The reaction of Fe(NO3)3⋅9 H2O with KOH under hydroflux conditions at about 200 °C produces red crystals of K2−xFe4O7−x(OH)x in a quantitative yield. In the crystal structure, edge‐sharing [FeO6] octahedra form ∞2[
Fe2O6] honeycomb nets. Pillars consisting of pairs of vertex‐sharing [FeO4] tetrahedra link the honeycomb layers and form columnar halls in which the potassium ions are located. The trigonal (P
true3‾
1m) and the hexagonal (P63/mcm) polytypes of K2−xFe4O7−x(OH)x show oriented intergrowth. The sub‐stoichiometric potassium content (x≈0.3) is compensated by hydroxide ions. K2−xFe4O7−x(OH)x is an antiferromagnet above 2 K and its magnetic structure was determined by neutron powder diffraction. Under ambient conditions, K2−xFe4O7−x(OH)x hydrolyzes and K2CO3 ⋅ H2O forms gradually on the surface of the K2−xFe4O7−x(OH)x crystals. Upon annealing at air at about 500 °C, the potassium atoms in the columnar halls start to order into a superstructure. The thermal decomposition of K2−xFe4O7−x(OH)x proceeds via a topotactic transformation into K1+x′Fe11O17, adopting the rhombohedral β’’ or the hexagonal β‐aluminate‐type structure, before γ‐Fe2O3 is formed above 950 °C, which then converts into thermodynamically stable α‐Fe2O3.
The reaction of chalcogen dioxides ChO2 (Ch=Se, Te) with As2O3 in a 30 molar KOH hydroflux at about 200 °C yielded crystals of potassium trichalcogenides K2Ch3 with dimensions up to 2 cm. Arsenic trioxide acts as electron donor and is oxidized to arsenate(V). The new heterochalcogenide anion (TeSe2)2− formed when starting from SeO2 and TeO2 simultaneously. The compound K2TeSe2 crystallizes isostructural to K2S3 and K2Se3. The unexpected redox reaction as well as the precipitation of hygroscopic compounds from an aqueous solution are attributed to a strongly reduced activity of water. The reactions were studied by Raman and UV/Vis spectroscopy. Depending on the concentration of As2O3, colorless monochalcogenide Ch2− or orange Se22− and purple Te22− anions are dominating the solutions.
Supramolecular microgel capsules based on polyethylene glycol (PEG) are a promising class of soft particulate scaffolds with tailored properties. An approach to fabricate such particles with exquisite control by droplet-based microfluidics is presented. Linear PEG precursor polymers that carry bipyridine moieties on both chain termini are gelled by complexation to iron(II) ions. To investigate the biocompatibility of the microgels, living mammalian cells are encapsulated within them. The microgel elasticity is controlled by using PEG precursors of different molecular weights at different concentrations and the influence of these parameters on the cell viabilities, which can be optimized to exceed 90% is studied. Reversion of the supramolecular polymer cross-linking allows the microcapsules to be degraded at mild conditions with no effect on the viability of the encapsulated and released cells.
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