European Journal of Inorganic Chemistry最新文献

The Front Cover illustrates how the oxygen atoms in [ReO₄]^– can be replaced by nitrogen atoms upon controlled addition of NH₄⁺ as a nitrogen source. From the reaction of NH₄[ReO₄] in an alkali metal hydroxide flux, Rb₃[ReO₄][ReO₃N] and Cs₃[ReO₄][ReO₃N] could be synthesized. In order to obtain monoanionic products, namely K₂[ReO₃N] and Cs₂[ReO₃N], NH₄Cl was added to the corresponding alkali metal hydroxide as an additional nitrogen source. More information can be found in the Research Article by J. Bruns and co-workers (DOI: 10.1002/ejic.202500036).

The Front Cover shows a sketchpad with the structure of the formal methanol activation product of an aluminum–carbon-based ambiphile that is formed by the elimination of ammonia. A water molecule is shown above the eliminated ammonia molecule, indicating that replacement by water can also be realized. On the left, other small molecules that do not react with the title compounds are shown. The product of trimerization of phenyl isocyanate, for which the ambiphiles act as catalysts, is shown on the left. To the right are shown the insertion products of carbon dioxide and acetonitrile. The ticked reaction product with carbon dioxide can be realized, the crossed-out acetonitrile product cannot. The reaction path bottom right shows that the insertion process of acetonitrile is endergonic overall and rather high activation barriers are predicted. More information can be found in the Research Article by I. Fernández, F. Breher and co-workers (DOI: 10.1002/ejic.202500165).

The Front Cover shows a local environmental effect on the electronic structure of the M-cluster of nitrogenase, which was examined by DFT calculations from the viewpoint of the hydrogen bonds and water molecules. Hydrogen bonds from Ser265 significantly contribute to the stability of the LUMO, while the water molecules around the HCA strongly stabilize the HOMO. The contribution of Ser265 is, however, suppressed when an outer environmental field is applied. The results provide suggestions for the ligand design of synthesized FeS clusters. More information can be found in the Research Article by Y. Kitagawa and co-workers (DOI: 10.1002/ejic.202500016).

The Front Cover shows truxenone (Tr), which has high C_3h symmetry and degenerated LUMO. It forms salts and complexes. Calculations predict Jahn–Teller distortions for Tr^⋅− that are enhanced by the asymmetric approach of Cp*₂Co⁺ to Tr^⋅−. The dianions should have a triplet state, but the asymmetric approach of Cs⁺ to the oxygen atoms of Tr²⁻ stabilizes the singlet ground state. Radical anions of Tr^⋅− coordinate with Tb^III(TMHD)₃ and Mn^II(acac)₂ providing asymmetric spin density localization on the coordinated oxygen atom and strong magnetic exchange of the ligand and paramagnetic metal spins. More information can be found in the Research Article by D. V. Konarev and co-workers (DOI: 10.1002/ejic.202400760).

The Cover Feature shows the preparation of solids based on a Pd--Te complex, [Pd₂(μ-TePh)₂(bipy)₂](PF₆)₂, immobilized over porous TiO₂ and over commercial TiO₂ to be used as photocatalysts for H₂ production by water splitting under sunlight. All the solids enhanced H₂ production compared to pure titania supports by up to 69-fold. This outcome inspires the investigation of metal complexes combined with semiconductors to improve their photocatalytic ability for H₂ production. More information can be found in the Research Article by S. Nakagaki and co-workers (DOI: 10.1002/ejic.202400806).

The Front Cover illustrates the use of amino-acid dithiocarbamate ligands as building blocks for heterometallic coordination polymers. As outlined in the Review by P. Köhler (DOI: 10.1002/ejic.202500007), these ligands form stable all-S coordinate complexes with different transition metal ions, and the resulting products can act as metalloligands for coordination of a second metal ion due to their free carboxylate groups. The illustration shows the assembly of dithiocarbamato-carboxylate metalloligands and oxophilic metal ions in a modular fashion, analogous to interlocking toy building bricks.

