Themed collection New molecules and materials from the f-block

An overview of the small molecule activation chemistry of polynuclear complexes of uranium supported by the tert-butoxysiloxide ligand.

Coordination complexes and supramolecules based on trivalent lanthanides for probing biological systems, in particular intracellular environments, are reviewed.

Electronic vs. steric effects of ligand ortho-substituents in (bis)phenolate yttrium-based complexes for preparation of a large scope of stereoregular poly(3-hydroxyalkanoate)s.

We present here the electrochemical oxidation of Am(III) to Am^VO₂⁺ and Am^VIO₂²⁺ in pH 1 nitric acid using a mesoporous tin-doped indium oxide electrode modified with a covalently attached dipyrazinylpyridine ligand.

A dithiopicolinamide analog selectively extracts Am(III) over Eu(III) under acidic conditions.

The synthesis of five new U(IV,V) and U(V,VI) silicates points toward moderate supercritical synthesis as a new route to the stabilization of mixed-valent uranium compounds.

Heterobimetallic An–Mo (An = U, Th) paddlewheel complexes featuring dative Mo → An bonds are reported.

Sandwich-like structures derived from organic polyanions and multi-centered cation assemblies.

Large crystals of Yb₁₄MgSb₁₁ prepared by Sn flux show the presence of Yb³⁺ making this compound a Zintl phase.

Pu L₃ HR-XANES fingerprints loss of inversion symmetry: rising pre-edge (d,e), shorter A–B distance (d,e), split Pu d-DOS (e).

Complexation of Pu(IV) with the actinide extractant CyMe₄-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was studied experimentally and by computational analysis.

Isomorphous lanthanides and actinides Prussian blue analogs showing distinct optical and vibrational properties are studied using nitrogen K edge and iron K edge.

Soluble molecular actinide(IV) fluorides can be prepared in high yield via redox or metathesis reactions of silver fluorides with actinide compounds containing ancillary iodide or fluorinated thiolate ligands.

Four novel Pu(IV) nitrato chloro complexes were crystallographically characterized and the Pu–ligand bond nature was delineated computationally.

A series of novel salan-ligated rare-earth metal amide complexes were prepared and employed as initiators for the ROP of rac-β-butyrolactone (rac-BBL).

Polyethyleneimine methylenecarboxylate (PEI-MC) is explored as a possible new class of macromolecular decorporation agents in case of plutonium contamination.

The synthesis, characterization, and electrochemical properties of a napthylsalophen and its uranyl (UO₂²⁺) complex are described.

The redox-active ligand as a route to heterobimetallic rare earth-transition metal compounds containing a semiquinone radical anion.

Cationic ytterbium hydrides [(Me₄TACD)₂Yb₂H_(2+n)]⁽²⁻ⁿ⁾⁺ (n = 0, 1) catalyzed the H₂/D₂ isotope exchange as well as hydrogenation and hydrosilylation of 1-hexene.

CASSCF and CASPT2 calculations are reported on EUF₃ (E = N, P, As, Sb, Bi), emphasising the influence of the size of the active space on the E–U bond.

Organoactinide-mediated chemoselective hydroboration of aldehydes and ketones. The catalytic regeneration of a Th–H bond from a Th–OR bond was achieved via hydroboration with HBpin.

Use of a new homoleptic U(III) tris-guanidinate system stabilizes the formation of the first U(V) hydrazido complex.

The syntheses, structural, and magnetic characterization of three new organometallic Ce complexes stabilized by PyCp₂²⁻ (PyCp₂²⁻ = [2,6-(CH₂C₅H₃)₂C₅H₃N]²⁻) are reported.

Interactions between H-donors and U(VI) and Np(V) oxo groups impact the thermal expansion properties of materials.

Neptunyl(VI) and plutonyl(VI) oxo-activation with reduction to tetravalent hydroxides was investigated in gas and condensed phases, and by density functional theory.

A spiral-type chiral Eu(III) coordination polymer showed strong luminescence, effective CD and CPL properties compared with a mono-nuclear chiral Eu(III) complex in the solid state.

In contrast with previous literature, this report notes einsteium's chemistry is a continuation of the earlier actinide series.

