Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure-property relationships, for example, with respect to band-gap tuning. Herein, we show that through a combination of one- and two-dimensional, multinuclear solid-state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X-ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a triazine ring. The two lithium ions within each cavity are positioned between two nitrogen atoms of neighbouring triazine rings. The thereby induced local dipole moments cause slight buckling of the framework and lateral displacements of the Cl ions at a coherence length below 2 nm. Nevertheless, the average structure conforms to space group P2 2 2 . In this way, we demonstrate that, in particular, the above-mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl.

Microporous organically pillared layered silicates (MOPS) are a class of microporous hybrid materials that, by varying pillar density, allows for optimization of guest recognition without the need to explore different framework topologies. MOPS are found to be capable of discriminating two very similar gases, carbon dioxide and acetylene, by selective gate-opening solely through quenching pillar dynamics. Contrary to conventional gate-opening in metal organic frameworks, the additional adsorption capacity is realized without macroscopic volume changes, thus avoiding mechanical stress on the framework. Of the two gases studied, only CO can accomplish freezing of pillar dynamics. Moreover, the shape of the slit-type micropores in MOPS can easily be fine-tuned by reducing the charge density of the silicate layers. This concomitantly reduces the Coulomb attraction of cationic interlayer space and anionic host layers. Surprisingly, we found that reducing the charge density then alters the gate-opening mechanism to a conventional structural gate-opening involving an increase in volume.

While polymorphism is a wide spread phenomenon, the number of reported polymorphic co-crystals is still very limited. Here we report the synthesis and structural characterisation of such a rare case of polymorphism with a co-crystal of benzoic acid (HBz) and sodium benzoate (NaBz). Flash evaporation yielded a new polymorph of this ionic co-crystal with a stoichiometry of 2 HBz?1 NaBz. The thermodynamic relationship between the known and the new polymorph was determined to be of enantiotropic nature. At room temperature, this new form B is metastable. While the known form A is composed of one dimensional tapes, form B is built from infinite rods. The coordination sphere of sodium, however, in both forms is octahedral and the packing around it is dense.

The glucocorticoide bethamethasone valerate was investigated for polymorphism. The commercially available modification (Form I) and one methanol solvate were characterized by single crystal structure analysis. DTA-TG and DSC investigations reveal that on solvent removal the methanol solvate decomposes into a new polymorphic modification (Form III), which, upon further heating, transforms into another modification (Form II) via melting and recrystallization. The crystal structures of forms II and III were determined by a combination of 13 C NMR spectroscopy and X-ray powder diffraction. In all modifications as well as in the methanol solvate differences in the conformation and the packing of the molecules are observed. Solvent mediated conversion experiments reveal that form I represents the thermodynamically stable form at room temperature. Thermomicroscopic, XRPD, and heating rate dependent DSC measurements on forms I−III do not show any interconversion of these forms via the solid. Further DSC measurements indicate both a higher melting point and heat of fusion for form I compared to form II and form III. Therefore, form I should also be the thermodynamically stable form over the whole temperature range and all forms seems to be monotropically related.

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