European Journal of Inorganic Chemistry最新文献

In this work polymer nanofibers were functionalized by incorporation of the spin transition (ST) compound [Fe(H₂btm)₂(H₂O)₂]Cl₂ (FeH2btm) (H2btm=di(1H-tetrazol-5-yl)methane). FeH2btm is an interesting compound due to its ability to reversibly and sensitively switch between high spin (HS) and low spin (LS) state when exposed to common volatile compounds (VOC) like ammonia and methanol. By using polyvinylidene fluoride (PVDF) as the main compound, inhibiting interactions between the complex and polymer were minimized. By using UV-Vis spectroscopy, the visible and reversible switching between HS and LS state when exposed to an ammonia or hydrochloric acid atmosphere was confirmed. Powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM) and energy dispersive X-Ray spectroscopy (EDX) show a homogenous distribution of FeH2btm with no major crystalline accumulations and a mean fiber diameter of 106±20 nm. The composite fiber has a similarly high thermal stability as the pure FeH2btm, as shown by thermogravimetric analysis (TGA). Mössbauer spectroscopy indicates an incomplete spin transition after exposition to ammonia. This could be due to low permeability of the VOC into the composite fiber.

The Cover Feature shows working miners, thus reflecting the importance of mining in Guanajuato (México) for the last five centuries. As an analogy to these efforts and their success, our contribution shows for the first time that Ir^I and Ir^III organometallic precursors can be bonded to the SacNac ligand, in bi- and monodentate flexible coordination modes. A fruitful catalytical hydroboration of styrene with neopentylglycolborane is reported too. More information can be found in the Research Article by J. Campos, O. Serrano, C. Cristobal and co-workers.

The Front Cover shows a novel water-soluble copper catalyst (NH₄)₈[Cu₂(H₂O)₈W₁₂O₄₂], synthesized via undecatungstate formed in situ. It efficiently oxidizes cyclohexanol to cyclohexanone by using H₂O₂ in water at 35 °C and ambient pressure, achieving 98 % yield. It can also catalyze the oxidation of other secondary alcohols, potentially affording an economical, green, and efficient ketone production method for industrial use. More information can be found in the Research Article by Z. Wei, G. Yang, and Y. Wei.

Four organometallic complexes featuring identical conjugated diimine ligands and varying transition metal centers (Rh(III), Ir(III), Ru(II), and Os(II)) were synthesized. A comprehensive investigation of the photophysical properties of these complexes and their corresponding diimine ligands was conducted by UV-vis absorption, emission, and transient absorption (TA) spectroscopy, as well as optical power limiting (OPL) measurements. The incorporation of fluorene components with alkyl chains enhanced the π-conjugation of the ligand, prevented intermolecular π-π stacking, and improved complex solubility. The diimine ligands showed a slight solvation effect in their emission spectra, indicating that the main property of their emissive state was intramolecular charge transfer (CT). According to the valence states of the four complexes, they can be divided into two classes (Rh(III), Ir(III)) and (Ru(II), Os(II)). For TA spectrum, the former group exhibited positive ΔOD values across the 400~800 nm range, while the latter showed large inverted peaks at 420~500 nm due to significant ground-state absorption in this wavelength range. Additionally, the optical limiting conduct of the complexes observed the order: 1 d>1 a>1 c>1 b. Complex 1 d exhibits powerful reverse saturable absorption (RSA) properties at 532 nm and could probably be used as an wonderful nonlinear absorbing material.

Materials based on small molecules characterized by multi-component short and long-lived emissive behaviour are extremely desirable for various applications. The derivative of cyclic triimidazole (TT) functionalized with a carboxylic group, namely TT-COOH, is isolated, investigated and used as coordinative ligand to obtain a series of isomorphous mononuclear complexes of general formula [M(TT-COO)₂(H₂O)₂] (M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)). Crystals of TT-COOH display aggregation induced enhanced emission (AIEE) comprising dual fluorescence and dual phosphorescence of molecular origin together with an aggregation induced long lived, low energy phosphorescence. Emissive features are retained in crystals of the Zn(II) and Cd(II) complexes, where the metal plays the role of an external heavy atom perturber, but strongly quenched in the others. The mechanisms involved in the photophysics of TT-COOH and its metal complexes have been disclosed thanks to combined structural, spectroscopic and computational investigations which reveal the presence of anti-Kasha emissions.

