A group of new polymolybdates was synthesized and tested in the catalytic oxidation of cycloalkanes. Investigated compounds exhibit broad structural diversity including polymolybdates with isolated anionic clusters (0-dim), polymeric anions (1-dim), Mo–O layers (2-dim) as well as hexagonal and orthorhombic molybdenum oxides (3-dim). All studied molybdenum complexes were found to be active in the reaction conditions yielding ketones and alcohols as main products. In the case of layered compounds (2-dim), dicarboxylic acid was detected in the mixture of reaction products. The structure of investigated molybdenum compounds was shown to have influence on yields and selectivities of the investigated reactions. Anionic layers separation (in 2-dim materials) as well as type and charge of organic cations present in the compounds are prime examples of structural factors influencing the oxidation reactions efficiencies. On the basis of obtained results and literature reports a mechanism for the oxidation of cycloalkanes by polymolybdates has been proposed. Graphical Abstract

We present an overview of very recent advances in the engineering of magnetic networks based on octacyanometalates. The selected magnetic networks of Cu^IIW^V, Ni^IIW^V and Mn^IILNb^IV (L – organic bridging linker) illustrate the possible strategies for tuning of the magnetic characteristics. The combination of magnetic ordering for 2D (two-dimensional) and 3D (three-dimensional) networks together with the solvent sensitivity of a cyano-bridged framework resulted in the development of a novel 3D {[Mn^II(imH)]₂[Nb^IV(CN)₈]} assembly with magnetic sponge character, characterized by T_c of 62 K, the highest ever observed for octacyanometalate-based networks.

Black AgSO₄, synthesized for the first time by a displacement reaction, differs considerably from anhydrous sulfates of its Group 11 congeners: it has a very small electronic band gap (ca. 0.2 eV) and an anomalously strong one-dimensional antiferromagnetic ordering ( J≈10 meV per Ag), which persists up to the onset of its thermal decomposition at about 120 °C. Ag gray, O red, S yellow.