Rare earth benzene tetraanion-bridged amidinate complexes.

The benzene tetraanion-bridged rare earth inverse arene amidinate complexes [{Ln(κ:η-Piso)}(μ-η:η-CH)] (2-Ln, Ln = Gd, Tb, Dy, Y; Piso = {(NDipp)C Bu}, Dipp = CH Pr-2,6) were prepared by the reduction of parent Ln(iii) bis-amidinate halide precursors [Ln(Piso)X] (Ln = Tb, Dy; X = Cl, I) or [Ln(Piso)I] (Ln = Gd, Y) with 3 eq. KC in benzene, or by the reaction of the homoleptic Ln(ii) complexes [Ln(Piso)] (Ln = Tb, Dy) with 2 eq. KC in benzene.

Passivation, phase, and morphology control of CdS nanocrystals probed using fluorinated aromatic amines and solid-state NMR spectroscopy.

Nanocrystals are widely explored for a range of medical, imaging, sensing, and energy conversion applications. CdS nanocrystals have been reported as excellent photocatalysts, with thin film CdS also highly important in photovoltaic devices. To optimise properties of nanocrystals, control over phase, facet, and morphology are vital.

A fluorobenzene-bound dysprosium half-sandwich dication single-molecule magnet.

Dysprosium single-molecule magnets (SMMs) with two mutually -anionic ligands have shown large crystal field (CF) splitting, giving record effective energy barriers to magnetic reversal ( ) and hysteresis temperatures ( ). However, these complexes tend to be bent, imposing a transverse field that reduces the purity of the projections of the CF states and promotes magnetic relaxation. A complex with only one charge-dense anionic ligand could have more pure CF states, and thus high and .

Probing decoherence in molecular 4f qubits.

We probe herein the fundamental factors that induce decoherence in ensembles of molecular magnetic materials. This is done by pulse Electron Paramagnetic Resonance measurements at X-band (∼9.6 GHz) on single crystals of Gd@Y(trensal) at 0.

Selective hydrogenolysis of the Csp-O bond in the furan ring using hydride-proton pairs derived from hydrogen spillover.

Selective hydrogenolysis of biomass-derived furanic compounds is a promising approach for synthesizing aliphatic polyols by opening the furan ring. However, there remains a significant need for highly efficient catalysts that selectively target the Csp-O bond in the furan ring, as well as for a deeper understanding of the fundamental atomistic mechanisms behind these reactions. In this study, we present the use of Pt-Fe bimetallic catalysts supported on layered double hydroxides [PtFe /LDH] for the hydrogenolysis of furanic compounds into aliphatic alcohols, achieving over 90% selectivity toward diols and triols.

Electron beam and thermal stabilities of MFM-300(M) metal-organic frameworks.

This work reports the thermal and electron beam stabilities of a series of isostructural metal-organic frameworks (MOFs) of type MFM-300(M) (M = Al, Ga, In, Cr). MFM-300(Cr) was most stable under the electron beam, having an unusually high critical electron fluence of 1111 e Å while the Group 13 element MOFs were found to be less stable. Within Group 13, MFM-300(Al) had the highest critical electron fluence of 330 e Å, compared to 189 e Å and 147 e Å for the Ga and In MOFs, respectively.

δ-Bonding modulates the electronic structure of formally divalent nd rare earth arene complexes.

Landmark advances in rare earth (RE) chemistry have shown that divalent complexes can be isolated with non-Aufbau 4f {5d/6s} electron configurations, facilitating remarkable bonding motifs and magnetic properties. We report a series of divalent bis-tethered arene complexes, [RE(NHAr )] (2RE; RE = Sc, Y, La, Sm, Eu, Tm, Yb; NHAr = {N(H)CH-2,6-(CH-2,4,6-Pr)}). Fluid solution EPR spectroscopy gives < 2.

Stable and accurate atomistic simulations of flexible molecules using conformationally generalisable machine learned potentials.

Computational simulation methods based on machine learned potentials (MLPs) promise to revolutionise shape prediction of flexible molecules in solution, but their widespread adoption has been limited by the way in which training data is generated. Here, we present an approach which allows the key conformational degrees of freedom to be properly represented in reference molecular datasets. MLPs trained on these datasets using a global descriptor scheme are generalisable in conformational space, providing quantum chemical accuracy for all conformers.

Relativistic Quantum Chemical Investigation of Actinide Covalency Measured by Electron Paramagnetic Resonance Spectroscopy.

We investigate actinide covalency effects in two [AnCp] (An = Th, U) complexes recently studied with pulsed electron paramagnetic resonance spectroscopy, using the Hyperion package to obtain relativistic hyperfine coupling constants from relativistic multiconfigurational wave functions. H and C HYSCORE simulations using the computed parameters show excellent agreement with the experimental data, highlighting the accuracy of modern relativistic ab initio methods. The extent of covalency indicated from the calculations on [ThCp] is in agreement with the original report based on traditional spectral fitting methods, while the covalency in [UCp] is found to be previously overestimated.

