European Journal of Inorganic Chemistry最新文献

The Front Cover shows that rare-earth acylpyrazolonate complexes can be used in several applications, from the creation of luminescent materials, such as the development of emitting and auxiliary layers in OLED devices, to magnetic materials. The electronic and structural properties of the ligands suggest that the donors are effective sensitizers of various lanthanides emitting in the visible and IR region. More information can be found in the Review by C. Pettinari and co-workers.

The Cu-SAPO-34 catalyst, a promising selective catalytic reduction (SCR) catalyst for the denitration of mobile sources, has attracted widespread research interest due to its wide temperature window, remarkable catalytic performance and good stability. In this study, a series of Cu-SAPO-34 catalysts with varying Cu contents were synthesized by the one-step hydrothermal method. The physicochemical properties of the catalysts were investigated by characterizations, and the reasons for the well-activity catalysts were analyzed. The acidic sites on the SAPO-34 zeolite can adsorb and activate NH₃, while the copper active sites can promote the activation and reduction of NO_x, accelerating the reaction process of SCR. In this study, Cu-SAPO-34 with Cu content of n(Cu)/n(C₉H₂₁AlO₃)=0.075 has good framework stability, which produced more free Cu²⁺ ions and the Cu species are evenly distributed on the carrier surface, and the appropriate amount of acid sites. Therefore, the Cu_0.075-SAPO-34 catalyst exhibits the highest NO conversion performance, maintaining a NO conversion rate above 90 % within the temperature range of 165–450 °C.

The reactions of iodoanilines IC₆H₄NRR′-2 with [Pd(PPh₃)₄] gave complexes [Pd(C₆H₄NRR′-2}I(PPh₃)₂] [R=H, R’=H (1 a), Me (1 b); R=R’=Me (1 c)] while a mixture of 1 a, and the dimeric [Pd{μ-C,N-C₆H₄NH₂-2)I(PPh₃)]₂ (2 a) was obtained when the appropriate iodoaniline was reacted with [Pd(dba)₂] (dba=dibenzylideneacetone) and 1 equiv. of PPh₃. The phosphonium salts [Ph₃PC₆H₄NRMe-2]OTf [R=H (3 b), Me (3 c)] formed upon reacting complexes 1 b,c with TlOTf (OTf=CF₃SO₃). Complexes of the type [Pd(C₆H₄NRR′-2}I(N N)] (4) were obtained from the reaction of [Pd(dba)₂] with the appropriate iodoaniline and a N N bidentate ligand (N N=4,4′-di-tert-butyl-2,2′-bipyridine or N,N,N′,N′-tetramethylethylenediamine). Complexes 4 reacted with TlOTf and PPh₃ or XyNC (Xy=C₄H₄Me₂-2,6) to give [Pd(C₆H₄NRR′-2)(N N)(PPh₃)]OTf (5) or [Pd{C,N-C(=NHXy)C₆H₄NRR′-2)(N N)]OTf (6), respectively. In the absence of any added ligand, the reactions of complexes 4 with TlOTf produced the dimeric complexes [Pd{μ-C,N-C₆H₄NHR-2)(N N)]₂(OTf)₂ (7) or the four-membered palladacycles [Pd(κ²-C₆H₄NMe₂-2)(N N)]OTf (8), depending on the substitution degree of the aniline reagent.

Based on our recent research experience, this review highlights the DNA binding of salen, salphen and salnaphen metal complexes, with a focus on G-quadruplex (G4) DNA, which is crucial in peculiar genomic regions and in cancer regulation. Such metal complexes have in fact shown significant ability to bind and stabilize G4 structures. We will point out the role of the metal center and of the ligand substituents affecting their binding and selectivity toward G4s, supported by experimental and computational studies.

Two high spin Fe(III) complexes, [Fe(L¹)₂]Cl ⋅ H₂O (1) and [Fe(L²)₂]Cl ⋅ 4H₂O ⋅ 0.5MeOH (2), of Schiff base ligands of aminoguanidine with salicylaldehyde and pyridoxal (isolated as the hydrochloride salts L¹H₂⁺Cl⁻ and L²H₃²⁺Cl⁻₂ respectively) are reported. X-ray crystal structure of both the complexes along with their spectroscopic and variable temperature magnetic properties are also investigated. It is found that complex 2 shows stronger zero field splitting (D=9.5 cm⁻¹) than complex 1 (D=5.5 cm⁻¹), probably due to greater distortion of the Fe(III) coordination polyhedron in complex 2. TD-DFT calculations are used to assign the electronic spectra of the complexes. Both the ligands show fluorescence at 450–460 nm with lifetime of nanosecond order and quantum yield of 0.04–0.07 at room temperature. Both the Fe(III) complexes are found to efficiently catalyze the aerial oxidation of DTBC to DTBQ with the turn over numbers 100–155 h⁻¹, which is among the highest for mononuclear Fe(III) complexes. The complexes also act as very good fluorometric sensor for S²⁻, and the limit of detection (LOD) is in the octa-molar region. The pH and temperature dependences of the sensing are also investigated.

