Themed collection Dalton Transactions HOT Articles

The preparation, heterostructure and application of hybrids containing layered double hydroxides as the main component are overviewed.

Metal dioxo chemistry and its diverse reactivity are presented with an emphasis on reaction mechanism.

The reactions of open-cage fullerenes with various metal complexes show a remarkable range of unanticipated behaviors, which are compared to the corresponding reactions with intact fullerenes.

Bacterial infections can lead to the development of large-scale outbreaks of diseases that pose a serious threat to human life and health.

Silver clusters composed exclusively of fused tetrahedra are analogous to simple saturated organic compounds. Copper clusters with central cuboctahedra and silver clusters with central icosahedra having interstitial metal atoms provide examples of metal superatoms.

The coordination of small molecules to low valent titanium complexes provides a powerful platform for the transformation of challenging substrates either through PCET reactions or bond-weakening induced by π-back donation of electrons from Ti.

This review focuses on the latest developments in luminescent lanthanide-based molecular materials as photosensitizers and their applications in photodynamic therapy.

This frontier presents Ln-based POMs in photoluminescence applications, focusing mainly on multi-color emission, fluorescent probes, fluorescent switch, drug activity, biomedical imaging, pH sensing and temperature sensing.

This article focuses on elucidating the fabrication and design of metal-organic framework derived metal-carbon nanostructures for oxygen evolution. It is categorized into three following topics: MOF selection, metal introduction and carbon structure.

Constructing a nickel based hierarchical structure is one of the important strategies for achieving high current density oxygen evolution reactions.

Metal-linker bonds serve as the “glue” that binds metal ions to multitopic organic ligands in the porous materials known as metal–organic frameworks (MOFs).

UiO-66 featuring hierarchical pores and abundant Lewis acid sites was successfully constructed through the linker selective retention strategy, and it exhibits excellent ODS performance for diphenylthiophene.

A series of proof-of-concept models of polyoxomolybdates were synthesized to study the mechanism governing the formation of the intermolecular charge transfer band.

A tetravalent praseodymium complex with field-induced slow magnetic relaxation is presented.

The triple para-substitution products B(C₆F₄P(SiMe₃)₂)₃ or [FP(C₆F₄P(SiMe₃)₂)₃][B(C₆F₅)₄] were prepared, while subsequent reactions gave (H₂O)B(C₆F₄PH₂)₃ and [(MeO)P(C₆F₄PH₂)₃][B(C₆F₅)₄].

The first cyclic (amino)(barrelene)carbene (CABC) Ru-complexes were synthesized. They demonstrated remarkable thermal stability at 110 °C and good performance in olefin metathesis.

Undercoordinated Cu nanowires are explored as an efficient catalyst for NO₂⁻ electroreduction to NH₃, arising from the created undercoordinated Cu sites to promote NO₂⁻-to-NH₃ energetics.

A hierarchical carbon foam-hosted Co₂P nanoparticles monolithic electrode (Co₂P@HCF) is developed and exhibits ultralow overpotentials and remarkable durability for ampere-level current density HER in both acidic and alkaline solutions.

A mechanism involving O–O bond formation via radical coupling of two subunits is proposed for a dinuclear iron complex. The mechanism can proceed at low overpotentials and agrees with the experimental kinetics.

Heterometallic Ag₆@Ti₁₂ and Ag₈@Ti₁₂ oxo clusters were prepared through a strategy of protecting polynuclear silver cores by a hollow Ti–O module in the presence of alkyne ligands, showing distinctive structures and optical limiting effects.

The fac–mer isomerisation in [MX₃(CO)₃]²⁻ (M = Re, ⁹⁹Tc) is induced by a PNP pincer-type ligand in the presence of a halide scavenger. The adaptation to the aqueous and saline chemistry of ^99mTc yields mer-[^99mTc(PNP)(CO)₃]⁺.

The generality of photo-induced generation of radicals with long T₁ and T₂ values in a series of acene-based metal–organic frameworks has been demonstrated.

An in-depth mechanistic probe of the Cu-catalysed electrophilic carboamination of terminal alkynes with benzyne and an hydroxylamine ester provided a computationally verified mechanistic view, thus enabling further rational catalyst improvement.

The incorporation of a novel N,N,N-linker into UiO-67 permits it to coordinate copper in an otherwise unattainable way.

