Search Results (21)

Three new asymmetrically coordinated lanthanide derivatives based on the bicompartmental salen-type ligands N,N′-bis(3-ethoxysalicylidene)propylene-1,3-diamine (H₂EtOsalpr) and 3-ethoxysalicylaldehyde (HEtvain) have been synthesized and structurally and photophysically characterized. All the compounds show dimeric structures of the general formula [Ln(H₂EtOsalpr)(NO₃)₂(Etvain)]₂ (Ln = Nd, Eu, Dy), with each salen-type ligand bridging two lanthanide ions. The Etvain ligand comes from the H₂EtOsalpr decomposition being coordinated to the corresponding lanthanide. The Nd(III) derivative shows fluorescence emission in the NIR region, but for the Eu(III) and Dy(III) compounds, only a broad band, attributed to the ligand emission, was observed. Full article

This review summarizes the structural characteristics and physicochemical properties of chiral 4f and 3d-4f complexes based on enantiopure salen-type Schiff base ligands. The chirality originates from the enantiopure diamines and is imparted to the Schiff base ligands and complexes and finally to the crystal structures. The reported enantiopure Schiff base ligands derive from the condensation of aromatic aldehydes, such as salicylaldehyde and its various derivatives, and the enantiopure diamines, (1R,2R) or (1S,2S)-1,2-diamino-cyclohexane, (1R,2R) or (1S,2S)-1,2-diamino-1,2-diphenylethane, (R) or (S)-2,2′-diamino-1,1′-binaphthalene, and 1,2-diaminopropane. Full article

Salen, Salan, and Salalen chromium (III) chloride complexes have been investigated as catalysts for the ring-opening copolymerization reactions of cyclohexene oxide (CHO) with CO₂ and of phthalic anhydride (PA) with limonene oxide (LO) or cyclohexene oxide (CHO). In the production of polycarbonates, the more flexible skeleton of salalen and salan ancillary ligands favors high activity. Differently, in the copolymerization of phthalic anhydride with the epoxides, the salen complex showed the best performance. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures from mixtures of CO₂, cyclohexene oxide, and phthalic anhydride with all complexes. In addition, all chromium complexes were revealed to be very active in the chemical depolymerization of polycyclohexene carbonate producing cyclohexene oxide with high selectivity, thus offering the opportunity to close the loop on the life of these materials. Full article

The tetranuclear iron(III) compounds [Fe₄(μ₃-O)₂(μ-L^Z)₄] (1–3) were obtained by reaction of FeCl₃ with the shortened salen-type N₂O₂ tetradentate Schiff bases N,N’-bis(salicylidene)-o-Z-phenylmethanediamine H₂L^Z (Z = NO₂, Cl and OMe, respectively), where the one-carbon bridge between the two iminic nitrogen donor atoms guide preferentially to the formation of oligonuclear species, and the ortho position of the substituent Z on the central phenyl ring selectively drives towards Fe₄ bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe₄(μ₃-O)₂} core, surrounded by the four Schiff base ligands, as depicted by both the X-ray molecular structures of 1 and 2 and the optimized geometries of all derivatives as obtained by UM06/6-311G(d) DFT calculations. The strength of the antiferromagnetic exchange coupling constants between the iron(III) ions varies among the three derivatives, despite their magnetic cores remain structurally almost unvaried, as well as the coordination of the metal ions, with a distorted octahedral environment for the two-body iron ions, Fe_b, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Fe_w. The different magnetic behavior within the series of examined compounds may be ascribed to the influence of the electronic features of Z on the electron density distribution (EDD) of the central {Fe₄(μ₃-O)₂} core, substantiated by a Quantum Theory of Atoms In Molecules (QTAIM) topological analysis of the EDD, as obtained by UM06 calculations 1–3. Full article

Conductive and electrochemically active polymers consisting of Salen-type metal complexes as building blocks are of interest for energy storage and conversion applications. Asymmetric monomer design is a powerful tool for fine-tuning the practical properties of conductive electrochemically active polymers but has never been employed for polymers of M(Salen)]. In this work, we synthesize a series of novel conducting polymers composed of a nonsymmetrical electropolymerizable copper Salen-type complex (Cu(3-MeOSal–Sal)en). We show that asymmetrical monomer design provides easy control of the coupling site via polymerization potential control. With in-situ electrochemical methods such as UV-vis-NIR (ultraviolet-visible-near infrared) spectroscopy, EQCM (electrochemical quartz crystal microbalance), and electrochemical conductivity measurements, we elucidate how the properties of these polymers are defined by chain length, order, and cross-linking. We found that the highest conductivity in the series has a polymer with the shortest chain length, which emphasizes the importance of intermolecular iterations in polymers of [M(Salen)]. Full article

