Di-ionizable calix[4]arene-1,2-crown-5 and -crown-6 ethers in cone conformations: synthesis and divalent metal ion extraction

Two series of di-ionizable calix[4]arene-1,2-crown-5 and -crown-6 ethers in cone conformations are synthesized. The ionizable groups are oxyacetic acid moieties and N-(X)sulfonyl oxyacetamide units with X=methyl, phenyl, 4-nitrophenyl, and trifluoromethyl, which ‘tunes’ their acidity. For competitive solvent extraction of alkaline earth metal cations from aqueous solutions into chloroform, the new ligands with N-(X)sulfonyl carbamoyl groups are efficient extractants with Ba²⁺ selectivity. On the other hand, the dicarboxylic acid analogues exhibit little selectivity in extraction of alkaline earth metal cations. For single species extractions of Pb²⁺, the ligands with both types of ionizable groups show very good extractions abilities. In single species extractions of Hg²⁺, the N-(X)sulfonyl carboxamide ligands are highly efficient, in contrast to the dicarboxylic acid compounds. Influences of the ionizable group identity, the crown ether ring size, and the presence of upper-rim p-tert-butyl groups on divalent metal ion extraction are explored.     

Lower-rim versus upper-rim functionalization in di-ionizable calix[4]arene-crown-5 isomers. Synthesis and divalent metal ion extraction

Two series of di-ionizable calix[4]arene-crown-5 isomers in the cone conformation are synthesized to probe the effect of the pendant acidic group location on their metal ion extraction properties. In one series, the ionizable groups are attached to the lower rim of the calix[4]arene scaffold, which orients them near the crown ether cavity. In the second series, the ionizable groups are connected to the upper rim positioning them away from the crown ether ring, but close to the hydrophobic pocket of the calix[4]arene unit. The metal ion extraction behaviors of the two series of ligands are compared in extractions of alkaline earth metal cations, Hg²⁺, and Pb²⁺.     

Synthesis and spectroscopic properties of Schiff bases derived from 3-hydroxy-4-pyridinecarboxaldehyde

A series of six new Schiff bases has been prepared by reacting aniline and 4-R-substituted anilines (R=CH₃, OCH₃, Br, Cl, NO₂) with 3-hydroxy-4-pyridinecarboxaldehyde. The ¹H, ¹³C, ¹⁵N and ¹⁷O NMR data of these compounds are used to discuss the tautomerism. ¹⁵N NMR and ¹⁷O NMR chemical shifts established the tautomer existing in solution as the hydroxy/imino. ¹³C CPMAS NMR confirms that the same tautomer is found in the solid state. The stabilities of the tautomeric forms have been approached using density functional calculations (B3LYP/6-31G**) in the gas phase. In all cases the neutral hydroxy/imino with E configuration is more stable than the oxo/enamino form (by ∼22 kJ mol⁻¹) and significantly more stable than the betaine (by ∼75 kJ mol⁻¹).     

An NMR study of the stoichiometry and stability of lithium ion complexes with 12-crown-4, 15-crown-5 an 18-crown-6 in binary Acetonitrile-Nitrobenzene mixtures

Proton NMR spectroscopy was used to study the complexation reaction between lithium ion and 12-crown-4, 15-crown-5 and 18-crown-6 in a number of binary acetonitrile-nitrobenzene mixtures. In all cases the exchange between free and complexed crowns was fast on the NMR time scale and only a single population average¹H signal was observed. Formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of acetonitrile in the mixed solvent. It was found that, in all solvent mixtures used, 15-crown-5 forms the most stable complex with Li⁺ ion in the series.     

Syntheses, spectroscopic characterization and metal ion binding properties of benzo-15-crown-5 derivatives and their sodium and nickel(II) complexes

New benzo-15-crown-5 derivatives containing nitro, amine and imine groups were prepared. Nitro compound (1) was prepared after the reaction?4′,5′-bis(bromethyl)benzo-15-crown-5 and o-nitrophenol in the presence of NaOH. After reduction process by using hydrazine hydrate and Pd/C amine compound (2) was formed. New crown ether imine compounds (3–5) were synthesized by the condensation of corresponding crown ether diamine (2) with salicylaldehyde derivatives. Sodium complexes of the crown compounds (1a–5a) form crystalline 1:1 (Na⁺: ligand) complexes with sodium perchlorate. Nickel(II) complexes (3b–5b) with 1:1 (Ni²⁺:ligand) stoichiometries were also been synthesized from the Schiff bases (3–5). The results indicated that the Schiff base ligands coordinated through the azomethine nitrogen and phenolic oxygen. The extraction ability of compounds (1, 3, 4 and 5) were also evaluated in chloroform by using several alkali and transition metal picrates such as Li⁺, Na⁺, K⁺, Cr³⁺, Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺.     

