European Journal of Inorganic Chemistry最新文献

Static catalysis using neutral and cationic Al(III) complexes, in which the oxidation state of the metal does not change, can be applied to a range of catalytic bond-forming reactions which have similar characteristics to transition metal analogues. This short review (although not intended to be comprehensive) highlights the current state of development in the areas of dehydrocoupling, alkene polymerisation, and other bond forming reactions involving single-site Al(III) catalysts, focusing in particular on the key factors involved in molecular activation and the mechanisms of catalysis.

In this paper, a series of KGaGeO4:0.01Cr³⁺, xIn³⁺ (KGGO:0.01Cr³⁺, xIn³⁺, x=0~0.08) phosphors were synthesized by high temperature method. KGGO:0.01Cr³⁺ has a far red emission in the range of 600~900 nm ascribing to the 4T2→4 A2 spin-allowed transition of Cr³⁺. With the incorporation of In³⁺, KGGO:Cr³⁺, In³⁺ shows a near-infrared (NIR) broadband emission in the range of 700~1200 nm, with red shift of the emission peak by 136 nm, and FWHM of 185 nm. The electroluminescence efficiency of NIR pc-LED prepared by KGGO:0.01Cr³⁺, 0.02In³⁺ is as high as 19 % under the output power of 25 mW, which can be applied in the night vision technology and microbial growth.

Chemists have developed sophisticated structural monomers and meticulously regulated the strength and directionality of non-covalent interactions to assemble a variety of novel supramolecular helices in accordance with the second strategy, resulting in significant research advancements. These investigations not only enhance our comprehension of the supramolecular assembly process but also inspire innovative approaches for the development of supramolecular materials and related domains within materials chemistry. In the strategy for constructing supramolecular helices, utilizing non-covalent interactions between monomers as a bonding force is an effective method for further assembling monomeric units with H-bonded meniscus structures into helical configurations. Hydrogen and and halogen bonds represent two distinct categories of non-covalent interactions that have increasingly attracted scholarly attention in recent years, demonstrating extensive and significant applications in the assembly of diverse supramolecular topologies. This paper provides a summary of several instances where these interactions facilitate the self-assembly of supramolecular helices. Moreover, although the development of chalcogen bonding has emerged relatively recently compared to their counterparts, and despite their limited application in complex assembly structures, they have nonetheless been effectively employed in the construction of supramolecular helices.

An innovative catalytic system for biodiesel synthesis starting from waste biomass (waste cooking oil, WCO) in the presence of waste material (steel slags) as the catalyst under microwave irradiation is described. The reaction conditions were optimized by using response surface methodology (RSM) based on Box-Behnken Design (BBD) taking time, temperature, and catalyst weight as factors. The optimum conditions, leading to 97 % conversion of WCO into FAMEs (fatty acid methyl esters) were found to be: 18 min reaction time, 134 °C and 380 mg of catalyst for 1.0 mL of WCO. The recyclability of the catalyst was tested at different experimental conditions, and by increasing the reaction times for subsequent cycles, the catalytic efficiency remained steady. The alkalinity of both as-received steel slags and steel slags recovered after three reaction cycles was tested with the Hammett indicator method. The steel slags were also characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Fluorescence (ED-XRF), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), X-ray Photoelectron Spectroscopy (XPS).

A new ruthenium(II) NAD (NAD=Nicotinamide Adenine Dinucleotide) type bis-carbonyl complex, [Ru(bpy)(pbn)(CO)₂]²⁺ [pbn = 2-(pyridin-2-yl)benzo[b]-1,5-naphthyridine; bpy = 2,2′-bipyridine] [1]²⁺, was successfully synthesized and fully characterized by single-crystal X-ray structural analysis, ESI-MS, IR and NMR spectroscopy. Complex [1]²⁺ together with [Ru(bpy)(pbn)(CO)(COOH)]⁺ and/or [Ru(bpy)(pbn)(CO)(CO₂)]⁰ complexes exist as equilibrium mixtures in aqueous solutions as evident from spectroscopic study. Chemical reduction of [1]²⁺ resulted the formation corresponding NADH form i. e., [Ru(bpy)(pbnHH)(CO)₂]²⁺ (pbnHH = 2-(pyridin-2-yl)-5,10-dihydrobenzo[b][1,5]naphthyridine) [1.HH]²⁺ as a two-electron-reduced species. The electrochemical behavior of complex [1]²⁺ in the presence of acid was investigated based on cyclic voltammetry analysis. A control potential electrolysis of [1]²⁺ afforded formate (HCOO⁻) as the major product with a lesser amount of CO and H₂, whereas that of [Ru(bpy)₂(CO)₂]²⁺ complex produced CO as the main product with a lesser amount of HCOO⁻ and H₂. The experimental results suggest that the selectivity of HCOO⁻ over CO should be due to catalytic hydride transfer from the NADH-type ligands of [1]²⁺ to CO₂.

