European Journal of Inorganic Chemistry最新文献

Multinuclear complexes have attracted great attention because of their superior properties originating from the cooperative effects between the metal ions. In this study, we synthesized polynuclear zinc complexes by chelation between the side-chains of polyhedral oligomeric silsesquioxane (POSS). From the NMR spectroscopy, high-resolution mass spectrometry and Fourier transform infrared spectroscopy (FT-IR), it was confirmed the four equivalents of zinc ions were coordinated to the single POSS molecule. Optical measurements indicated that luminescent properties can be preserved even in the solid state. The three-dimensional structure of POSS should play a significant role in suppressing concentration quenching followed by solid-state emission properties.

Efficient removal of propyne impurities from propylene is essential for producing high-purity propylene. In this study, we utilize the flexible metal-organic frameworks (MOFs) material, MOF-508, for C₃H₄/C₃H₆ separation. Propyne (C₃H₄) induces a “Gate-opening” effect in MOF-508, transitioning it from a narrow-pore phase to a large-pore phase at low pressure. In contrast, propylene (C₃H₆) only triggers this effect at a higher pressure of 0.55 bar. Notably, at 298 K and 0.5 bar, MOF-508 adsorbs 71.9 cm³/g of C₃H₄, compared to just 7.9 cm³/g of C₃H₆. This selective adsorption significantly enhances C₃H₄/C₃H₆ separation (50/50, v/v), as further demonstrated by dynamic breakthrough experiments.

The Cover Feature illustrates the uneven fight between our gaseous hero Gas-Face (“He He He”) and the evil PP-Pig-Man “coordinating” cationic Pt^II-thiomethoxymethyl complexes. By virtue of Gas-Face′s superpower—to be everywhere—collisions of the (PP-Pig-Man-)diphospine complexes with helium cause their gas-phase fragmentation. Depending on the bite angle, different neutrals are lost: while neutral dimethylsulfide is preferentially ejected for bite angles >90° (here dPPb), the loss of ethene and thioformaldehyde dominates for bite angles <90° (here dPPm). More information can be found in the Research Article by B. Butschke and co-workers.

The Front Cover indicates the conversion of waste into a resource. The letters make up the word “FAMEs”, which is the chemical description of biodiesel. Each letter occupies its own quadrant, describing the process with an image: waste cooking oil (F) was converted by using waste steel slags (A) as the catalyst, due to their alkaline features (M), under microwave irradiation (Es), thus preserving the environment. More information can be found in the Research Article by M. M. Dell'Anna, P. Mastrorilli and co-workers.

A new mononuclear, four-coordinate heteroleptic cobalt(II) complex 1 was synthesised utilising N,N′-1,2-Phenylenebis-(4-methylbenzenesulfonamide) and 6,6′-Dimethyl-2,2′-bipyridine as ligands and structurally characterised. Magnetic susceptibility and magnetisation measurements, along with ab initio calculations, revealed a large easy-axis type magnetic anisotropy of the cobalt(II) centre. Frequency-dependent ac susceptibility measurements revealed out-of-phase signals, indicating a slow relaxation of magnetisation, even in the absence of an additional static magnetic field. The corresponding relaxation behaviour can be attributed to a combination of Orbach and phonon-assisted processes within the observable temperature range. Using FD-FT THz-EPR spectroscopy, the magnetic anisotropy barrier was determined to be unexpectedly large with a value of 146.4 $$. The deviation from the expected barrier, based on correlations with the elongation parameter $$, is attributed to the charge distribution in the coordination environment.

Although the chemistry of monodentate N-heterocyclic carbenes (NHCs) with s-block metals has been investigated, the coordination chemistry of phenyl dicarbene (CCC=bis(diisopropylphenyl-imidazol-2-ylidenemethyl)phenyl) complexes remains largely underexplored. We report the synthesis and characterization of the free phenyl dicarbene precursors (^BrCCC^Dipp and ^BrCCC^Mes) and the ensuing reactivity with Grignard reagents (3,5-(CF₃)₂-Ph)MgBr and MeMgCl to afford the cyclic dimeric complexes, (^BrCCC^DippMg3,5-(CF₃)₂PhBr)₂, (^BrCCC^MesMg3,5-(CF₃)₂PhBr)₂, and (^BrCCC^DippMgMeCl)₂. Further exploration of various routes to activate the central C−Br bond of the ligands with alkali metals resulted in isolation of the respective NHC adducts of LiN(SiMe₃)₂ and KN(SiMe₃)₂. Notably, these studies imply that flexibility of the pincer framework engenders dimeric complexes of s-block precursors over the monomeric complexes. The identity of the complexes was ascertained using multinuclear NMR spectroscopy and X-ray crystallography.