A new borylation reagent is introduced for preparing B–N doped conjugated organic frameworks via direct borylation of aryl substituted pyridines and naphthyridines.

Catalytic methane and ethane oxidation activities by μ-nitrido-bridged iron porphyrinoid dimers containing one or two porphyrins in aqueous solutions containing excess H₂O₂ were compared with those by a μ-nitrido-bridged iron phthalocyanine dimer.

Three new isostructural MOFs (ZnTIA, CoTIA and CdTIA) were synthesized by solvothermal method for enhanced electrocatalytic oxygen evolution reaction.

A novel 1,5-naphthalene based metalloviologen complex with reversible photochromism and intrinsic white light emission was synthesized.

The first quaternary telluride, Mn_1.8(1)In_0.8(1)Si₂Te₆, of the Mn–In–Si–Te system has been synthesized and characterized. The phase shows ultralow thermal conductivity (0.28 W m⁻¹ K⁻¹ at 773 K) values.

We performed the first computational study focused on the deposition of a magnetically coupled binuclear complex over a metallic surface.

We investigated the impact of calcination conditions of layered double hydroxide on the formation of layered double oxides and its relationship with CO₂ capture.

The detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) is not only of great significance in the areas of biomedicine and neurochemistry but also helpful in disease diagnosis and pathology research.

Macrocyclic copper(II) complex 1 decomposes forming a robust, heterogeneous, electrocatalytically active deposit for hydrogen evolution from water.

We used DFT+U to explore high-P structures and energetics of CeSiO₄, and found the stetindite → scheelite transition at ∼15 GPa (>8.4 GPa predicted by enthalpy) is driven by lattice instability, due to softening and imaginary state of the E_g¹ mode.

Nonhydrolytic siloxane bond formation reactions between cage siloxanes modified with dimethylsilyl and dimethylethoxysilyl groups in the presence of B(C₆F₅)₃ catalyst are conducted to produce nanoporous materials with well-defined 3D networks.

Ionic liquid post-modified carboxylate-rich MOFs, which were synthesized and characterized, are highly efficient for catalytic epoxides and CO₂ cycloaddition under solvent-free conditions.

The synthesis of ribbon-shaped cool white-emitting ZnO:xDy³⁺ nanophosphors and the quantitative evaluation of their radiative parameters using Judd–Ofelt analysis.

Temperature-dependent variation of flexible hexyl groups in an iron(III) complex influences cation-to-cation and cation-to-anion interactions, leading to an unusual two-step SCO transition in the 400–10 K temperature range.

LiCa₈[Cr^IVN₃]₂N₂F is a nitridochromate fluoride featuring trigonal planar [CrN₃]⁵⁻ anions with tetravalent chromium and highly polar covalent Cr–N bonds. The compound exhibits diamagnetic and semiconducting behavior.

The introduction of diamino groups into UiO-67 enhances its ability to absorb visible light and facilitates the separation of photogenerated electron/hole pairs, leading to higher photocatalytic activity for H₂O₂ production from H₂O and O₂.

Three novel Cu(I) clusters (1–3) were synthesized and characterized by strategically by introducing pargyline and phosphine ligands (PPh₃ or dppy) to tune the structure and photophysical features. Clusters 1 and 3 exhibit excellent luminescent and are employed for the construction of LEDs.

Molybdenum disulfide (MoS₂)-based electrocatalysts have been considered as promising alternatives to platinum for use in the hydrogen evolution reaction (HER).

The copper enzymes lytic polysaccharide monooxygenases (LPMOs) oxidatively cleave strong C–H bonds in recalcitrant polysaccharide substrates. Based on crystal structures, we analyse the roles of the priming reduction, substrate and H₂O₂ binding.

Carbon substituted cobalt bis(dicarbollide) alkyl halides [(1-X-(CH₂)_n-1,2-C₂B₉H₁₀)(1,2-C₂B₉H₁₁)-3,3′-Co]Me₄N (X = Br, I; n = 1–3) are prepared in high yields (>90%) from their corresponding alcohols without side skeletal substitutions.

The synthesis and characterization of NHC-ligated nickel(II) cyanoborate (CB) complexes and salts is reported. The diverse character of CBs as weakly to medium coordinating anions is demonstrated, which dependents on the nature of the CB and the NHC.

Unusual crystal structure of new sodium tellurate NaTeO₃(OH) synthesized by hydrothermal synthesis.