Correction: f-Element heavy pnictogen chemistry.

[This corrects the article DOI: 10.1039/D3SC05056D.].

Metal-carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy.

We examine lanthanide (Ln)-ligand bonding in a family of early Ln complexes [Ln(Cp)] (1-Ln, Ln = La, Ce, Nd, Sm; Cp = CHBu-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin and relaxation times of 12 and 0.2 μs (1-Nd), 89 and 1 μs (1-Ce) and 150 and 1.

Synthesis and photoinduced behavior of DPP-anchored nitronyl nitroxides: a multifaceted approach.

Understanding and controlling spin dynamics in organic dyes is of significant scientific and technological interest. The investigation of 2,5-dihydropyrrolo[4,3-]pyrrolo-1,4-dione derivatives (DPPs), one of the most widely used dyes in many fields, has so far been limited to closed-shell molecules. We present a comprehensive joint experimental and computational study of DPP derivatives covalently linked to two nitronyl nitroxide radicals (DPP-NN).

What is the nature of the uranium(iii)-arene bond?

Complexes of the form [U(η-arene)(BH)] where arene = CH; CHMe; CH-1,3,5-R (R = Et, iPr, Bu, Ph); CMe; and triphenylene (CH) were investigated towards an understanding of the nature of the uranium-arene interaction. Density functional theory (DFT) shows the interaction energy reflects the interplay between higher energy electron rich π-systems which drive electrostatic contributions, and lower energy electron poor π-systems which give rise to larger orbital contributions. The interaction is weak in all cases, which is consistent with the picture that emerges from a topological analysis of the electron density where metrics indicative of covalency show limited dependence on the nature of the ligand - the interaction is predominantly electrostatic in nature.

Navigating the challenges of lipid nanoparticle formulation: the role of unpegylated lipid surfactants in enhancing drug loading and stability.

Lipid nanoparticles have proved an attractive approach for drug delivery; however, the challenges of optimising formulation stability and increasing drug loading have limited progression. In this work, we investigate the role of unpegylated lipid surfactants (helper lipids) in nanoparticle formation and the effect of blending helper lipids with pegylated lipid surfactants on the formation and stability of lipid-based nanoparticles by nanoprecipitation. Furthermore, blends of unpegylated/pegylated lipid surfactants were examined for ability to accommodate higher drug loading formulations by means of a higher weight percentage (wt%) of drug relative to total mass of formulation components ( drug, surfactants and lipids).

C nuclear magnetic resonance chemical shift analysis confirms Ce[double bond, length as m-dash]C double bonding in cerium(iv)-diphosphonioalkylidene complexes.

Diphosphonioalkylidene dianions have emerged as highly effective ligands for lanthanide and actinide ions, and the resulting formal metal-carbon double bonds have challenged and developed conventional thinking about f-element bond multiplicity and covalency. However, f-element-diphosphonioalkylidene complexes can be represented by several resonance forms that render their metal-carbon double bond status unclear. Here, we report an experimentally-validated C Nuclear Magnetic Resonance computational assessment of two cerium(iv)-diphosphonioalkylidene complexes, [Ce(BIPM)(ODipp)] (1, BIPM = {C(PPhNSiMe)}; Dipp = 2,6-diisopropylphenyl) and [Ce(BIPM)] (2).

f-Element heavy pnictogen chemistry.

The coordination and organometallic chemistry of the f-elements, that is group 3, lanthanide, and actinide ions, supported by nitrogen ligands, amides, imides, and nitrides, has become well developed over many decades. In contrast, the corresponding f-element chemisty with the heavier pnictogen analogues phosphorus, arsenic, antimony, and bismuth has remained significantly underdeveloped, due largely to a lack of suitable synthetic methodologies and also the inherent hard(f-element)-soft(heavier pnictogen) acid-base mismatch, but has begun to flourish in recent years. Here, we review complexes containing chemical bonds between the f-elements and heavy pnictogens from phosphorus to bismuth that spans five decades of endeavour.

A ring of rotaxanes: studies of a large paramagnetic assembly in solution.

Here we report the synthesis and structural characterization of four [7]rotaxanes formed by coordinating hybrid inorganic-organic [2]rotaxanes to a central {Ni} core. X-ray single crystal diffraction demonstrate that [7]rotaxanes are formed, with a range of conformations in the crystal. Small angle X-ray scattering supported by molecular dynamic simulations demonstrates that the large molecules are stable in solution and also show that the conformers present in solution are not those found in the crystal.

