The iron(ii)-based extended metal atom chains [Fe₄(tpda)₃X₂] (X = Cl, Br) have a weakly magnetic ground state but display SMM properties, which are detectable even in zero DC field when X = Br.

We designed [VO(bdhb)] (1') as a new electronic qubit containing an oxovanadium(IV) ion (S = 1/2) embraced by a single bis(β-diketonato) ligand [H₂bdhb = 1,3-bis(3,5-dioxo-1-hexyl)benzene]. The synthesis afforded three different crystal phases, all of which unexpectedly contain dimers with formula [(VO)₂(bdhb)₂] (1). A trigonal form (1h) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1m and minor amounts of a triclinic solventless phase (1a). In a static magnetic field, 1h and 1m have detectably slow magnetic relaxation at low temperatures through quantum tunneling and Raman mechanisms. Angle-resolved electron paramagnetic resonance (EPR) spectra on single crystals revealed signatures of low-dimensional magnetic behavior, which is solvatomorph-dependent, being the closest interdimer V···V separations (6.7-7.5 Å) much shorter than intramolecular V···V distances (11.9-12.1 Å). According to ¹H diffusion ordered spectroscopy (DOSY) and EPR experiments, the complex adopts the desired monomeric structure in organic solution and its geometry was inferred from density functional theory (DFT) calculations. Spin relaxation measurements in a frozen toluene-d₈/CD₂Cl₂ matrix yielded T_m values reaching 13 μs at 10 K, and coherent spin manipulations were demonstrated by Rabi nutation experiments at 70 K. The neutral quasi-macrocyclic structure, featuring nuclear spin-free donors and additional possibilities for chemical functionalization, makes 1' a new convenient spin-coherent building block in quantum technologies.

Lantern complexes containing VO²⁺ and Pt²⁺ ions show electron spin coherence with phase memory times above 10 μs at 10 K. EPR spectra prove the delocalization of the unpaired spin density to the heavy metal ion through both π and δ coupling channels.

Although water is considered detrimental for Li-ion battery technology, a 1% w/w amount of water in a melt of LiCl in ionic liquid 1-butyl-3-methylimidazolium chloride promotes the reduction of lithium into a LiAl intermetallic along with water oxidation to O₂ gas. The electrodeposition of an intermetallic layer of several micrometers thickness is demonstrated by combining complementary techniques, such as galvanostatics, X-ray diffraction, electron energy-loss spectroscopy, mass spectrometry, and ¹H nuclear magnetic resonance. The concentration of water in the ionic liquid is found to be a critical feature, as no Li is deposited when ionic liquid is dried. Our findings highlight an innovative and simple method to produce a LiAl intermetallic by using water and lithium chloride as chemical reagents.

A triple stranded [Ni( ii ) ₂ ] coordination helicate acts as the host of a Cl ⁻ or a Br ⁻ ion in the solid state and in solution, with a selective preference for the former, as shown by paramagnetic ¹ H NMR, mass spectrometry and DFT calculations.

Oligo-α-pyridylamides offer an appealing route to polyiron complexes with short Fe-Fe separations and large room-temperature magnetic moments. A derivative of tris(2-aminoethyl)amine (H₆tren) containing three oligo-α-pyridylamine branches and 13 nitrogen donors (H₆L) reacts with [Fe₂(Mes)₄] to yield an organic nanocage built up by two tripodal ligands with interdigitated branches (HMes = mesitylene). The nanocage has crystallographic D₃ symmetry but hosts a remarkably unsymmetric hexairon-oxo core, with a central Fe₅(μ₅-O) square pyramid, two oxygen donors bridging basal sites, and an additional Fe center residing in one of the two tren-like pockets. Bond valence sum (BVS) analysis, density functional theory (DFT) calculations, and electrochemical data were then used to establish the protonation state of oxygen atoms and the formal oxidation states of the metals. For this purpose, a specialized set of BVS parameters was devised for Fe²⁺-N^3- bonds with nitrogen donors of oligo-α-pyridylamides. This allowed us to formulate the compound as [Fe₆O₂(OH)(H₃L)L], with nominally four Fe^II ions and two Fe^III ions. Mössbauer spectra indicate that the compound contains two unique Fe^II sites, identified as a pair of closely spaced hydroxo-bridged metal ions in the central Fe₅(μ₅-O) pyramid, and a substantially valence-delocalized Fe^II₂Fe^III₂ unit. Broken-symmetry DFT calculations predict strong ferromagnetic coupling between the two iron(II) ions, leading to a local S = 4 state that persists to room temperature and explaining the large magnetic moment measured at 300 K. The compound behaves as a single-molecule magnet, with magnetization dynamics detectable in zero static field and dominated by an Orbach-like mechanism with activation parameters U_eff/k_B = 49(2) K and τ₀ = 4(2) × 10^-10 s.