Synthesis,structural and spectroscopic properties of asymmetric Schiff bases derived from 2,3-diaminopyridine

Two Schiff base derivatives, 4-(2-amino-3-pyridyliminomethyl)phenol (I) and 3-(2-amino-3-pyridyliminomethyl)nitrobenzene (II), were synthesised and characterised by spectroscopy. The structure of I was determined by single crystal X-ray diffraction studies. The asymmetric Schiff base derived from 2,3-diaminopyridine selectively recognise transition and heavy metal cations, and some anion. Ligands I and II form stable complexes with Cu²⁺, Zn²⁺, Pb²⁺, Al³⁺ whereas ligand I also binds F~ ions. The stoichiometry for the host: cation is 1: 1 and 2: 1. The addition of F~ ion in CH₃CN to ligand I causes a colour change of the solution from colourless to yellow. The binding behaviour of ligand I towards several ions was investigated using density functional theory calculations.     

Simultaneous separation of common mono- and divalent cations on a zirconium-modified silica gel column by ion chromatography with non-suppressed conductimetric detection and tartaric acid–15-crown-5 as eluent

The application of laboratory-made zirconium-modified silica gels (Zr-silicas) as cation-exchange stationary phases to ion chromatography with conductimetric detection (IC–CD) for common mono- and divalent cations (Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) was carried out. Zr-silicas were prepared by the reaction of the silanol group on the surface of silica gel with zirconium tetrabutoxide (Zr(OCH₂CH₂CH₂CH₃)₄) in ethanol. Zr-silica adsorbed on 10 mg zirconium g⁻¹ silica gel was a suitable cation-exchange stationary phase in IC–CD for the separation of these mono- and divalent cations. Excellent simultaneous separation and highly sensitive detection for these cations were achieved in 10 min by IC–CD using a Zr-silica column (150×4.6 mm I.D.) and 10 mM tartaric acid containing 10 mM 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane) as the eluent. The proposed IC–CD method was successfully applied to the determination of major mono- and divalent cations in natural water samples.     

Synthesis and antibacterial activities of metal(II) complexes with Schiff bases derived from 3,5-diiodosalicylaldehyde

Two new Schiff bases (2,4-diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol and 2,4-diiodo-6-[(3-morpholin-4-yl-propylimino)-methyl]-phenol), condensed from 3,5-diiodosalicylaldehyde with 2-morpholinoethylamine and 3-morpholinopropylamine, have been designed and synthesized. Reaction of the Schiff bases with Zn(OAc)₂ · 2H₂O, Cu(OAc)₂ · H₂O, Ni(OAc)₂ · 4H₂O, Co(OAc)₂ · 4H₂O, Cd(OAc)₂ · 2H₂O, Mn(OAc)₂ · 4H₂O, Fe(SO4)₂ · 7H₂O, and Hg(OAc)₂ led to the formation of 16 new mononuclear complexes. The complexes were characterized by UV, Infrared, ESI-MS, and elemental analyses, and 3,5-diiodosalicylalidene-2-morpholinoethylaminozinc(II) (1) and 3,5-diiodosalicylalidene-2-morpholinoethylaminocopper(II) (2) were characterized by single crystal X-ray diffraction. Based on crystal structural analysis of 1 and 2, coupled with their spectral similarity with 3–16, it can be concluded that 3–16 have structures similar to 1 and 2. All the complexes were assayed for antibacterial activities against three Gram positive bacterial strains (Bacillus subtilis, Staphylococcus aureus, and Streptococcus faecalis) and three Gram negative bacterial strains (Escherichia coli, Pseudomonas aeruginosa, and Enterobacter cloacae) by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide method. Among the complexes tested, 8 and 16 showed the most favorable antibacterial activity with minimum inhibitory concentration of 0.781, 12.5, 6.25, 3.125, 3.125, 6.25 and 1.562, 6.25, 1.562, 3.125, 3.125, 1.562 µg mL^?1 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli, and E. cloacae, respectively.     