This review presents representative examples illustrating how the Lewis acidic character of the Zn(II) metal center in Zn(salen)-type complexes, as well as in complexes of other tetradentate ligands, and the nature of the medium govern their supramolecular aggregation, leading to the formation of a variety of supramolecular structures, either in solution or in the solid state. Stabilization of these Lewis acidic complexes is almost always reached through an axial coordination of a Lewis base, leading to a penta-coordinated square-pyramidal geometry around the metal center. The coverage is not exhaustive, mainly focused on their crystallographic structures, but also on their aggregation and sensing properties in solution, and on their self-assembled and responsive nanostructures, summarizing their salient aspects. The axial ligands can easily be displaced, either in solution or in the solid state, with suitable Lewis bases, thus being responsive supramolecular structures useful for sensing. This contribution represents the first attempt to relate some common features of the chemistry of different families of Zn(II) complexes of tetradentate ligands to their intrinsic Lewis acidic character. Full article

In this work, over 500 structures of tri-ring aromatic Schiff bases with different substitution patterns were investigated to develop a unified description of the substituent effect on the intramolecular hydrogen bridge. Both proximal and distal effects were examined using Density Functional Theory (DFT) in the gas phase and with solvent reaction field (Polarizable Continuum Model (PCM) and water as the solvent). In order to investigate and characterize the non-covalent interactions, a topological analysis was performed using the Quantum Theory of Atoms In Molecules (QTAIM) theory and Non-Covalent Interactions (NCI) index. The obtained results were summarized as the generalized, empirical model of the composite substituent effect, assessed using an additional group of simple ring-based Schiff bases. The composite substituent effect has been divided into separate increments describing the different interactions of the hydrogen bridge and the substituent: the classical substituent effect, involving resonance and induction mediated through the ring, steric increment based on substituent proximity to the bridge elements, and distal increment, derived from substitution on the distal ring. Full article

New heterotrinuclear complexes with the general formula [Cu₂Ln(H₂L)(HL)(NO₃)₂]·MeOH (Ln = Ho (1), Er (2), H₄L = N,N′-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane) were synthesized using compartmental Schiff base ligand in conjugation with auxiliary ligands. The compounds were characterized by elemental analysis, ATR-FTIR spectroscopy, X-ray diffraction, TG, DSC, TG-FTIR and XRD analysis. The N₂O₄ salen-type ligand coordinates 3d and 4f metal centers via azomethine nitrogen and phenoxo oxygen atoms, respectively, to form heteropolynuclear complexes having CuO₂Ln cores. In the crystals 1 and 2, two terminal Cu(II) ions are penta-coordinated with a distorted square-pyramidal geometry and a Ln^III ion with trigonal dodecahedral geometry is coordinated by eight oxygen atoms from [Cu^II(H₂L)(NO₃)]⁻ and [Cu^II(HL)(NO₃)]²⁻ units. Compounds 1 and 2 are stable at room temperature. During heating, they decompose in a similar way. In the first decomposition step, they lose solvent molecules. The exothermic decomposition of ligands is connected with emission large amounts of gaseous products e.g., water, nitric oxides, carbon dioxide, carbon monoxide. The final solid products of decomposition 1 and 2 in air are mixtures of CuO and Ho₂O₃/Er₂O₃. The measurements of magnetic susceptibilities and field dependent magnetization indicate the ferromagnetic interaction between Cu^II and Ho^III ions 1. Full article

Here, we describe the synthesis, characterization, and in vitro biological evaluation of a series of transition metal complexes containing benzothiazole aniline (BTA). We employed BTA, which is known for its selective anticancer activity, and a salen-type Schiff-based ligand to coordinate several transition metals to achieve selective and synergistic cytotoxicity. The compounds obtained were characterized by NMR spectroscopy, mass spectrometry, Fourier transform infrared spectroscopy, and elemental analysis. The compounds L, MnL, FeL, CoL, and ZnL showed promising in vitro cytotoxicity against cancer cells, and they had a lower IC₅₀ than that of the clinically used cisplatin. In particular, MnL had synergistic cytotoxicity against liver, breast, and colon cancer cells. Moreover, MnL, CoL, and CuL promoted the production of reactive oxygen species in HepG2 tumor cell lines. The lead compound of this series, MnL, remained stable in physiological settings, and docking results showed that it interacted rationally with the minor groove of DNA. Therefore, MnL may serve as a viable alternative to platinum-based chemotherapy. Full article

