Themed collection Dalton Discussion 14: Advancing the chemistry of the f-elements

Welcome to this Dalton Transactions themed issue including papers from Dalton Discussion 14 – Advancing the chemistry of the f-elements.

Actinide single-molecule magnets compose a small yet complex consortium, presenting new design and characterization challenges for magnetochemists and physicists.

Uranium (as UO₂²⁺), technetium (as TcO₄⁻) and neptunium (as NpO₂⁺) are highly mobile radionuclides that can be reduced enzymatically by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble species. Riboflavin is secreted by this organism and can accelerate radionuclide bioreduction.

A series of 2,2′-bipyridyl uranium complexes shows that bipy is found as a radical anion or a neutral ligand such that uranium is in the +4 oxidation state.

The structure and photophysical properties of the nano-drum [Eu₈Cd₂₄L₁₂(OAc)₄₈] are described as well as imaging capabilities using commercial microscopy platforms.

Charge transfer from the ligand to valence hybrid (mainly d) metal orbitals nearly equally stabilizes cationic Eu^III and Am^III TODGA complexes.

DFT/MM-MD simulations highlight the structure and dynamics of mixed uranyl/nitrato/monoamides (L) complexes at an “oil”/water interface.

A series of tetravalent uranium terephthalates has been solvothermally synthesized in the solvent N,N-dimethylformamide (DMF) at temperature 100–150 °C with different water amounts.

The complexation of U(VI) at the proteinaceous surface layer (S-layer) of the archaeal strain Sulfolobus acidocaldarius was investigated at the molecular scale using TRLFS and EXAFS spectroscopy.

Multimetallic cooperativity plays an important role in U(III) mediated CS₂ reduction: the reductive dimerization of CS₂ occurs preferentially at a heterodimetallic U, K complex while the reductive disproportionation pathway is favoured by the “ate” complex [K(18c6)][U(OSi(O^tBu)₃)₄].

New predictions of structural, electronic and mechanical properties of layered uranium oxides using DFT + U calculations.

An unprecedented molecular [ErN₉] chromophore emits simultaneous dual green (542 nm) and near-infrared (1540 nm) light upon indirect excitation.

A summary of innovative techniques using synchrotron radiation for actinide studies in nuclear research, including X-ray spectroscopy and imaging.

The synthesis of thorium complexes of the type Th(COT^TIPS2)Cp*X (X = Cl, I, CH₂Ph, H) and their reactivity towards CO₂, including reductive coupling to form an oxalate complex, are reported.

Hydroporphyrin-linked lanthanide complexes with variations in tetrapyrrole structure, linker length and mode of attachment are reported.

Structural characterization of U(VI) : (Al(III), Fe(III)) : citrate complexes provides insight into the formation of polynuclear clusters present in environmentally-relevant aqueous solutions.

Isomerisation of buta-1,2-diene to but-2-yne by (Me₅C₅)₂Yb is a thermodynamically favourable reaction, with the Δ_rG° estimated from experimental data at 298 K to be −3.0 kcal mol⁻¹.

The 20 kHz sonication of aqueous nitric solutions generates active species which can further react with Pu(IV) and Pu(III) ions.

Excellent correlation is found between standard QTAIM metrics and An–N bond lengths, and with N–N bond lengths and vibrational frequencies, but much poorer correlations exist with An–N and An–O interaction energies. Superior correlations are found between interaction energies and the change in the QTAIM charge on compound formation.

We report M(IV) M = Ti, Zr, Hf, Ce, and Th, complexes of a selenium bis(phenolate) ligand, 2,2′-selenobis(4,6-di-tert-butylphenol), (H₂^ArOSeO).