Simultaneous separation of common mono- and divalent cations on silica gel modified with aluminium by non-suppressed ion chromatography with conductimetric detection and nitric acid–15-crown-5 as eluent

The modification of silica gel with aluminium by a coating method was very effective for the preparation of silica-based stationary phases which acted as a cation exchanger under strongly acidic conditions. However, the separation of common mono- and divalent cations (Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) on an aluminium-adsorbing silica (Al-Silica) column was moderate by a conductimetric detection ion chromatography (IC) with strongly acidic eluents. Then, the addition of various crown ethers (12-crown-4, 15-crown-5 and 18-crown-6) in acidic eluent was carried out. As a result, it was found that 15-crown-5 was most effective for the improvement of peak resolution. Excellent separation of these cations was achieved in 20 min by elution with 2 mM nitric acid–2 mM 15-crown-5. The proposed IC was successfully applied to the determination of major cations in various natural waters.     

Synthesis, complexation properties and crystal structure of 4'''',5''''-dibromo-oxylyl-17-crown-5 ether

4',5'-Dibromo-o-xylyl-17-crown-5 ether (2BrB17C5) was synthesized,starting from 1,2-dibromo-4,5-bis(bromomethyl)-benzene and tetraethylene glycol,and was characterized by 1H NMR,MS and elemental analysis.Pale yellow prismatic single crystal obtained from anhydrous ethanol was investigated by X-ray structural analysis.The complexation properties toward alkali metal ions were examined using the solvent extraction method and UV absorption spectroscopy.The crown ether was found to be conformationally deformed and oblate-like and is highly selective for lithium ion.     

Structural,spectroscopic and redox properties of transition metal complexes of dipyrido[3,2-f:2′,3′-h]-quinoxaline (dpq)

The chemistry of first row transition metal complexes obtained from the ligand dipyrido[3,2-f:2′,3′-h]-quinoxaline (dpq) have been reported. The reaction between Cu(ClO₄)₂ · 6H₂O with dpq under different reaction conditions led to the isolation of three polymorphic copper(II) complexes [Cu(dpq)₂(H₂O)](ClO₄)₂ · H₂O (2), [Cu(dpq)₂(ClO₄)](ClO₄) (3) and [{Cu(dpq)₂(H₂O)}{Cu(dpq)₂(ClO₄)}](ClO₄)₃ (4). The bluish-green compound 2, obtained by reacting Cu(ClO₄)₂ · 6H₂O with dpq in methanol, has a distorted trigonal bipyramidal structure with τ = 0.55. The reaction between Cu(ClO₄)₂ · 6H₂O and dpq in dry acetonitrile produced the blue compound 3 in which the copper(II) centre has a distorted square planar geometry. When the condensation reaction between 1,10-phenanthroline-5,6-dione and 1,2-diaminoethane was carried out in the presence of Cu(ClO₄)₂ · 6H₂O in methanol, the green copper(II) complex 4 was isolated along with 1. The structure determination of 4 has established the presence of two different complex cations in the asymmetric unit and they are considered as co-crystals. In the zinc(II) compound [Zn(dpq)₂(ClO₄)₂] (5), the two perchlorates are unidentately coordinated to the metal centre, providing a distorted octahedral geometry. The quinoxaline ring in 5 is involved in intermolecular π–π interactions, leading to the generation of a sinusoidal chain. The proton NMR spectra, especially those of the paramagnetic complexes [Ni(dpq)₃](ClO₄)₂ (6) and [Co(dpq)₃](ClO₄)₂ (7), have been studied in detail. The electronic absorption spectra and the redox behaviour of the copper(I), copper(II), cobalt(II) and cobalt(III) complexes have been studied. The three copper(II) compounds 2–4 show identical absorption spectra and redox properties when measured in acetonitrile, although in nitromethane they show small but definite differences in their spectral and redox features.     

