European Journal of Inorganic Chemistry最新文献

We report the reactivity of the cationic zinc hydride [PMDETAZnH][A] (1) {PMDETA = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine and A = B[C₆H₃(CF₃)₂]₄} for the selective reduction of heterocumulenes via insertion into the ZnH bond. This enables the formation of well-defined cationic zinc amidinate, formamidinate, thioformamidinate, and hydrazone complexes. Further, 1 catalyzes the hydroboration of isocyanate and carbodiimide, yet remains inactive toward isothiocyanate and ethyl diazoacetate, emphasizing its chemoselectivity and utility in main-group hydride-mediated transformations.

A new 1D iron(II) spin crossover (SCO) coordination polymer, [Fe(but-trz)₃][Pt(CN)₄]•H₂O (1), based on 4-butyl-1,2,4-triazole (but-trz), has been synthesized and structurally and magnetically characterized. Compound 1 exhibits an abrupt and reversible high-spin (HS) to low-spin (LS) transition at T_1/2 = 272 K without significant hysteresis, as confirmed by magnetic susceptibility and differential scanning calorimetry measurements. Single crystal X-ray diffraction studies at 296 K (HS) and 150 K (LS) reveal significant anisotropic structural changes and a reversible symmetry-breaking transition involving a shift of the cationic chains. These changes are accommodated without crystal degradation, indicating exceptional mechanical resilience upon cycling. In contrast to its parent compound [Fe(bn-trz)₃][Pt(CN)₄]•H₂O, compound 1 features additional direct interchain interactions at room temperature, likely arising from the flexible butyl side groups. These interactions may enhance elastic cooperativity within the lattice and could also have a limited influence on the higher transition temperature, offering new insights into structure–property relationships in triazole-based SCO systems.

The practical realization of all-solid-state batteries is a key technology for achieving future environmental sustainability. In this context, sulfide solid electrolyte Li₄SnS₄ has attracted attention because of its superior moisture stability compared to that of other sulfide materials. Li₄SnS₄ crystallizes in two crystal structures, hexagonal and orthorhombic; however, the relationship between the structure and moisture stability remains unclear. In this study, both crystal structures of Li₄SnS₄ were synthesized and systematically examined under controlled moisture exposure by monitoring H₂S evolution and evaluating electrochemical performance. The electrolytes were exposed to Ar gas at a dew point of 0°C for 1 h, during which H₂S release was continuously monitored. Post-exposure X-ray diffraction and electrochemical impedance spectroscopy revealed that the orthorhombic phase produced significantly more H₂S than the hexagonal phase. By contrast, the hexagonal phase displayed a higher degree of lithium ionic conductivity degradation. Both phases formed thermodynamically stable hydrate Li₄SnS₄·4H₂O after moisture exposure, with the hexagonal phase yielding a larger fraction. These results indicate that hydrate formation suppresses H₂S generation but accelerates conductivity degradation. Overall, this study establishes the correlation among crystal structure, hydrate formation, and hydrolytic decomposition and proposes a revised definition of “moisture stability” for sulfide solid electrolytes.

Three derivatives of hydrazone-based N, O-chelated half-sandwich ruthenium complexes were synthesized via a convenient synthetic route, yielding satisfactory results. In the context of mild reaction conditions, the prepared air-stable ruthenium complexes give sheen to exhibit efficient catalytic properties in the process of dehydrogenation of aromatic primary alcohols, resulting in the formation of the corresponding carboxylic acids. This reaction has been demonstrated to yield high productivities in open vessels, exhibit a broad substrate scope, and demonstrate good tolerance toward sensitive functional groups. Such half-sandwich ruthenium catalyst systems have been shown exceptional catalytic activity and stability, thus highlighting their potential for industrial application. Ruthenium complex Ru1 molecular structure was confirmed via single crystal X-ray analysis.

2,5-Furandicarboxylic acid (FDCA), a biobased monomer with the potential to replace petroleum-derived terephthalic acid (PTA), is widely used in eco-friendly applications such as bioplastics and high-performance polyesters. In this study, the post-synthetic ligand exchange (PSLE) strategy was employed to synthesize MOF catalysts functionalized with distinct N-heterocyclic carbene (NHC) ligands. The successful preparation and elemental composition of the catalysts were confirmed by ¹H nuclear magnetic resonance (¹H NMR), X-ray photoelectron spectroscopy (XPS), and X-ray powder diffraction (XRD). Under alkaline conditions, UIO-NHC-OCH₃-Pd, with the highest electron density on Pd center demonstrated superior catalytic performance, achieving a reaction rate constant (k = 2.11 h⁻¹) 18.5% higher than that of UIO-NHC-CF₃-Pd and the lowest activation energy (E_a = 25.15 kJ·mol⁻¹). These findings propose an effective ligand-driven electronic modulation strategy for optimizing 5-HydroxyMethylFurfural (HMF) oxidation catalysts, providing a blueprint for sustainable chemical synthesis.

