The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.

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The formation of guest-mediated π-donor/acceptor stacks within electroactive metal–organic frameworks activates long-range charge mobilization, boosting the electrical conductivity of the doped materials.

In this proof of concept study, the ionic liquids, 2-hydroxyethylhydrazinium nitrate and 2-hydroxyethylhydrazinium dinitrate, ignited on contact with preheated Shell 405 (iridium supported on alumina) catalyst and energetically decomposed with no additional ignition source, suggesting a possible route to hydrazine replacements.

Four new uranyl phosphonate compounds have been synthesized via ionothermal flux in the ionic liquids 1butyl-3-methylimidazolium chloride ([Bmim][Cl]) and 1ethyl-3-methylimidazolium bromide ([Emim][Br]).) form one-dimensional chains, two-dimensional sheets, or three-dimensional frameworks. For comparison, analogous reactions were carried out hydrothermally, which lead to one new framework structure, [C 8 H 15 N 2 ] 2 [(UO 2 ) 5 (HO 3 P(CH 2 ) 3 PO 3 ) 4 ] (β-[Bmim][UC 3 DPO]), and one previously characterized tubular uranyl phosphonate. It was found that the structure is equally dictated by the choice of flux method, the choice of ligand, and the choice of ionic liquid.