Spectroscopic and electrochemical studies of ruthenium and osmium complexes of salicylideneimine-2-thiophenol Schiff base

The reactions between [M(3)(CO)(12)], M = Ru and Os, and salicylideneimine-2-thiophenol Schiff base in THF under reflux gave [Ru(CO)(4)(satpH)] and [Os(CO)(3)(satpH(2))] complexes. Structures of the two complexes were proposed on the basis of spectroscopic studies. Magnetic study of [Ru(CO)(4)(satpH)] suggested that a change in oxidation state of the ruthenium atom from zero to +1 was achieved via oxidative addition of the SH group with a proton displacement to give a low-spin d(7) electronic configuration. UV-Vis spectra of the two complexes in different solvents exhibited visible bands due to metal-to-ligand charge transfer. Electrochemical investigation of the free ligand and complexes showed some cathodic and anodic irreversible peaks due to interconversions through electron transfer.     

Synthesis,structural characterisation and electrochemical and antibacterial studies of Schiff base copper complexes

Neutral complexes of Cu^II have been synthesised from the Schiff bases derived from salicylidene-4-aminoantipyrine and PhNH₂/substituted anilines. The structural features have been determined from their microanalytical, i.r., u.v.–vis., ¹H-, ¹³C-n.m.r., mass and e.s.r. spectral data. All the complexes exhibit square-planar geometry. Their magnetic susceptibility measurements and low conductance data provide evidence for the monomeric and non-electrolytic natures of the complexes respectively. The electrochemical behaviour of the complexes in MeCN at 298 K was studied. The kinetic parameters were determined and are discussed. The X-band e.s.r. spectra of the complexes in DMSO at 300 and 77 K were recorded and their salient features are reported. The powder XRD diffraction patterns for all the complexes are found to be similar. The antimicrobial activity of the ligands and their copper complexes against the bacteria Staphylococcus aureus, Klebsiella pneumoniae, Salmonella typhi, Pseudomonas aerugenosa and Bacillus subtilis are also reported. The complexes have higher activities than those of the free Schiff bases. Moreover, they have higher activity than the control (ampicillin) except for Klebsiella pneumoniae and Pseudomonas aerugenosa.     

Mesomorphism of lanthanide-containing Schiff's base complexes with chloride counterions

Liquid crystalline complexes [Ln(LH)3Cl3] have been synthesized, where Ln is a trivalent lanthanide ion (Pr-Lu, except Pm) and where LH is the Schiff's base ligand N-octadecyl4-tetradecyloxysalicylaldimine. Although the ligand does not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry and high temperature X-ray diffraction. The lanthanide complexes have much higher melting and clearing points than comparable complexes with nitrate or dodecyl sulphate counterions. In addition, the transition temperatures are virtually independent of the type of lanthanide ion. This behaviour is opposite to that observed for similar complexes with nitrate counterions [Ln(LH)3(NO3)3]. The differences in temperature dependence can be related to structural differences. Whereas in the nitrate complexes the Schiff's base ligand binds in a zwitterionic form, two-dimensional 1H NMR correlation spectroscopy (COSY) of [Lu(LH)3Cl3] gives an indication that in the chloride complexes, besides coordination via the oxygen of molecules in the zwitterionic form, some of the Schiff's base ligands bind in a bidentate fashion (via the phenolic oxygen and the imine nitrogen).     

Mesomorphism of lanthanide-containing Schiff's base complexes with chloride counterions

Liquid crystalline complexes [Ln(LH) 3 Cl 3 ] have been synthesized, where Ln is a trivalent lanthanide ion (Pr-Lu, except Pm) and where LH is the Schiff's base ligand N -octadecyl4-tetradecyloxysalicylaldimine. Although the ligand does not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry and high temperature X-ray diffraction. The lanthanide complexes have much higher melting and clearing points than comparable complexes with nitrate or dodecyl sulphate counterions. In addition, the transition temperatures are virtually independent of the type of lanthanide ion. This behaviour is opposite to that observed for similar complexes with nitrate counterions [Ln(LH) 3 (NO 3 ) 3 ]. The differences in temperature dependence can be related to structural differences. Whereas in the nitrate complexes the Schiff's base ligand binds in a zwitterionic form, two-dimensional 1H NMR correlation spectroscopy (COSY) of [Lu(LH) 3 Cl 3 ] gives an indication that in the chloride complexes, besides coordination via the oxygen of molecules in the zwitterionic form, some of the Schiff's base ligands bind in a bidentate fashion (via the phenolic oxygen and the imine nitrogen).     