Synthesis,structural characterization,and antibacterial activity of mononuclear cobalt(III) azido complexes of two pentadentate Schiff bases derived from 2-hydroxynaphthaldehyde

The structural, spectroscopic, and electrochemical properties of [Co{(naph)₂dien}(N₃)] and [Co{(naph)₂dpt}(N₃)], where (naph)₂dien?=?bis-(2-hydroxy-1-naphthaldimine)-N-diethylenetriaminedianion and (naph)₂dpt?=?bis-(2-hydroxy-1-naphthaldimine)-N-dipropylenetriaminedianion have been investigated. These complexes are characterized by elemental analyses, IR, and UV–Vis spectroscopy. The crystal structures of these complexes have been determined by X-ray diffraction. The geometry around cobalt is distorted octahedral. The electrochemical behavior of these complexes in acetonitrile solution was also investigated. Both complexes show an irreversible Co^III–Co^II reduction at ca. ?0.8?V, accompanied by dissociation of the axial Co^II–N₃ bond. The in vitro antibacterial activities of these complexes were tested against Staphylococcus aureus and Bacillus licheniformis.     

Assembly of 12-tungstosilicic acid and 4-aminobenzo-15-crown-5 ether based on the electrostatic attraction through bridging of oxonium ions on different substrates

Based on the electrostatic attraction Keggin-type polyoxometalate H₄SiW₁₂O₄₀ (SiW₁₂) and small molecule 4-aminobenzo-15-crown-5 ether (4-AB15C5) were alternately deposited on poly (allylamine hydrochloride) (PAH)-derived indium tin oxide (ITO) substrate through a layer-by-layer (LBL) self-assembly, forming a supramolecular multilayer film (film-A). SiW₁₂ was also deposited on a glassy carbon electrode (GCE) derived by 4-AB15C5 via covalent bonding in 0.1 M NaCl aqueous solution and formed a composite monolayer film (film-B). UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy measurements demonstrated that the interactions between SiW₁₂ and 4-AB15C5 in both two film electrodes were the same and caused by the bridging action of oxonium ions. But, the nanostructure in the two film electrodes was different. 4-AB15C5 in film-A was oriented horizontally to ITO substrate, however, that in film-B was oriented vertically to GCE. Namely film-A corresponded to a layer structure, and film-B corresponded to an intercalation structure.     

Binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes with Schiff-bases derived from crown ether platforms: Rare examples of ether oxygen atoms bridging metal centers

Bibracchial lariat ethers L³ and L⁴, derived from the condensation of N,N′-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 or N,N′-bis(2-aminobenzyl)-4,13-diaza-18-crown-6 with salicylaldehyde, form binuclear complexes with Co(II), Ni(II), Cu(II) and Zn(II). Our studies show that the different denticity and crown moiety size of the two related receptors give rise to important differences on the structures of the corresponding complexes. Single crystal X-ray diffraction analysis shows that the [Ni₂(L³)(H₂O)₂]²⁺ and [Cu₂(L³)(NO₃)]⁺ complexes constitute a rare example in which an oxygen atom of the crown moiety is bridging the two six coordinate metal ions. In contrast, none of the oxygen atoms of the crown moiety is acting as a bridging donor atom in the [Co₂(L⁴)(CH₃CN)₂]²⁺, [Cu₂(L⁴)]²⁺ and [Zn₂(L⁴)]²⁺ complexes. This is attributed to the larger size the crown moiety and the higher denticity of L⁴ compared to L³. In [Co₂(L⁴)(CH₃CN)₂]²⁺ the metal ions show a distorted octahedral coordination, while in the Cu(II) and Zn(II) analogues the metal ions are five-coordinated in a distorted trigonal bipyramidal environment. In [Cu₂(L³)(NO₃)]⁺ the coordinated nitrate anion acts as a bidentate bridging ligand, which results in the formation of a 1D coordination polymer.     

Binuclear and polynuclear transition metal complexes with macrocyclic ligands. 5. Novel complexes of asymmetric polydentate macrocyclic Schiff bases. Step-by-step synthesis

Reactions of 2,6-bis(3-aminopropylaminocarbonyl)pyridine (1) with 4-tert-butyl-2,6-diformylphenol and 2,5-diformylpyrrole in the presence of Ba(ClO₄)₂ in EtOH afford barium complexes with asymmetric macrocyclic Schiff bases as soft and hard ligands. The reaction of compound 1 with Cu(OCOCMe₃)₂ involves closure of a tetrahydropyrimidine ring to give a mononuclear complex, which was structurally characterized by X-ray diffraction analysis.     