Hydrophobic deep eutectic solvents (HDESs) are regarded as the green and new generation solvents for the separation of metal ions and other valuables from their waste solutions. In this context, a strongly HDES based on trioctylphosphine oxide and decanoic acid is employed in its undiluted condition for the solvent extraction of Eu(III) (taken as Ln(III) representative) from a broad range of nitric acid solutions. The projected HDES is highly hydrophobic and less viscous in nature. Various solvent extraction parameters are tuned to realize the extractant behavior of the proposed HDES. Though the extraction shows a decline at high feed acidity, the system is efficient to extract Eu(III) from pH range to concentrated acid solution with a high % extraction. The involvement of two HDES in the metal–solvate species (metal–ligand complex) formation with fast extraction kinetics corroborates the suitability of the extractant for extracting Eu(III) from the acidic phase. The phase volume ratio is changed to affirm the best possible extraction factors at the expense of minimum volume of HDES. The stripping performance of Eu(III) from the loaded HDES phase is investigated using Milli-Q water as the stripping solution, thereby establishing the sustainability of the system.

The lanthanides form a chemically cohesive series, and identifying differences that can be leveraged to separate near neighbors remains an ongoing need. Here, the synthesis, structural chemistry, and spectroscopic properties of a neodymium-acetylacetonate monomer, [Nd(acac)₃(H₂O)₂] (Nd-1), and an acac-bridged Nd-dimer, [Nd₂(acac)₆(H₂O)₂] (Nd-2), are described. Interestingly, the Nd-dimer readily precipitates from solution; however, efforts to crystallize the Dy analog using the same synthetic approach are unsuccessful. Yet heterometal dimers, [Nd_2-xDy_x(acac)₆(H₂O)₂] (NdDy-2), can be prepared from mixed-metal solutions. To understand these differences in crystallization behavior of Nd- and Dy-acac complexes, solution speciation of Ln-acac systems is examined using nano-electrospray ionization-mass spectrometry (nESI-MS). Both homometal and heterometal solutions are prepared (Ln = Nd, Dy, Nd/Dy). nESI-MS of the solutions showed presence of homometallic dimeric species for Nd and Dy and peaks consistent with both homometallic and heterometallic complexes in mixed-metal solutions. Density functional theory is used to further understand the intrinsic differences in nucleation energetics in dimeric homo- and heterometallic species. Overall, this work provides fundamental insight into the correlation between solution- and solid-state structural units and differences in the crystallization behavior of Ln complexes; the latter is particularly relevant to separating metal ions with otherwise very similar chemical behavior.

The preparation of cyclic carbonate from CO₂ is one of the effective ways to utilize its resources. Herein, a series of N-heterocyclic carbenes (NHCs) Ag(I)–based UiO-67-type metal-organic frameworks (MOFs), UiO-bpdc-NHC/Ag, UiO-(bpdc-NH₂)-NHC/Ag, and UiO-(bpdc-F₃)-NHC/Ag are reported. These MOFs are characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and ¹⁹F NMR (nuclear magnetic resonance), confirming Ag(I) integration. Among them, due to the affinity of trifluorocarbonamide group for CO₂ and the high activity of NHC/Ag, UiO-(bpdc-F₃)-NHC/Ag possesses the best catalytic performance for the CO₂ conversion to cyclic carbonates. Notably, the catalyst exhibits robust activity under diluted CO₂ akin to flue gas, demonstrating high stability and recyclability. Mechanistic insights implicate Ag(I)-mediated polarization of propargylic alcohols’ CC bond, facilitating CO₂ insertion and ring-closure to α-alkylidene cyclic carbonates. This study underscores MOF-based catalysts’ potential in sustainable CO₂ utilization, offering a pathway for efficient chemical synthesis in environmentally sensitive contexts.

Achieving efficient photoelectrochemical oxygen evolution reaction (OER) is a key to reduce the high overpotential barriers associated with overall water splitting. The OER performance of many semiconducting metal oxide catalysts is hindered by weak charge separation at the interface, fast carrier recombination, low electrical conductivity, and lack of adsorption properties. A promising approach to overcome these issues is the integration of OER catalysts with porous and highly conductive semiconductor templates. However, the strategic selection of the template is important to facilitate the formation of heterojunction, which can promote effective carrier transport and boost photoelectrochemical performance. Herein, a novel binder-free photoelectrocatalyst for efficient alkaline water oxidation is reported. This catalyst is developed through an in situ incorporation of OER active nickel oxide (NiO) catalyst into a porous, conductive antimony-doped tin oxide (ATO) semiconductor using a resorcinol-formaldehyde polymer supported sol–gel method. The prepared NiO/ATO binder-free porous catalyst exhibits greatly improved photoelectrochemical performance toward water oxidation with a remarkable low onset potential of 1.39 V and an overpotential of 282 mV (at 10 mA cm⁻²). This significant enhancement of OER performance is due to improved charge transport properties at the NiO/ATO heterojunction and increased surface area with more active catalytic sites.