Interaction of perfluorinated group 13 element Lewis acids E(C₆F₅)₃ (E=B, Al, Ga, In) and Al{OC(CF₃)₃}₃ with diatomic halogens and interhalogens was studied computationally. Boron-containing derivative is predicted to form weak complexes with halogens and to be thermodynamically stable with respect to iodination, while its heavier derivatives form stronger complexes that are unstable with respect to E−C bond oxidation. The reactivity of E(C₆F₅)₃ with iodine and iodine monochloride and Al{OCR₃}₃ (R=CF₃, C₆F₅) with iodine was explored experimentally. Experimental data confirm that B(C₆F₅)₃ does not react with ICl at room temperature and with molecular iodine in temperature range 233–350 K. Heavier group 13 element derivatives E(C₆F₅)₃ upon reaction with I₂ and ICl undergo oxidation processes with C₆F₅I evolution. Both Al{OC(CF₃)₃}₃*C₆H₅F and Al{OC(C₆F₅)₃}₃ do not form stable complexes with molecular iodine.

The separation of ethylene (C₂H₄) and acetylene (C₂H₂) is challenging due to their similar molecular dimensions and boiling points, making conventional methods like cryogenic distillation and solvent extraction inefficient and environmentally harmful. Fluorinated metal-organic frameworks (MOFs) have been proven to be an effective material for the separation of C₂H₄ and C₂H_2. However, their direct synthesis is relatively expensive and challenging. In this study, we report a facile post-synthetic modification strategy to introduce fluorinated alkane pores into a zirconium-based MOF, MOF-808. The construction of fluorine-containing pores within the MOFs prefers adsorption for C₂H₂ attributed to the interaction between the fluorine atoms and C₂H₂. This series of fluorinated MOFs demonstrates potential for gas separation processes, with the highest separation ratio reaching 2.67 (1 : 99) at 298 K. Breakthrough experiments for C₂H₂/C₂H₄ mixtures confirmed that fluorinated MOF is capable of separating C₂H₂/C₂H₄, making it a potential candidate for industrial application. Moreover, the simplicity of the post-synthetic modification method suggests a viable strategy for the synthesis of fluorinated MOFs.

The reaction of boroles with organic azides is known to straightforwardly yield 1,2-azaborinines, which have generated significant interest as benzene bioisosteres. We show that this powerful synthetic pattern extends to a variety of structurally and chemically diverse boron azides, including recently reported diborane(4) azides. This provides a general, powerful borylation method to expand the chemistry of 1,2-azaborinines.

Pyrrophen ligands are acyclic hexadentate ligands containing salen-type N donors: two phenolic O donors, two pyrrolic N-type donors, and two oxo-carbonyl coordinating units. Uranyl complex derivatives of pyrrophen UO₂L_1–2a-c (L1=H); (L2=CH₃); (L=2-pyridinemethanol (a), N-(2-pyridinylmethyl) (b), N-benzyl (c), were synthesized and characterized by x-ray diffraction (XRD), nuclear magnetic resonance (NMR), and UV-vis. Each uranyl-containing structure was found to crystalize in a hexagonal bipyramidal coordination environment. We observed solid-state coordination deviations caused by the amide/ester substituent. The inductive effects and structural features were examined, and the effects on the bond lengths of the uranyl coordination and deviations in the -yl oxygen bond lengths and angles were studied.

The fluorination of the peri-substituted acenaphthyl scaffolds 5-PhE-Ace-6-PPh₂ (1E, E=O, S, Se, Te) using XeF₂ afforded the difluorinated products 5-PhE-Ace-6-PF₂Ph₂ (2E, E=O, S, Se, Te) and tetrafluorinated products 5-PhEF₂-Ace-6-PF₂Ph₂ (3E, E=Se, Te) depending on the stoichiometry applied. Fluoride abstraction of 2E using Me₃SiOTf gave rise to the chalcogenide supported fluorophosphonium ions [5-PhE-Ace-6-P(F)Ph₂](OTf) (4O and 5E, E=S, Se, Te). The molecular structure of 4O features a tetrahedral P atom, whereas those of the heavier analogues (5E, E=S, Se) contain trigonal bipyramidal P atoms that arise from intramolecular LP(E)→σ*(P−F) interactions.