European Journal of Inorganic Chemistry最新文献

Sb₂S₃ has excellent photovoltaic properties, but the performance of its photovoltaic devices still needs to be improved. The main issues hindering its photovoltaic performance are the poor carrier transport ability and the significant charge recombination. Doping strategies play a key role in addressing these issues. This study investigates the effect of Pb(CH₃COO)₂ (Pb) and [Pb(DMF)₇]₂[SiW₁₂O₄₀] 2DMF (Pb-SiW₁₂) doping on the photovoltaic properties of Sb₂S₃ thin films. It is found that the intensity of diffraction peaks on the (130) crystal plane of Pb-doped Sb₂S₃ and the (221) crystal plane of Pb-SiW₁₂@Sb₂S₃ is increased, which enhances the crystallinity of the films. Meanwhile, Pb and Pb-SiW₁₂ doping narrow the bandgap (1.69 eV) of Sb₂S₃ to 1.65 eV and 1.62 eV. Electrochemical tests show that the carrier concentration and carrier lifetime are increased. The Pb-doped Sb₂S₃ photodetector photocurrent of 14 μA, 7 times higher than the 2 μA pristine Sb₂S₃ photodetector. It exhibits a responsivity of 13.9 mA/W and detectivity of 1.2×10¹¹ Jones. The Pb-SiW₁₂@Sb₂S₃ photodetector photocurrent is 11 μA. Pb-SiW₁₂ can immobilize Pb while reducing the amount of Pb. The methodology in this work provides a way to improve the performance of Sb₂S₃ thin-film photodetectors.

The dehydrogenation of ammonia borane in the presence of a variety of Lewis acids such as ICl, IBr, Br₂, CuCl₂, AlCl₃, GaCl₃, InCl₃, and [Ph₃C]BF₄ at a concentration of 7.5 mol % was effective in selectively producing aminodiborane (μ-NH₂B₂H₅, ADB) at 80 °C. Compounds such as ICl, IBr, Br₂, AlCl₃, and GaCl₃ at the same concentration could also generate ADB at lower temperatures of 35 °C and 50 °C. In contrast, BX₃ (X=Cl, Br) at the same concentration of 7.5 mol % was found to give exclusively B₂H₆. Further, selective synthesis of diborane or ADB was achieved by adjusting the stoichiometry of the boron trihalides. A concentration of 7.5 mol % (upto 1 equivalent) of BBr₃ favored the formation of B₂H₆, while 1 mol % BBr₃ predominantly yielded ADB. Interestingly, both ADB and B₂H₆ facilitated the reduction of acetanilides. A mechanism has been proposed for both diborane and ADB formation using these Lewis acids.

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.

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.