European Journal of Inorganic Chemistry最新文献

The Front Cover shows a cobalt tetraphenylporphyrinate-chitosan-based microsphere excited by a 930 nm pulsed laser. This excitation induces an intense second harmonic generation (SHG)emission,aswellasdynamic and magnetic properties in the microsphere. The chitosan coating allows for the biocompatibility of the nanospheres for applications such as SHG biosensors and in dynamic and magnetic anticancer therapies. More information can be found in the Research Article by D. Marabello and co-workers (DOI: 10.1002/ejic.202500452).

The Front Cover shows a family photo gallery illustrating the components of a new class of porous porphyrin nanotubes (PNTs). A series of nanotubes incorporating a range of dicationic metal centres and carboxylate ligands has been synthesised. All nanotubes within the family assemble as isostructural crystals with an approximately hexagonal cross-section, offering the scope for structural tailoring to meet desired functional requirements. More information can be found in the Research Article by J. M. White and co-workers (DOI: 10.1002/ejic.202500493).

The Front Cover highlights the synthesis, characterization and photophysics of tetra-cationic porphyrins containing peripheral tricarbonyl-Re^I complexes in interaction with bio-macromolecules such as bovine serum albumin (BSA). More information can be found in the Research Article by B. A. Iglesias and co-workers (DOI: 10.1002/ejic.202500530).

The reaction of difluoro(mesityl)borane (1), as its adduct with 4-(dimethylamino)pyridine (dmap), with (naphthalen-1,8-diyl)dilithium results in the formation of the aryl-substituted naphtho[1,8-bc]borete (3)—the boron-containing analogue of an elusive cyclobuta[de]naphthalenium cation—as a dmap adduct (3·dmap). This trapped borete, as well as 1·dmap and the analogous adducts of 1 with pyridine (py) and 3,5-lutidine (lut) have been fully characterised by multinuclear NMR spectroscopy and X-ray crystallography using Hirshfeld atom refinement with custom-generated aspherical atomic scattering factors. Free borete 3 is transient in the absence of dmap, and density-functional theory calculations support a rapid dimerisation to the corresponding 1,5-borocine (2) via (4 + 4) cycloaddition, i.e., σ-bond metathesis. While the 3·dmap adduct proved highly kinetically stable, the release and dimerisation of 3 was observed under mass-spectrometric conditions.

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.

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.