution has been revealed for an edible metal-organic framework, g-CD-MOF-1, formed using g-cyclodextrin and KOH base. In addition, a new polymorph of g-CD-MOF-1 has been obtained. The trigonal structure is a symmetry sub-group modification of the cubic form. The pressure-induced dissolution of g-CD-MOF-1 and its polymorphism are shown to be closely related and regulated by adsorption in the pores, as well as the guest framework interactions.

Solid-state synthesis (S 3 ) is an attractive approach to organic synthesis as in principle it offers minimal solvent waste and high yield. However, many functional groups are ill-suited for S 3 reactions, which tend to only proceed when substrates are aligned in the solid-state according to the topochemical principle. The aim of this work is to use high yield, low-waste synthetic methods to develop a library of novel Schiff bases that can be utilized as linker ligands to prepare coordination networks. Herein, we report that eight pyridyl-and/or imidazolyl-substituted Schiff bases, 1−8, five of which are new chemical entities, can be prepared via reaction of an amine and an aldehyde without the use of solvent. All eight compounds were prepared via solvent-drop grinding (SDG) in multigram scale in >95% yield and each was characterized by FTIR, 1 H and 13 C NMR spectroscopies and single crystal X-ray diffraction. One of the aldehydes used is a liquid under ambient conditions so its reactions to form 1−4 are not classified as S 3 reactions whereas the other aldehydes are solids and 5−8 are therefore S 3 reactions. The SDG solvents were selected in accordance with guidelines used by industry. 1−4 were also prepared quantitatively via addition of the liquid aldehyde (4-pyridinecarboxaldehyde) to a solution of the corresponding amine. That 1− 8 contain functional groups suitable for coordinating with metal cations will enable 1−8 to serve as linker ligands in coordination networks as exemplified by 5, which forms a parallel interpenetrated coordination network with square lattice, sql, topology.

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.

Benzocaine (BZC), an efficient and highly permeable anaesthetic and an active pharmaceutical ingredient of many commercially available drugs, was studied under high pressure up to 0.78 GPa. As a result, new BZC polymorph (IV) was discovered. The crystallization of polymorph (IV) can be initiated by heating crystals of polymorph (I) at a pressure of at least 0.45 GPa or by their compression to 0.60 GPa. However, no phase transition from polymorph (I) to (IV) was observed. Although polymorph (IV) exhibits the same main aggregation motif as in previously reported BZC polymorphs (I)–(III), i.e. a hydrogen-bonded ribbon, its molecular packing and hydrogen-bonding pattern differ considerably. The N—H...N hydrogen bonds joining parallel BZC ribbons in crystals at ambient pressure are eliminated in polymorph (IV), and BZC ribbons become positioned at an angle of about 80°. Unfortunately, crystals of polymorph (IV) were not preserved on pressure release, and depending on the decompression protocol they transformed into polymorph (II) or (I).