Hybrid organic–inorganic perovskites (HOIPs) are promising materials in optoelectronics, particularly for photovoltaic applications, due to their tunable properties and ease of fabrication. Among them, chiral HOIPs are gaining attention for their unique chiroptical properties, by the incorporation of chiral organic molecules into their structure. Despite their potential, the relationship between chiral HOIP structures and their chiroptical properties, such as circular dichroism (CD) spectra, remains challenging to decrypt. This study introduces a simulation workflow based on Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) to model the CD spectrum of the chiral 2D perovskite encapsulating S-1-(3-bromophenyl)-ethylamine (S-(3Br-MBA)₂PbI₄). The approach combines ab-initio molecular dynamics (AIMD) with TD-DFT calculations evaluating the contributions on the whole chiral hybrid perovskite scaffold and those of the isolated ligands, allowing us to dissect the contributions to the CD spectrum of chiral ligands and of the metal-halide sublattice. Additionally, the absorption dissymmetry factor g_abs has been also computed finding good agreement with the experimental value.

This work provides valuable insights for the design of advanced chiroptoelectronic materials.

The Front Cover shows the redox reaction of a substitution-inert and electrically neutral [Ru^III(pic)₃] (pic⁻=picolinate) complex with sulfite in aqueous solution. Studies revealed that, despite being a considerably more weakly electron-accepting oxidant than those reported previously for S^IV oxidation, [Ru^III(pic)₃] can effectively and selectively oxidize sulfite to sulfate through an outer-sphere electron-transfer pathway. More information can be found in the Research Article by O. Impert and D. Chatterjee.

Halide perovskite crystals are garnering significant interest as a promising material for next-generation solar cells. They are also anticipated to be applicable in devices used across a wide temperature range, including X-ray and γ-ray detectors, as well as in solar cells designed for satellite environments. The coefficient of thermal expansion of halide perovskite crystals is a critical physical property to understand, especially given the potential for mechanical degradation in layered devices due to abrupt temperature fluctuations, which may result in mismatched expansion coefficients among different layers. In this study, we employed single crystal X-ray diffraction (XRD) techniques to investigate the coefficient of thermal expansion of halide perovskite crystals, with a specific focus on CH₃NH₃PbI₃, across an extensive temperature range. Our findings reveal that the lattice parameters exhibit discontinuous changes during the phase transition from the β-phase to the γ-phase, in stark contrast to the α to β phase transition. This observation implies that structural phase transitions at low temperatures could significantly affect the longevity and reliability of devices incorporating these materials. The methodology we have utilized for assessing coefficient of thermal expansion via single crystal structural analysis at low temperatures presents a substantial advancement in the research of halide perovskite crystals.

The synthesis and characterization of nine palladium(II) complexes featuring β-ketoiminato ligands of type [Pd(ArNacac)₂] (4) with Ar=2-chlorolphenyl (a); 3-chlorophenyl (b); 4-chlorophenyl (c); 2,3-dichlorophenyl (d); 2,4-dichlorophenyl (e); 2,6-dichlorophenyl (f); 3,5-dichlorophenyl (g); 2,4,5-trichlorophenyl (h); 2,4,6-trichlorophenyl (i) is reported. The molecular structure of 4 a–f, 4 h and 4 i in the solid state was confirmed by single-crystal X-ray diffraction studies. All eight crystal structures are centrosymmetric, with the metal positioned in a slightly distorted square plane. Intermolecular non-covalent interactions such as C−H⋅⋅⋅Pd, Cl⋅⋅⋅Cl, Cl⋅⋅ π, C−H⋅⋅⋅Cl, Cl⋅⋅⋅O, C−H⋅⋅ π, and π⋅⋅⋅π play crucial roles in the formation of the supramolecular structures. The crystal structures of 4 b, 4 c, and 4 e revealed unique intermolecular C−H⋅⋅⋅Pd anagostic interactions between the hydrogen atom on the substituted ligand and the palladium centers, which enable the formation of 1-D polymeric chains. The intermolecular non-covalent interactions were analyzed using Hirshfeld surface. The proportional contributions of each individual atom to the formation of these non-covalent interactions are shown in the 2D fingerprint plots. Furthermore, density functional theory (DFT) has been used to compute the energetic estimation of non-covalent interactions in 4 b, 4 c and 4 e. Furthermore, computational methods such the non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) analysis have been used to study the non-covalent interactions in 4 b, 4 c, and 4 e.

Complexes [Pt(moppy)(PPh₂Py)Cl] (1), [Pt(moppy)(PPh₂Py)]PF₆ (2) and [Pt₂(moppy)₂(CH₃CN)₂Ag(μ-PPh₂Py)₂](PF₆)₃ (3) have been synthesized through choosing suitable experimental condition to modulate the coordination mode of PPh₂Py. Crystal structures indicate that 1 and 2 show distinct mononuclear structures, and complex 3 is a [Pt−Ag-Pt] cluster. In a CH₂Cl₂–H₂O mixed solvent, complexes 1 and 2 can be interconverted upon alternately adding AgPF₆ and NaCl. Complex 3 can dissociate into complex 2 in solution. These complexes reveal different luminescence. In deaerated acetone, complex 1 is non-luminescent, while 2 show green luminescence with main emission bands at 511 and 534 nm. Complexes 1 and 2 in solid state show similar green luminescence, but significant differences in quantum yield, Φ=7.4 % for 1, and Φ=17.6 % for 2. Compared to 1 and 2, complex 3⋅CH₃COCH₃ exhibits yellow solid-state luminescecne (Φ=14.1 %). In this paper, we discuss structural transitions among complexes 1–3 and luminescence modulation.