Rare-earth complexes of mesomorphic Schiff's base ligands

Rare-earth complexes of mesomorphic Schiff 's bases, 4-[(alkylimino)methyl]-3-hydroxyphenyl 4-alkyloxybenzoates, were synthesized. Whereas the ligands LH display a nematic and/or a smectic C phase, the metal complexes show a viscous smectic A phase and decompose at the clearing point. The mesophase was investigated by hot-stage polarizing optical microscopy, by differential scanning calorimetry and by high temperature X-ray diffraction. Two types of complex were found, [Ln(LH)₃ (NO₃)₃] and [Ln(LH)₂L(NO₃)₂], depending on the ligand or the central metal ion. The first coordination sphere of the rare-earth ion in these metallomesogens is comparable to that in the structure of complexes with 4-alkoxy-N-alkyl2-hydroxybenzaldimine ligands.     

Rare-earth complexes of mesomorphic Schiff's base ligands

Rare-earth complexes of mesomorphic Schiff 's bases, 4-[(alkylimino)methyl]-3-hydroxyphenyl 4-alkyloxybenzoates, were synthesized. Whereas the ligands LH display a nematic and/or a smectic C phase, the metal complexes show a viscous smectic A phase and decompose at the clearing point. The mesophase was investigated by hot-stage polarizing optical microscopy, by differential scanning calorimetry and by high temperature X-ray diffraction. Two types of complex were found, [Ln(LH)₃ (NO₃)₃] and [Ln(LH)₂L(NO₃)₂], depending on the ligand or the central metal ion. The first coordination sphere of the rare-earth ion in these metallomesogens is comparable to that in the structure of complexes with 4-alkoxy-N-alkyl2-hydroxybenzaldimine ligands.     

Tri- and tetranuclear copper(II) complexes consisting of mononuclear Cu(II) chiral building blocks with a sugar-derived Schiff's base ligand

A new sugar-derived Schiff's base ligand N-(3-tert-butyl-2-hydroxybenzylidene)-4,6-O-ethylidene-beta-D-glucopyranosylamine (H3L1) has been developed which afforded the coordinatively labile, alcoholophilic trinuclear Cu(II) complex [Cu3(L1)2(CH3OH)(H2O)] (1). Complex 1 has been further used in the synthesis of a series of alcohol-bound complexes with a common formula of [Cu3(L1)2(ROH)2] (R = Me (2), Et (3), nPr (4), nBu (5), nOct (6)). X-ray structural analyses of complexes 2-6 revealed the collinearity of trinuclear copper(II) centers with Cu-Cu-Cu angles in the range of 166-172 degrees . The terminal and central coppers are bound with NO3 and O4 atoms, respectively, and exhibit square-planar geometry. The trinuclear structures of 2-6 can be viewed as the two {Cu(L1)}- fragments capture a copper(II) ion in the central position, which is further stabilized by a hydrogen-bonding interaction between the alcohol ligands and the sugar C-3 alkoxo group. Complex 2 exhibits a strong antiferromagnetic interaction between the Cu(II) ions (J = -238 cm(-1)). Diffusion of methanol into a solution of complex 1 in a chloroform/THF mixed solvent afforded the linear trinuclear complex [Cu(3)(L1)2(CH3OH)2(THF)2] (7). The basic structure of 7 is identical to complex 2; however, THF binding about the terminal coppers (Cu-O(THF) = 2.394(7) and 2.466(7) A) has introduced the square-pyramidal geometry, indicating that the planar trinuclear complexes 2-6 are coordinatively unsaturated and the terminal metal sites are responsible for further ligations. In the venture of proton-transfer reactions, a successful proton transfer onto the saccharide C-3 alkoxo group has been achieved using 4,6-O-ethylidene-d-glucopyranose, resulting in the self-assembled tetranuclear complex, [Cu4(HL1)4] (8), consisting of the mononuclear Cu(II) chiral building blocks, {Cu(HL1)}.     

