No abstract

Two polymorphic structures of Form II and Form III of agomelatine were determined by single and powder X-ray diffraction, respectively, in which the agomelatine molecules are linked through the intermolecular hydrogen bonding interactions to form a one-dimensional (1D) chain, and the 1D chains are further packed through interchain π 3 3 3 π and C-H 3 3 3 π interactions to generate the three-dimensional (3D) structures. Two agomelatine cocrystals with acetic acid (1) and ethylene glycol (2) were synthesized, and their structures were determined by single and powder X-ray diffraction, respectively, in which the acetic acid molecules in 1 alternately link the agomelatine molecules to form 1D right-handed and left-handed helical chains, while the alternately linking of agomelatine molecules by ethylene glycol molecules in 2 generates the homochiral right-handed helical chains. After the formation of cocrystals of 1 and 2, the melting points dramatically decrease, and the solubility is approximately twice as large as that of Form II.

The cruciform linker molecule here features two designer functions: the pyrazole donors for framework construction, and the vicinal alkynyl units for benzannulation to form nanographene units into the Ni 8 -pyrazolate scaffold. Unlike the full 12 connections of the Ni 8 (OH) 4 (H 2 O) 2 clusters in other Ni 8pyrazolate networks, significant linker deficiency was observed here, leaving about half of the Ni(II) sites capped by acetate ligands, which can be potentially removed to open the metal sites for reactivity. The crystalline Ni 8 -pyrazolate scaffold also retains the crystalline order even after thermal treatments (up to 300 °C) that served to partially graphitize the neighboring alkyne units. The resultant nanographene components enhance the electroactive properties of the porous hosts, achieving hydrogen evolution reaction (HER) activity that rivals that of topical nickel/palladium-enabled materials.

Organic radicals feature unpaired electrons, and these compounds may have applications in biomedical technology and as materials for solar energy conversion. However, unpaired electrons tend to pair up (to form chemical bonds), making radicals unstable and hampering their applications. Here we report an organic radical system that is stable even at 350 °C, surpassing the upper temperature limit (200 °C) observed for other organic radicals. The system reported herein features a sulfur-rich organic linker that facilitates the formation of the radical centers; on the solid-state level, the molecules are crystallized with Eu(III) ions to form a 3D framework featuring stacks of linker molecules. The stacking is, however, somewhat loose and allows the molecules to wiggle and transform into sulfur-stabilized radicals at higher temperatures. In addition, the resulting solid framework remains crystalline, and it is stable to water and air. Moreover, it is black and features strong broad absorption in the visible and near IR region, thereby enhancing both photothermal conversion and solar-driven water evaporation.

Metal-thiolate networks are topical electronic materials, but hard to crystallize: this one makes big single crystals, and boasts small band gap, stable radical organic linkers, and facile exfoliation into nanosheets.