Unsymmetrically N,N’-substituted metal amides of silicon, germanium and aluminium were synthesized starting from N-ethyl-2-(n-propylaminomethyl)phenylamine (1, Et,ⁿPr-ampaH₂). Reaction of the dilithium compound of 1 with SiCl₄ gave spirocyclic Si(Et,ⁿPr-ampa)₂ (2) and Cl₂Si(Et,ⁿPr-ampa) (3). Reduction of 3 with potassium resulted in the formation of the corresponding cyclotetrasilane [Si(Et,ⁿPr-ampa)]₄ (4), whereas the reaction of 3 with lithium triethylborohydride gave the dihydro silane H₂Si(Et,ⁿPr-ampa) (5). The corresponding germanium(IV) compounds Ge(Et,ⁿPr-ampa)₂ (6) and Cl₂Ge(Et,ⁿPr-ampa) (7) were synthesized starting from GeCl₄, amine 1 and NEt₃ using appropriate stoichiometric ratios. Reaction of Ge[N(SiMe₃)₂]₂ with amine 1 provided the germylene [Ge(Et,ⁿPr-ampa)]₂ (8). The aluminium dichloro compound Cl₂Al(Et,ⁿPr-ampaH) (9) was obtained either by reaction of the dichlorogermine 7 with lithium aluminium hydride or by reaction of the dilithium salt of 1 with AlCl₃. Reaction of trimethylaluminium with amine 1 provided the amido-amine (CH₃)₂Al(Et,ⁿPr-ampaH) (10) which was converted into the diamide CH₃Al(Et,ⁿPr-ampa) (11) by methane elimination.

The solid-state syntheses and the structures of three new europium carbodiimide chlorides are reported: Eu₄(NCN)₃Cl₃=Eu⁽³⁺⁾Eu₃⁽²⁺⁾(NCN)₃Cl₃ (1), LiEu₂(NCN)Cl₃ (2) and Na₂Eu₁₄(NCN)₃Cl₂₄ (3). 1 is the second example of mixed-valent rare-earth carbodiimide after Eu₄F₅(NCN)₂. 2 belongs to a group of mixed carbodiimide compounds related to the Bideauxite group. 3 being the first Na-containing rare-earth carbodiimide. Syntheses in the field of rare-earth carbodiimides benefit from the usage of different alkali carbodiimides to direct reaction pathway into individual compounds. High-yield syntheses of 1–3, their crystal structures, and the photoluminescence properties of 3 are reported.

We reported here a one-step chemical route to prepare nanocomposites comprising CuS nanophases supported on GO sheets with magnetic properties. The synthesis reported here combines such materials in single-nanostructures that show morphological features well-suited for wastewater treatment. The photocatalytic performance of CuS/GO nanocomposites was first investigated towards the removal of a common organic dye (rhodamine B) and sulfamethoxazole (SMX), which is an antibiotic considered a water contaminant of emerging concern. The RhB and SMX adsorption efficiency of CuS/GO and Fe₃O₄/GO/CuS hybrids, as well as of CuS particles, was significantly higher than GO or Fe₃O₄/GO. Overall, the CuS-based magnetic and CuS/GO hybrids have shown the capacity to uptake more than 80 % of RhB or SMX, after 120 minutes. Under blue-led irradiation, almost complete degradation of RhB was achieved in the presence of CuS/Fe₃O₄/GO, after 180 minutes; and higher than 85 % degradation of SMX, after 240 minutes of irradiation. The photocatalytic behaviour of nanocomposites was best described by the first–order kinetic model, for which k values for degradation of RhB and SMX followed the order: CuS/Fe₃O₄/GO>CuS/GO>CuS. The tricomponent CuS/Fe₃O₄/GO can be easily recovered after use and be reused maintain their high photocatalytic performance, thus providing a sustainable and cost-effective hybrid solution for water treatment.

The Front Cover shows the molecular structures of two ruthenium–indane complexes: one is a binuclear Ru complex bridged by 1,2-bis(diphenylphosphino)ethane (dppe) ligand and the other is a mononuclear chelating 1,3-bis(diphenylphosphino)propane (dppp) complex. For the mononuclear complex, the Ru−P (P trans to In) bond distance (2.4076(11) Å) is shorter than the Ru−P (P trans to CO) one (2.4227(11) Å). It is known that both InCl₃ and CO exhibit electron-withdrawing properties, but no comparison of their electron-withdrawing strengths has been reported. This result is the first to show that the InCl₃ ligand withdraws electron density from Ru more strongly than the CO ligand. In addition, the mononuclear Ru−In complexes exhibit catalytic activity for the double hydrosilylation of organonitriles. More information can be found in the Research Article by M. Itazaki and co-workers.

In this work, a linear-hexaborane(8) B₆(NMe₂)₆(CH₂SiMe₃)₂ was synthesized using a new method. By replacing one chlorine atom of Cl₂B₃(NMe₂)₃ with CH₂SiMe₃ group, compound ClB₃(NMe₂)₃CH₂SiMe₃ was prepared. Reductive dehalogenative coupling of ClB₃(NMe₂)₃CH₂SiMe₃ led to linear-hexaborane(8). Moreover, the six-membered boron ring, cyclo-hexaborane B₆(NEt₂)₆ was synthesized by reductive dehalogenation of Br₂BNEt₂. The first linear-hexaborane(8) and cyclo-hexaborane B6(NEt₂)₆ crystal structures were fully characterized by X-ray structural analysis and ¹¹B, ¹H, and ¹³C NMR spectroscopy. While the B₁⋅⋅⋅B₆ chain in linear-hexaborane(8) is strongly twisted at all B−B bonds, the B₆ ring cyclo-hexaborane B₆(NEt₂)₆ has a chair conformation similar to cyclohexane.