New homodi-and heterotrinuclear metal complexes of Schiff base compartmental ligand: interaction studies of copper complexes with calf thymus DNA

The new homodinuclear complexes 1–4 of the type [LM^II ₂Cl₂], heterotrinuclear complexes 5 and 6 of the type [LM^II ₂Sn^IVCl₆] where M = Cu^II, Mn^II, Co^II, Ni^II and Cu^II and Ni^II, respectively have been synthesized and characterized by elemental analysis and various spectroscopic techniques. The homodinuclear complexes possess two different environments (N₂ and N₂O₂donor sets) for holding the metal ions. The metal ion in N₂ set exhibits square planar geometry with two chloride ions in the inner sphere but rhombic structure is found in tetradentate N₂O₂ Schiff base cavity while in heterotrinuclear complexes Sn^IV atom is in the octahedral environment. The interaction of complexes 1 and 5 with calf thymus DNA was carried out by absorption spectroscopy and cyclic voltammetry. The intrinsic binding constants (K _b ) of complex 1 and 5 were determined as 3.2 × 10³ M⁻¹ and 9.6 × 10³ M⁻¹, respectively suggesting that complex 5 binds more strongly to CT-DNA than complex 1. Fluorescence studies along with viscosity measurements have also been checked to authenticate the binding of metal complexes with DNA.     

Mesomorphism of lanthanide-containing Schiff's base complexes with dodecyl sulphate counterions

Liquid crystalline complexes of the formula [Ln(LH)₃(DOS)₃] have been synthesized, where Ln is a trivalent rare earth-ion (Y, La-Lu, except Pm), LH is the ligand N-octadecyl-4-tetradecyloxysalicylaldimine and DOS is the dodecyl sulphate counterion. Although the Schiff 's base ligands do not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry, high temperature X-ray diffraction and thermogravimetric analysis. The stoichiometry of the complexes remains constant throughout the lanthanide series.     

Mesomorphism of lanthanide-containing Schiff's base complexes with dodecyl sulphate counterions

Liquid crystalline complexes of the formula [Ln(LH)₃(DOS)₃] have been synthesized, where Ln is a trivalent rare earth-ion (Y, La-Lu, except Pm), LH is the ligand N-octadecyl-4-tetradecyloxysalicylaldimine and DOS is the dodecyl sulphate counterion. Although the Schiff 's base ligands do not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry, high temperature X-ray diffraction and thermogravimetric analysis. The stoichiometry of the complexes remains constant throughout the lanthanide series.     

The crystal structures and electrochemical studies of two naphthalenic Schiff base copper(II) complexes

The Schiff base ligands, 2-hydroxy-N-cyclohexyl-l-naphthaldimine (I), and 3-hydroxy-N-cyclohexyl-2-naphthaldimine (II), and their corresponding Cu^II complexes (1–2) respectively were synthesized and characterized. The crystal and molecular structures of bis-{(cyclohexyl)[(2-oxo-1H-naphth-1-ylidene)-methyl]aminato}copper(II) (1) and bis-{(cyclohexyl)[(3-oxo-2H-naphth-2-ylidene)-methyl]aminato} copper(II) (2), were determined. The X-ray diffraction study shows that the geometry around the metal atom for (1), is stepped square planar with a step of 1.063 Å while for (2), the geometry around the metal atom for square planar with an angle between the coordination planes O(1)---Cu---N(1) and O(1a)---Cu---N(1a) of 39.9°. Electrochemical studies show a dependence of the Cu^II/Cu^I potentials on the ligand structure.     

Synthesis,spectroscopic and electrochemical studies of mixed ligand ruthenium(II) chiral Schiff base complexes with nitrogen donors

Summary Mixed ligand complexes (1)-(18) of composition [RuL-(PPh₃)Y] and [RuL(PPh₃)(H₂O)Y]^- (L = chiral Schiff bases derived from l-alanine, l-valine, l-serine, l-cystein, l-arginine or l-aspartic acid with salicylaldehyde; Y = azide, 2,2-bipyridyl or 1,10-phenanthroline) have been prepared and characterized by microanalysis, spectroscopy and polarography. The conformational aspects regarding the relationship of the asymmetric carbon atom to the nitrogen donors around the Ru^II are discussed. All complexes showed quasi-reversible c.v. behaviour and the redox potentials of the Ru^II/Ru^I couple lie in the -0.31 to-0.16 V range.     