The reactivity of [Rh(GePh₃)(PEt₃)₃] (1) with perfluoro(methyl vinyl ether) [PMVE, CF₂CF(OCF₃)] is investigated. The reaction proceeds via CO bond activation of PMVE and transformation of the OCF₃ into carbonyl ligands. Concomitant release of FGePh₃ ultimately furnishes the fluorovinyl rhodium complex trans-[Rh(CFCF₂)(CO)(PEt₃)₂] (2). Complex 2 is alternatively obtained by the reaction of the rhodium hydrido complex [Rh(H)(PEt₃)₃] (5) with chlorotrifluoroethylene in the presence of CO gas. In the absence of CO, the π-bonded olefin complexes [Rh(Cl)(η²-CF₂CFH)(PEt₃)₂] (7) and [Rh(Cl)(η²-CF₂CFCl)(PEt₃)₂] (8) are formed. Although catalyst deactivation occurs rapidly due to carbonyl complex formation, catalytic derivatization of PMVE with HGePh₃ affords unique germane products such as CF₂HCFHGePh₃ and CF(GePh₃)CF₂.

Birefringence is a key property of optical functional crystals, underpinning their vital applications in angle phase-matching, polarization control, and various advanced photonic technologies. Currently, TiO₂ exhibits a large birefringence in the visible region, serving as a benchmark material. With the advancement of science and industry, the exploration of new birefringent materials in this wavelength band has become increasingly important. In this work, we proposed a mixed anion strategy to enhance the optical anisotropy, using the Hf-O-N system as a case study. Structures with Hf-O-N were screened from the NOEMD database for further first-principles calculations. Six structures with (E_hull ≤ 0.05 eV/atom) possess large bandgaps (1.67–5.02 eV) and significant birefringence (0.17–0.403 @1064 nm). Four structures exhibit potential birefringence in the visible region, I4/mmm-Hf₂N₂O (0.37 @1064 nm), Cm-Hf₅N₆O (0.219 @1064 nm), C2/m-Hf₇N₈O₂ (0.333 @1064 nm), and Cm-Hf₇N₈O₂ (0.403 @1064 nm). The birefringence of three of these structures exceeds that of TiO₂(0.256 @1064 nm). Through structural analysis, we identified that the [Hf₄NO₂], [Hf₄NO], and [Hf₂NO₄] polyhedra are outstanding optical functional units, which tend to offer significant optical anisotropy. This result offers novel potentialities for the application of birefringent materials and guideline for novel uses of Hafnium oxynitride materials.

Dye-Sensitized solar cells have emerged as promising photovoltaic devices due to their low cost and excellent low-light performance. Two pairs of copper redox mediators were investigated to assess the influence of ligand donor atoms on the device performance. The sulfur-containing ligand effectively delocalizes electron density around the central metal, thereby enhancing the redox potential and ultimately achieving a high open-circuit voltage of 1.0 V in the device, together with a power conversion efficiency of 8.62%. This study establishes a novel electrolyte structural engineering strategy for the device performance enhancement.

The ion-separated salts [K(18-crown-6)][(Me₂-cAAC)GeE(SiMe₃)₃] (1a,b) and [K(2.2.2-cryptand)][(Me₂-cAAC)GeE(SiMe₃)₃] (2a,b) (a, E = Si; b, E = Ge; Me₂-cAAC = 1-(2′,6′-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidine-2-ylidene) were synthetised via stoichiometric reaction of K[(Me₂-cAAC)GeE(SiMe₃)₃] and 18-crown-6 or [2.2.2]cryptand in THF at room temperature. Structural, spectroscopic, and computational characterisation of the ‘naked’ anions [(Me₂-cAAC)GeE(SiMe₃)₃]⁻ showed that they can be described with a resonance between base-stabilised germylidenide and germenyl anion formulations. The reaction of CO₂ with 1a gave a formal [2+2] cycloaddition product $$ (3), whereas the contact ion pair salts K[(Me₂-cAAC)GeE(SiMe₃)₃] give μ-CO₂-κC:κO complexes [(Me₂-cAAC)Ge{C(O)OSiMe₃}E(SiMe₃)₃] or radicals [(Me₂-cAAC)GeE(SiMe₃)₃]^•. The mechanism for the formation of 3 was analysed computationally, and the differing reactivity of 1 and K[(Me₂-cAAC)GeE(SiMe₃)₃] with CO₂ was rationalised in terms of the electronic structure of the anion that is modulated by the coordinating vs. noncoordinating nature of the counter ion.

Lanthanide-binding tag (LBT) optimized for protein labeling was engineered into calmodulin by inserting a variant sequence (W₇Y₈ → Y₇I₈) at Site 1 of the N-terminal domain while inactivating Site 2, and the resulting CaMLBT was examined for its Ln-binding properties. CaMLBT forms 1:1 complexes with all lanthanides. Fluorescence spectroscopy and CE-ICP-MS revealed dissociation constants ranging from sub-nanomolar for La (Kd = 437 ± 259 pM) to the low picomolar range for Tb–Lu, reaching Kd = 1.1 ± 0.4 pM for Lu at pH 6. This corresponds to a ∼1000-fold affinity increase over the original LBT, approaching the stabilities of lanmodulins. In contrast to lanmodulins, however, Ln–CaMLBT complex stability increases with decreasing Ln(III) ionic radius, consistent with trends reported for LBT. ATR-FTIR spectroscopy indicates that the enhanced stability arises from changes in coordination number and ligand properties: Glu₉ would evolve from tight bidentate (La to Pr) to more asymmetric or weaker (Yb and Lu) coordination, while Asp₃ and Asp₅ evolve from pseudo-bridging to strong monodentate ligands. Notably, no evidence for water ligation was found for early lanthanides. CaMLBT emerges as a highly stable and versatile scaffold to investigate structural factors underlying lanthanide selectivity and complex stability.