Most non-metalized Salen-type ligands form passivation thin films on electrode surfaces upon electrochemical oxidation. In contrast, the H₂(3-MeOSalen) forms electroactive polymer films similarly to the corresponding nickel complex. There are no details of electrochemistry, doping mechanism and charge transfer pathways in the polymers of pristine Salen-type ligands. We studied a previously uncharacterized electrochemically active polymer of a Salen-type ligand H₂(3-MeOSalen) by a combination of cyclic voltammetry, in situ ultraviolet–visible (UV–VIS) spectroelectrochemistry, in situ electrochemical quartz crystal microbalance and Fourier Transform infrared spectroscopy (FTIR) spectroscopy. By directly comparing it with the polymer of a Salen-type nickel complex poly-Ni(3-MeOSalen) we elucidate the effect of the central metal atom on the structure and charge transport properties of the electrochemically doped polymer films. We have shown that the mechanism of charge transfer in the polymeric ligand poly-H₂(3-MeOSalen) are markedly different from the corresponding polymeric nickel complex. Due to deviation from planarity of N₂O₂ sphere for the ligand H₂(3-MeOSalen), the main pathway of electron transfer in the polymer film poly-H₂(3-MeOSalen) is between π-stacked structures (the π-electronic systems of phenyl rings are packed face-to-face) and C-C bonded phenyl rings. The main way of electron transfer in the polymer film poly-Ni(3-MeOSalen) is along the polymer chain, while redox processes are ligand-based. Full article

Conductive polymers are widely used as active and auxiliary materials for organic photovoltaic cells due to their easily tunable properties, high electronic conductivity, and light absorption. Several conductive polymers show the cathodic photogalvanic effect in pristine state. Recently, photoelectrochemical oxygen reduction has been demonstrated for nickel complexes of Salen-type ligands. Herein, we report an unexpected inversion of the photogalvanic effect caused by doping of the NiSalen polymers with anionic porphyrins. The observed effect was studied by means of UV-Vis spectroscopy, cyclic voltammetry and chopped light chronoamperometry. While pristine NiSalens exhibit cathodic photopolarization, doping with porphyrins inverts the polarization. As a result, photoelectrochemical oxidation of the ascorbate proceeds smoothly on the NiSalen electrode doped with zinc porphyrins. The highest photocurrents were observed on NiSalen polymer with o-phenylene imine bridge, doped with anionic zinc porphyrin. Assuming this, porphyrin serves both as a catalytic center for the oxidation of ascorbate and an internal electron donor, facilitating the photoinduced charge transport and anodic depolarization. Full article

The reaction of organic molecules mediated by a metal center (template synthesis) can result in a final connectivity that may differ from the one obtained in the absence of the metal. The condensation of carbonyl fragments with primary amines form C=N iminic bonds, the so-called Schiff bases, which can act as ligands for the templating metal center by means of the lone pair on the nitrogen atom. This review focuses on the template methods for the reaction between a carbonyl compound (mainly salicylaldehyde) and a primary aliphatic diamine able to prevent the double condensation on both amine groups and obtain tridentate N₂O ligands. These adducts, still having one free amino group, can further react, yielding tetradentate salen-type Schiff base ligands. A screening over the transition metals able to show such a template effect will be presented, with particular attention to copper(II), together with their peculiar reactivity and the available crystal structure of the metal complexes and related coordination geometries. Full article