In silico prediction and experimental validation to reveal the protective mechanism of Puerarin against excessive extracellular matrix accumulation through inhibiting ferroptosis in diabetic nephropathy.

Ethnopharmacological Relevance: Puerarin (PUR) isolated from the root of Pueraria lobata (Willd.) Ohwi is considered as one of the main medicines to alleviate asthenic splenonephro-yang of diabetic nephropathy (DN). Whereas, the exact mechanism of Puerarin on diabetic nephropathy is still unclear.

Development of an Fe sensing system based on the inner filter effect between upconverting nanoparticles and ferrozine.

The ferrozine (FZ) assay is a vital oxidation state-specific colorimetric assay for the quantification of Fe ions in environmental samples due to its sharp increase in absorbance at 562 nm upon addition of Fe. However, it has yet to be applied to corresponding fluoresence assays which typically offer higher sensitivites and lower detection limits. In this article we present for the first time its pairing with upconverting luminescent nanomaterials to enable detection of Fe the inner filter effect using a low-power continuous wave diode laser (45 mW).

Origin of the superior oxygen reduction activity of zirconium nitride in alkaline media.

The anion exchange membrane fuel cell (AEMFC), which can operate in alkaline media, paves a promising avenue for the broad application of earth-abundant element based catalysts. Recent pioneering studies found that zirconium nitride (ZrN) with low upfront capital cost can exhibit high activity, even surpassing that of Pt in alkaline oxygen reduction reaction (ORR). However, the origin of its superior ORR activity was not well understood.

CrystalClear: an open, modular protocol for predicting molecular crystal growth from solution.

We present a new protocol for the prediction of free energies that determine the growth of sites in molecular crystals for subsequent use in Monte Carlo simulations using tools such as CrystalGrower [Hill , , 2021, , 1126-1146]. Key features of the proposed approach are that it requires minimal input, namely the crystal structure and solvent only, and provides automated, rapid generation of the interaction energies. The constituent components of this protocol, namely interactions between molecules (growth units) in the crystal, solvation contributions and treatment of long-range interactions are described in detail.

Highly selective CO photoreduction to CO on MOF-derived TiO.

Metal-Organic Framework (MOF)-derived TiO, synthesised through the calcination of MIL-125-NH, is investigated for its potential as a CO photoreduction catalyst. The effect of the reaction parameters: irradiance, temperature and partial pressure of water was investigated. Using a two-level design of experiments, we were able to evaluate the influence of each parameter and their potential interactions on the reaction products, specifically the production of CO and CH.

Electronic structure comparisons of isostructural early d- and f-block metal(iii) bis(cyclopentadienyl) silanide complexes.

We report the synthesis of the U(iii) bis(cyclopentadienyl) hypersilanide complex [U(Cp''){Si(SiMe)}] (Cp'' = {CH(SiMe)-1,3}), together with isostructural lanthanide and group 4 M(iii) homologues, in order to meaningfully compare metal-silicon bonding between early d- and f-block metals. All complexes were characterised by a combination of NMR, EPR, UV-vis-NIR and ATR-IR spectroscopies, single crystal X-ray diffraction, SQUID magnetometry, elemental analysis and calculations. We find that for the [M(Cp''){Si(SiMe)}] (M = Ti, Zr, La, Ce, Nd, U) series the unique anisotropy axis is conserved tangential to ; this is governed by the hypersilanide ligand for the d-block complexes to give easy plane anisotropy, whereas the easy axis is fixed by the two Cp'' ligands in f-block congeners.

Activity and stability studies of H-transfer reduction reactions of aldehydes and ketones over aluminium isopropoxide heterogenised catalysts.

Aluminium isopropoxide Al(OPr) immobilised on various mesoporous supports (SiO, TiO and γ-AlO) was tested for H-transfer reductions of various aldehydes and ketones in the presence of 2-propanol as a sacrificial agent. The heterogenised catalysts were characterised by N physisorption, XRD, SEM-EDX, FTIR and ICP-OES. The characterisation results show a successful grafting of the homogeneous aluminium isopropoxide catalyst, covalently bound to the solid surface, with high dispersion over the mesoporous supports.

Facile ZnO-based nanomaterial and its fabrication as a supercapacitor electrode: synthesis, characterization and electrochemical studies.

In recent times, tremendous efforts have been devoted to the efficient and cost-effective advancements of electrochemically active metal oxide nanomaterials. Here, we have synthesized a facile nanomaterial of ZnO@PdO/Pd by employing extracted fuel from leaves following a hydrothermal route. The phyto-fueled ZnO@PdO/Pd nanomaterial was fabricated into a supercapacitor electrode and was scrutinized by galvanostatic charge-discharge, electrochemical impedance spectroscopy and cyclic voltammetry to evaluate its energy storage potential, and transport of electrons and conductivity.