Search Results (5)

This paper presents the results of the first application of N,N'-bis(salicylidene)ethylenediamine (salen) as an extractant in classical liquid–liquid extraction and as a carrier in membrane processes designed for the recovery of noble metal ions (Pd²⁺, Ag⁺, Pt²⁺, and Au³⁺) from aqueous solutions. In the case of the utilization of membranes, both sorption and desorption were investigated. Salen has not been used so far in the sorption processes of precious metal ions. Recovery experiments were performed on single-component solutions (containing only one type of metal ions) and polymetallic solutions (containing ions of all four metals). The stability constants of the obtained complexes were determined spectrophotometrically. In contrast, electrospray ionization high-resolution mass spectrometry (ESI-HRMS) was applied to examine the elemental composition and charge of the generated complexes of chosen noble metal ions and salen molecules. The results show the great potential of N,N'-bis(salicylidene)ethylenediamine as both an extractant and a carrier. In the case of single-component solutions, the extraction percentage was over 99% for all noble metal ions (molar ratio M:L of 1:1), and in the case of a polymetallic solution, it was the lowest, but over 94% for platinum ions and the highest value (over 99%) for gold ions. The percentages of sorption (%Rs) of metal ions from single-component solutions using polymer membranes containing N,N'-bis(salicylidene)ethylenediamine as a carrier were highest after 24 h of the process (93.23% for silver(I) ions, 74.99% for gold(III) ions, 69.11% and 66.13% for palladium(II) and platinum(II) ions, respectively), similar to the values obtained for the membrane process conducted in multi-metal solutions (92.96%, 84.26%, 80.94%, and 48.36% for Pd(II), Au(III), Ag(I), and Pt(II) ions, respectively). The percentage of desorption (%R_des) was very high for single-component solutions (the highest, i.e., 99%, for palladium solution and the lowest, i.e., 88%, for silver solution), while for polymetallic solutions, these values were slightly lower (for Pt(II), it was the lowest at 63.25%). Full article

This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the composition [Fe(L)₂]X (L = 3,6-bis[(3′,6′-di-tert-butyl-9-carbazol)-9-carbazol]benzoyloxy-4-salicylidene-N′-ethyl-N-ethylenediamine, X = NO₃⁻, Cl⁻, PF₆⁻) were synthesized by the reaction of metal salts with Schiff bases in a mixture of solvents. The UV–Vis absorption properties were studied in dichloromethane and rationalized via time-dependent density functional theory (DFT) calculations. Upon excitation at 350 nm, the compounds exhibited an intense dual fluorescence with two emission bands centered at ~445 and ~485 nm, which were assigned to π_carb–π* intraligand and π_carb–d_Fe ligand-to-metal charge-transfer excited states. EPR spectroscopy and SQUID magnetometry revealed solid-state partial spin crossover in some compounds, and antiferromagnetic interactions between the neighboring Fe(III) ions. Full article

In total, 13 ligands R-salen (N,N’-bis(5-R-salicylidene)ethylenediamine (where R = MeO, Me, OH, H, Cl, Br, NO₂) and R-salphen (N,N’-bis(5-R-salicylidene)-1,2-phenylenediamine (where R = MeO, Me, OH, H, Cl, Br) and their 13 nickel complexes NiRsalen and NiRsalphen were synthesized and characterized using IR (infrared) spectroscopy, mass spectrometry, elemental analysis, magnetic susceptibility, NMR (nuclear magnetic resonance), UV-vis (ultraviolet-visible) spectroscopy, cyclic voltammetry, and X-ray crystal diffraction. Previous studies have shown that all complexes have presented a square planar geometry in a solid state and as a solution (DMSO). In electrochemical studies, it was observed that in N/N aliphatic bridge complexes, the Ni^II underwent two redox reactions, which were quasi-reversible process, and the half-wave potential followed a trend depending on the ligand substituent in the 5,5’-R position. The electron-donor substituent—as -OH, and -CH₃ decreased the E_1/2 potential—favored the reductor ability of nickel. The crystals of the complexes NiMesalen, NiMeOsalen, NiMeOsalphen, and Nisalphen were obtained. It was shown that the crystal packaging corresponded to monoclinic systems in the first three cases, as well as the triclinic for Nisalphen. The Hirshfeld surface analysis showed that the packaging was favored by H∙∙∙H and C∙∙∙H/H∙∙∙C interactions, and C-H∙∙∙O hydrogen bridges when the substituent was -MeO and π-stacking was added to an aromatic bridge. Replacing the N/N bridge with an aromatic ring decreased distortion in square-planar geometry where the angles O-Ni-N formed a perfect square-planar. Full article

In this paper, three main methods of metal ion separation, i.e., liquid–liquid extraction, transport across polymer inclusion membranes (PIMs), and sorption/desorption, are described. In all of them, N,N’-bis(salicylidene)ethylenediamine (salen) was used as an active compound, i.e., as an extractant or as a carrier for the recovery of Ni(II), Cu(II), or Zn(II) ions from aqueous solutions. In each case, the recovery was performed on a model solution, which contained only a single metal ion. The obtained results were compared with the author’s previous results for the separation of metal ions using β-diketones, since both β-diketones and salen form the so-called Werner-type complexes. Electrospray ionization high-resolution mass spectrometry (ESI-HRMS) was also applied to confirm the ability of the carrier to form complexes with metal ions in a solution. Moreover, spectrophotometry was used to determine the stability constant of the obtained complexes. Full article

Salen ligands are a class of Schiff bases simply obtained through condensation of two molecules of a hydroxyl-substituted aryl aldehyde with an achiral or chiral diamine. The prototype salen, or N,N′-bis(salicylidene)ethylenediamine has a long history, as it was first reported in 1889, and immediately, some of its metal complexes were also described. Now, the salen ligands are a class of N,N,O,O tetradentate Schiff bases capable of coordinating many metal ions. The geometry and the stereogenic group inserted in the diamine backbone or aryl aldehyde backbone have been utilized in the past to efficiently transmit chiral information in a variety of different reactions. In this review we will summarize the important and recent achievements obtained in stereocontrolled reactions in which Al(salen) metal complexes are employed. Several other reviews devoted to the general applications and synthesis of chromium and other metal salens have already been published. Full article