The reactivity of the shortened salen-type ligands H₃salmp, H₂salmen and H₂sal(p-X)ben with variable para-substituent on the central aromatic ring (X = tBu, Me, H, F, Cl, CF₃, NO₂) towards the trivalent metal ions manganese(III) and iron(III) is presented. The selective formation of the dinuclear complexes [M₂(μ-salmp)₂], M = Mn (1a), Fe (2a), [M₂(μ-salmen)₂(μ-OR)₂)], R = Et, Me, H and M = Mn (3a–c) or Fe (4a–c), and (M₂(μ-sal[p-X]ben)₂(μ-OMe)₂), X = tBu, Me, H, F, Cl, CF₃, NO₂ and M = Mn (5a–g) or Fe (6a–g), could be identified by reaction of the Schiff bases with metal salts and the base NEt₃, and their characterization through elemental analysis, infrared spectroscopy, mass spectrometry and single-crystal X-ray diffraction of 2a·2AcOEt, 2a·2CH₃CN and 3c·2DMF was performed. In the case of iron(III) and H₃salmp, when using NaOH as a base instead of NEt₃, the dinuclear complexes [Fe₂(μ-salmp)(μ-OR)(salim)₂], R = Me, H (2b,c) could be isolated and spectroscopically characterized, including the crystal structure of 2b·1.5H₂O, which showed that rupture of one salmp³⁻ to two coordinated salim⁻ ligands and release of one salH molecule occurred. The same hydrolytic tendency could be identified with sal(p-X)ben ligands in the case of iron(III) also by using NEt₃ or upon standing in solution, while manganese(III) did not promote such a C–N bond breakage. Cyclic voltammetry studies were performed for 3b, 4b, 5a and 6a, revealing that the iron(III) complexes can be irreversibly reduced to the mixed-valence Fe^IIFe^III and Fe^II₂ dinuclear species, while the manganese(III) derivatives can be reversibly oxidized to either the mixed-valence Mn^IIIMn^IV or to the Mn^IV₂ dinuclear species. The super-exchange interaction between the metal centers, mediated by the bridging ligands, resulted in being antiferromagnetic (AFM) for the selected dinuclear compounds 3b, 4b, 5a, 5e,5f, 6a and 6e. The coupling constants J (–2JŜ₁·Ŝ₂ formalism) had values around −13 cm⁻¹ for manganese(III) compounds, among the largest AFM coupling constants reported so far for dinuclear Mn^III₂ derivatives, while values between −3 and −10 cm⁻¹ were obtained for iron(III) compounds. Full article

Manganosalen complexes are coordination compounds that possess a chelating salen-type ligand, a class of bis-Schiff bases obtained by condensation of salicylaldehyde and a diamine. They may act as catalytic antioxidants mimicking both the structure and the reactivity of the native antioxidant enzymes active site. Thus, manganosalen complexes have been shown to exhibit superoxide dismutase, catalase, and glutathione peroxidase activities, and they could potentially facilitate the scavenging of excess reactive oxygen species (ROS), thereby restoring the redox balance in damaged cells and organs. Initial catalytic studies compared the potency of these compounds as antioxidants in terms of rate constants of the chemical reactivity against ROS, giving catalytic values approaching and even exceeding that of the native antioxidative enzymes. Although most of these catalytic studies lack of biological relevance, subsequent in vitro studies have confirmed the efficiency of many manganosalen complexes in oxidative stress models. These synthetic catalytic scavengers, cheaper than natural antioxidants, have accordingly attracted intensive attention for the therapy of ROS-mediated injuries. The aim of this review is to focus on in vivo studies performed on manganosalen complexes and their activity on the treatment of several pathological disorders associated with oxidative damage. These disorders, ranging from the prevention of fetal malformations to the extension of lifespan, include neurodegenerative, inflammatory, and cardiovascular diseases; tissue injury; and other damages related to the liver, kidney, or lungs. Full article

To identify the effects of halogen bonding in the architecture of Schiff base complex supramolecular networks, we introduced halogenated Schiff-base 3-Br-5-Cl-salen as ligand and isolated a new salen-type manganese(III) complex [Mn^III(Cl)(H₂O)(3-Br-5-Cl-salen)] (1) where 3-Br-5-Cl-salen = N,N’-bis(3-bromo-5-chlorosalicylidene)-1,2-diamine. The complex was investigated in the solid-state for halogen bonds (XBs) by single crystal X-ray structure analysis. Meanwhile, theoretical calculations were carried out to rationalize the formation mechanism of different types of XBs in the complex. The analysis result of electronic structure of the halogen bonds indicated that the chlorine atom coordinated to the Mn(III) center possesses the most negative potential and acts as anionic XB acceptor (electron donor) to the adjacent substituted halogens on the ligand, meanwhile the intermolecular Mn-Cl···X-C halogen bonding plays a significant role in directing the packing arrangement of adjacent molecules and linking the 2D layers into a 3D network. In order to verify the above results and acquire detailed information, the title complex was further analyzed by using the Hirshfeld surface analyses. Full article