NMR studies of novel Schiff bases derived from L-alpha-amino methyl esters and 3-hydroxypyridin-4-carboxaldehyde

Schiff bases of 3-hydroxypyridin-4-carboxaldehyde and L-alpha-amino esters as well as those derived from the structurally related amines lacking the ester function have been synthesised. In two cases a tetrahydro-1H-imidazo[4,5-c]pyridine was formed as a by-product. (1)H, (13)C, (15)N-NMR spectral data and density functional theory (DFT) calculations established the structure of all compounds.     

Speciation of water-soluble titanium citrate: Synthesis,structural, spectroscopic properties and biological relevance

Titanium(IV) citrate complexes with different anions Na₃[Ti(H₂cit)₂(Hcit)] · 9H₂O (1), K₄[Ti(H₂cit)(Hcit)₂] · 4H₂O (2), K₅[Ti(Hcit)₃] · 4H₂O (3) and Na₇[TiH(cit)₃] · 18H₂O (4) (H₄cit = citric acid) were isolated in pure forms from the solutions of titanate and citrate at various pH values. X-ray structural analyses revealed the presence of a monomeric tricitrato titanium unit in the four complexes. Each Ti(IV) ion is coordinated octahedrally by the three citrate ligands in different protonated forms. The citrate ligand chelates bidentately to the titanium ion through its negatively charged α-alkoxy and α-carboxy groups. This is consistent with the large downfield ¹³C NMR shifts for the carbon atoms bearing the α-alkoxy and α-carboxy groups. The very strong hydrogen-bonds existing in the protonated and deprotonated β-carboxy groups may be the key factor for the stabilization of the titanium citrate complexes. When the pH value is lower than 7.0, ¹³C NMR spectra of 1:3 Ti:citrate solutions are similar to those of the titanium citrate complexes isolated at the corresponding pH values. The dissociation of free citrate increases with the rise of pH value. However, ¹³C NMR spectra of 1:3 Ti:citrate solutions indicate that there may exist different citrate titanium species when the pH value is higher than 7.0.     

Syntheses, characterizations and crystal structures of triorganotin(IV) derivatives with 2-mercapto-4-quinazolinone

The triorganotin(IV) derivatives of 2-mercapto-4-quinazolinone (HSqualone) of the type, R₃SnL (R = Ph 1, CH₃2, PhCH₂3, p-F-PhCH₂4, o-F-PhCH₂5, n-Bu 6), were obtained by the reaction of the R₃SnCl and HSqualone with 1:1 molar ratio in benzene. All complexes 1-6 were characterized by elemental analyses, IR, ¹H and ¹³C NMR spectroscopy and the crystal structures of complexes 1-3 were also confirmed by X-ray crystallography. The structure analyses reveal that the tin atoms of complexes 1-3 are all distorted tetrahedral geometries. Furthermore, the dimeric structures in complexes 1-3 have also been found linked by intermolecular O-H?N or N-H?O hydrogen bonding interaction. Interestingly, the dimers of complexes 2 and 3 are further linked into one-dimensional chain through intermolecular C-H?S and C-H?O weak hydrogen bonding interactions, respectively.     

Tin(IV) Schiff base complexes derived from pyridoxal: Synthesis,spectroscopic properties and cytotoxicity

The synthesis of monomeric pentacoordinated diorganotin(IV) complexes derived from pyridoxal hydrochloride and 4‐ or 5‐R ‐substituted ortho ‐aminophenols is described. The complexes were characterized using UV–visible, infrared, mass, ¹H NMR, ¹³C NMR and ¹¹⁹Sn NMR spectral techniques. The molecular structure of three complexes was established using X‐ray diffraction: 3b and 3d show a distorted trigonal bipyramidal geometry, in which the basal plane is defined by the butyl groups and the iminic nitrogen atom, whereas the oxygen atoms from the aromatic ring occupy axial positions; in contrast, complex 3e exhibits a square pyramidal geometry. The cytotoxic activity of all complexes against human cell lines U‐251 (glioblastoma), K‐562 (chronic myelogenous leukemia), HCT‐15 (human colorectal cancer), MCF‐7 (human breast cancer) and SKLU‐1 (non‐small‐cell lung cancer) was evaluated, and the inhibitory percentage values indicated higher activity than the reference standard, cisplatin. Acute toxicity studies were performed in vivo for the prepared complexes to determine the lethal medium dose (LD₅₀) after intraperitoneal administration to mice.