A composite with a hierarchical structure composed of NiCo₂O₄ microspheres and MnS particles exhibits excellent specific capacitance and cyclic stability.

Doping of the SiW₉Co₃@rGO composite into the perovskite layer of photodetectors improves perovskite crystallinity and stability.

A Cu^II-mCPBA adduct without any intricate ligand framework was characterized spectroscopically at room temperature, with remarkable electron transfer and amphoteric reactivity. This adduct decays to form a Cu^II paddle wheel complex.

The antiferromagnetic transition temperatures (T_N) of the perovskite family A₂CoTeO₆ or AA′CoTeO₆ are positively correlated to the average radius of the A-site cations.

(TeCl₄)₄(TiCl₄) with isolated (TeCl₄)₄ heterocubanes and isolated TiCl₄ tetrahedra shows second harmonic generation (SHG) with 1.6-times stronger intensity than potassium dihydrogen phosphate/KDP.

Synthesis, characterization, solution speciation, binding affinity towards biomolecules and anticancer activity of organometallic Ru(II), Rh(III) and Re(I) complexes of (N,N) donor 5α-dihydrotestosterone-based hybrid ligands.

The activation of silica-supported Ti(NEt₂)₄ with anilines gives an efficient, versatile and readily accessible oxo/imido heterometathesis catalyst.

White-light-emitting diodes are realized from a high-brightness zirconium-based metal–organic gel driven by the AIE effect.

Transition metal complexes exhibiting selective toxicity towards a broad range of cancer types are highly desirable as potential anticancer agents.

We show that the emitting ⁵D₄ level in Tb(III) luminescence can be mapped using high resolution optical spectroscopy.

An innovative and scalable method for the preparation of BiOI nanoplates, via a slow basification of the KI/Bi(NO₃)₃ precursor using NH₃ vapor, is described. The resultant BiOI nanoplates can be used for preparing active BiVO₄ photoanodes.

A simple and cost-effective method to prepare a novel multilayer-structured Kevlar®@nickel-phosphorus-boron@copper@copper stearate composite fabric with outstanding properties is successfully developed.

Biscarborane dithiol and its bis(methyl)thioether feature exceedingly long intracluster C–C bond lengths, consistent with the increased π-backdonation of sulfur atom lone pairs into the electron-accepting boron cluster.

Cu+ZnO-X catalysts exhibit a synergistic effect in ester hydrogenation due to the strong adsorption of ester groups by ZnO and H₂ activation by metallic Cu, with a proposed mechanism involving hydrogen spillover.

In situ Raman and FTIR spectroscopies complemented by ¹⁸O labelling are used under oxidative dehydrated conditions at 120–400 °C to explore the speciation of the dispersed (ReO_x)_n phase on monoclinic ZrO₂ at coverages of 0.71–3.7 Re nm⁻².

Two advanced energetic materials were synthesized via introducing carbonyl and o-NH₂–NO₂ groups into energetic fused-ring compounds. A comparative study has demonstrated that the density and detonation performance of these energetic materials could be effectively improved.

The photocatalytic activity of g-CN directly correlates with its production yield, which is controlled by the polymerization kinetics and thus sensitive to synthesis conditions. The synthesis–structure–property relationship has been discussed.

Iron complexes with newly designed silyl-NHC bidentate ligands showed high performance in the catalytic double hydroboration of nitriles to produce N,N-bis(boryl)amines.

Chemically and thermally stable permanently porous coordination cages are appealing candidates for separations, catalysis, and as the porous component of new porous liquids.

Bulk quantities of “helmet” type phthalogens are now achievable with broad variation of their substituents allowing to study their thermal and electrochemical decomposition to CoPcs.

By regulating the proportion of the reaction raw materials in the “one-pot” synthesis process, we obtained a recognition function of the supramolecular self-assembly process to simulate the assembly mode of nucleotides.

A BODIPY-modified Ru(II) photosensitizer displayed efficient PDT, and also reduced side-effects thanks to its fast photo-degradation in water.

Here we describe the synthesis, structures, and volatility of lanthanide complexes containing N₄O₃ ligands decorated with different fluoroalkyl substituents. The results show how ligand fluorination does not necessarily enhance complex volatility.

The T_1/2 of complexes decreases with the increase of the electron-donating ability of C_CN-terminal fragments (increasing the number of methyl substituents on a cyclopentadiene ligand or replacing Ru with Fe).