The synthesis and characterization of U(IV) and Np(IV) selenium bis(phenolate) complexes are reported.

The first example of molecular lanthanide tungstate clusters for photochemical and electrochemical hydrogen evolution catalysis is reported.

We developed a computationally-efficient protocol based on Density Functional Theory (DFT) and a continuum solvation model (CSM) to predict reaction free energies of complexation reactions of uranyl in liquid ammonia.

The migration of Me₃Si groups (“Wanderlust”) in rare-earth triple-decker sandwich complexes of the type Ln₂(COT′′)₃ (COT′′ = bis(trimethylsilyl)cyclooctatetraenyl) has been elucidated by a combined experimental and computational study.

Uranium-in-cryptand complexes can be readily synthesized by reacting UI₃ with 2.2.2-cryptand.

The dinuclear Sm^II complex [Sm₂L₄(dme)] (L = OSi(OtBu)₃) reacts slowly with toluene, resulting in the isolation of the triple decker arene-bridged Sm^II complex [{Sm₂L₃}₂(μ-η⁶:η⁶-C₇H₈)] in 44% yield. This reactivity provides the first example of an unambiguous arene reduction by an isolated Sm^II species.

A methoxy-substituted tripodal hydroxylamine ligand, H₃TriNOx^OMe, was synthesized and coordinated to rare earth cations for separation purposes.

The Gd^III complex of Ph-HP-DO3A shows the highest contribution to the relaxivity by the intramolecular proton exchange of the –OH group.

The poly-oxo clusters of neptunium, {Np₃₈}, fill the gap in the largest poly-oxo cluster series of tetravalent actinides.

Uranyl, ligand and solvent interactions lead to unique supramolecular assembly.

The valence band electronic structures of mixed uranium oxides (UO₂, U₄O₉, U₃O₇, U₃O₈, and β-UO₃) have been studied using the resonant inelastic X-ray scattering (RIXS) technique at the U M₅ edge and computational methods.

The inverse trans influence is quantified in uranyl and its analogues via analysis of quantum chemically-derived electron density distributions.

A set of self-assembled tri- and tetrapodal metal coordination cage structures (cage-1 and cage-2, respectively) constructed from the uranyl dication (UO₂²⁺) and a dibenzoic acid functionalised cis-calix[4]pyrrole (1) are described.

A series of lanthanide metallocenium cations [Ln(Cp^ttt)₂]⁺ (Ln = Y, Gd, Dy, Ho, Er, Tm, Yb, Lu; Cp^ttt = C₅H₂^tBu₃-1,2,4) were recently prepared, but curiously the Tb analogue was elusive. Here we access [Tb(Cp^ttt)₂]⁺via an alternative strategy, completing the heavy [Ln(Cp^ttt)₂]⁺ family.

[U(η⁵-C₅H₄SiMe₃)₃] reductively couples three C₃O₂ molecules to form a tetranuclear complex with a central cyclobutane-1,3-dione ring, via an intermediate bridging ketene complex.

Double protonolysis of [Ln(CH₂Ph)₂]_n (Ln = Eu and Yb) with 2,6-diisopropylaniline gives efficient access to [(thf)Ln(μ₃-NDipp)]₄ featuring a heterocubane structure.

The synthesis and characterization of a Pu(IV) salen complex reveals the stabilization of the +4 oxidation state with respect to that observed with Ce(IV).

Reported, for the very first time, are the synthesis and structures of two new compounds, discovered in well-studied binary phase diagrams.

The pentalene-ligated dysprosium complex [(η⁸-Pn^†)Dy(Cp*)] (1_Dy) (Pn^† = [1,4-(ⁱPr₃Si)₂C₈H₄]²⁻) and its magnetically dilute analogue are single-molecule magnets, with energy barriers of 245 cm⁻¹.

The synthesis of the first transuranium Metal–Organic Frameworks (TRU-MOFs) is reported here.

The synthesis and structures of a new class of homoleptic f-metal borohydride complexes (phosphinodiboranates) are described with U, Nd, and Er.

A new type of double uranium oxo cation [O–U–O–U–O]⁴⁺ is prepared by selective oxygen-atom abstraction from macrocyclic uranyl complexes using either boranes or silanes.