Organophosphate compounds (OPC) are chemical species with a broad range of applications from agricultural to medicinal chemistry, which however rose sadly to the fore for their use as chemical weapons worldwide. Several efforts are therefore carried out to contrast their toxic effects or to repurpose OPC for chemical synthesis. In this regard, metal-containing systems, like metal-organic frameworks or complexes, represent a valid solution for the treatments of OPC in a number of fields. Our work has been inspired by the recent findings concerning the reactivity of (^iPrPN^HP)Mn(CO)₂(OH) (1) complex with P−F bond containing organophosphate compounds. We, in particular, have investigated three different OPC, which are diisopropylfluorophosphate (a), isopropylfluorophosphoric acid (b) and fluorophosphoric acid (c), extending the complex 1 reactivity to the nerve gas sarin (sa). The reaction concerns the leaving of fluoride from OPC, to produce relative defluorinated phosphates and the (^iPrPN^HP)Mn(CO)₂(F) complex. Analysis of the calculations revealed that the reaction is favored from both thermodynamic and kinetical points of view for a substrate. Our results are in agreement with the available experimental data and represent a further confirmation of versatility of such metal-complex to interact with P−F containing toxic agents.

Artificial ion channels and transporters designed to recognise and transport specific ions and molecules have been extensively studied. These biomimetic single-crystal materials have gained particular attention for their potential to reveal the complex mechanisms of biological functions and to provide functionalities based on molecular design. In the present study, we found that Li⁺ ions in the ion channels of Li₂([18]crown-6)₃[Ni(dmit)₂]₂(H₂O)₄ (1) crystals exchange with R-NH₃⁺ (R=Me, Et, nPr) ions in aqueous solution. After ion exchange, the resultant (R-NH₃⁺)([18]crown-6)[Ni(dmit)₂]⁻ (1-R, R=Me, Et, nPr) crystals are missing one [18]crown-6 molecule per two cations compared to 1. During ion exchange, some of the [18]crown-6 molecules, which constitute the channels, are released into the aqueous solution along with Li⁺ ions. The ion exchange of 1 in mixed aqueous solutions of organic ammonium cations shows selectivity for MeNH₃⁺, which is attributed to the stability of the 1-Me. These results demonstrate the potential for transporting molecular cations in channel structures composed of crown ethers, which will facilitate the development of transporters for drugs and other substances essential for biological functions.

We present co-crystallization as an approach to tuning spin crossover (SCO) properties of mononuclear Mn(III) Schiff-base complexes. Complexes [Mn(5-F-sal-N-1,5,8,12)]ClO₄ ⋅ 0.5carbazole (cocrystal 1 a) and [Mn(5-F-sal-N-1,5,8,12)]PF₆ ⋅ 0.5carbazole (cocrystal 2 b) are synthesized by the co-crystallization of their parent complexes ( [Mn(5-F-sal-N-1,5,8,12)]Y, Y=ClO₄⁻ (1); Y=PF₆⁻ (2) ) with the carbazole and they both exhibit HS electronic configurations between 2 and 300 K. While, the parent complex 1 shows a nearly complete SCO with T_1/2=100 K and complex 2 maintains a high-spin (HS) state. The introduction of carbazole as the third component has a great influence on cation-anion crystal packing and finally the cooperative effects of the SCO complexes.

Copper is arguably one of the most strategic metals for the energy transition, particularly in the shift from fossil fuel-based engines to sustainable and renewable energy sources, with related and broader electrification efforts. While global copper mineral resources are far from depleted, their uneven distribution poses significant supply risks, especially in regions like Europe. In 2023, the European Union (EU) recognized this risk by designating copper as a strategic raw material (SRM), highlighting the need for innovative copper recovery processes. Copper recovery from industrial and electronic waste has been approached through various methods, primarily categorized into pyrometallurgy and solvo- and hydrometallurgy. The latter offers greater tunability and potential for sustainability, particularly when leveraging coordination chemistry. This review focuses on the most promising hydrometallurgical processes for copper recovery from industrial and e-waste (i. e., electronic waste), with a special emphasis on the role of coordination chemistry in supporting these methods. We posed particular focus on the adaptability and versatility of the coordination chemistry-based processes to the highly heterogenous composition of the copper-containing wastes.