Complexation of actinide cations by polyoxometalates results in assemblies with exciting electronic properties and highly attractive potential as models for hetereogeneous systems based on actinides supported by metal oxide surfaces.

Ten newly synthesized non-symmetric benzo[b]-fused BODIPYs are compared with an extended series of nine related families (23 compounds) to gain insights into their structure–property relationship. The insertion of a fused indole moiety into the dipyrromethene core and various substituents on the proximal aryl including fused aromatic groups, lead to pronounced changes in the properties of compounds 1–10. By taking advantage of this versatile synthetic platform that allows facile substituent modifications and extension of the π-conjugated system, significant bathochromic shifts in the absorption (λ_max = 511–597 nm) and emission (601–757 nm) bands are achieved. Although the oxidation potentials of the compounds vary considerably throughout the series (+1.28–+1.65 V) due to the significant contribution of the aryl function to the HOMO, the reduction remains much more consistent (−0.61 to −0.79 V) as the LUMO resides primarily on the dipyrromethene core with little aryl contribution as calculated by DFT. For example, installation of a dimethylamine substituent in the para position of the aryl group leads to drastic modification of the optoelectronic properties of the absorption (597 nm) and emission (757 nm) maxima. The full electrochemical, photophysical and computational analyses of the compounds along with the structural characterization of compounds 1, 5, 8, and 9 are used to rationalize the potential of this powerful platform.

We provide a systematic overview of the mechanochemical reactions of inorganic solids, notably simple binary compounds, such as oxides, nitrides, carbides, sulphides, phosphides, hydrides, borides, borane derivatives, and related systems. Whereas the solid state has been traditionally considered to be of little synthetic value by the broader community of synthetic chemists, the solid-state community, and in particular researchers focusing on the reactions of inorganic materials, have thrived in building a rich and dynamic research field based on mechanically-driven transformations of inorganic substances typically seen as inert and high-melting. This review provides an insight into the chemical richness of such mechanochemical reactions and, at the same time, offers their tentative categorisation based on transformation type, resulting in seven distinct groupings: (i) the formation of adducts, (ii) the reactions of dehydration; (iii) oxidation–reduction (redox) reactions; (iv) metathesis (or exchange) reactions; (v) doping and structural rearrangements, including reactions involving the reaction vessel (the milling jar); (vi) acid–base reactions, and (vii) other, mixed type reactions. At the same time, we offer a parallel description of inorganic mechanochemical reactions depending on the reaction conditions, as those that: (i) take place under mild conditions (e.g., manual grinding using a mortar and a pestle); (ii) proceed gradually under mechanical milling; (iii) are self-sustained and initiated by mechanical milling, i.e., mechanically induced self-propagating reactions (MSRs); and (iv) proceed only via harsh grinding and are a result of chemical reactivity under strongly non-equilibrium conditions. By elaborating on typical examples and general principles in the mechanochemistry of hard and high-melting substances, this review provides a suitable complement to the existing literature, focusing on the properties and mechanochemical reactions of inorganic solids, such as nanomaterials and catalysts.

A new class of cationic iridium( iii ) complexes of the form [(C ^∧ N) ₂ Ir(N ^∧ N)][PF ₆ ] is reported, where C ^∧ N = cyclometallating 2-phenylpyridinato, ppy, or 2-(2,4-difluorophenyl)-5′-methylpyridinato, dFMeppy, and N ^∧ N = guanidyl-pyridine, gpy, or -pyrazine, gpz, as the ancillary ligand.