Synthesis and electrochemical studies of heterobinuclear complexes containing copper and molybdenum nitrosyl groups linked by Schiff base ligands

The reaction of [MoCl(NO)T_p ^* = tris(3,5-dimethylpyrazolylborate] with copper Schiff base complexes derived by condensation of one mole each of 2,5-dihydroxybenzaldehyde and salicylaldehyde with α,ω diamines [NH₂(CH₂) _n NH₂, n = 2–4] yields heterobinuclear complexes with two potential redox centres. I.r., electronic and e.s.r. spectroscopic properties of these complexes are described. Cyclic voltammetric data of the base complexes in DMSO reveal that the copper redox centres undergo irreversible one electron reduction at potentials which vary slightly with the polymethylene carbon chain backbone of the Schiff base ligands. Incorporation of [MoCl(NO)T_p ^*]⁺ groups in the copper Schiff base complexes, results to a slight anodic shift (100 mV) in the reduction potential of the copper centre which remains invariant as the polymethylene carbon chain lengthens. Electrochemical data of the heterobinuclear complexes using CH₂Cl₂ and DMSO as solvents indicate the solvent dependence of the reduction potentials of these complexes. In CH₂Cl₂, the reduction potential of the copper centre shifts cathodically by 100 mV, while that of the molybdenum centre shifts anodically by 200 mV. However, accumulated electrochemical data of the heterobinuclear complexes indicate minimal electronic interactions between the copper and molybdenum redox centres. This revised version was published online in June 2006 with corrections to the Cover Date.     

Spectroscopic and electrochemical studies of DNA breakage induced by dopamine and copper ion.

Dopamine may show some biological activities in antitumor and cell apoptosis. Herein, we attempted to employ UV-Vis, CD, and electrochemical methods to investigate the interaction between DNA and dopamine. Both the spectroscopic and electrochemical evidence indicated that dopamine, which was a cation, could interact with polyanion DNA. However, this kind of interaction, mainly by a static electronic force, did not result in any damage of the DNA structure. This situation was quite different when Cu ion was added to the dopamine-DNA system; an obvious change in the color of the solution and in the spectra of UV-Vis and CD showed that some chemical changes occurred in this system, and that the DNA native structure was destroyed. The results of gel electrophores further revealed that DNA might be broken into small segments by dopamine in the presence of Cu ion. The possible reaction mechanisms are discussed.     

Spectroscopic and electrochemical characterization of an aqua ligand exchange and oxidatively induced deprotonation in diiron complexes

Reaction of the unsymmetrical phenol ligand 2-((bis(2-pyridylmethyl)amino)methyl)-6-(((2-pyridylmethyl)benzylamino)methyl)-4-methylphenol (HL-Bn) or its 2,6-dichlorobenzyl analogue (HL-BnCl(2)) with Fe(H(2)O)(6)(ClO(4))(2) in the presence of disodium m-phenylenedipropionate (Na(2)(mpdp)) followed by exposure to atmosphere affords the diiron(II,III) complexes [Fe(2)(L-Bn)(mpdp)(H(2)O)](ClO(4))(2) and [Fe(2)(L-BnCl(2))(mpdp)(CH(3)OH)](ClO(4))(2), respectively. The latter complex has been characterized by X-ray crystallography. It crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.3095(14) A, b = 20.1073(19) A, c = 19.4997(19) A, alpha = 90 degrees, beta = 94.471(2) degrees, gamma = 90 degrees, V = 5202.6(9) A(3), and Z = 4. The structure of the compound is very similar to that of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) determined earlier, except for the replacement of a water by a methanol on the ferrous site. Magnetic measurements of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) reveal that the two high-spin Fe ions are moderately antiferromagnetically coupled (J = -3.2(2) cm(-)(1)). Upon dissolution in acetonitrile the terminal ligand on the ferrous site is replaced by a solvent molecule. The acetonitrile-water exchange has been investigated by various spectroscopic techniques (UV-visible, NMR, M?ssbauer) and electrochemistry. The substitution of acetonitrile by water is clearly evidenced by M?ssbauer spectroscopy by a reduction of the quadrupole splitting value from 3.14 to 2.41 mm/s. In addition, it causes a 210 mV downshift of the oxidation potential of the ferrous site and a similar reduction of the stability domain of the mixed-valence state. Exhaustive electrolysis of a solution of [Fe(2)(L-Bn)(mpdp)(H(2)O)](2+) shows that the aqua diferric species is not stable and undergoes a chemical reaction which can be partly reversed by reduction to the mixed-valent state. This and other electrochemical observations suggest that upon oxidation of the diiron center to the diferric state the aqua ligand is deprotonated to a hydroxo. This hypothesis is supported by M?ssbauer spectroscopy. Indeed, this species possesses a large quadrupole splitting value (DeltaE(Q) >or= 1.0 mm.s(-)(1)) similar to that of analogous complexes with a terminal phenolate ligand. This study illustrates the drastic effects of aqua ligand exchange and deprotonation on the electronic structure and redox potentials of diiron centers.     

X-ray and magnetic birefringence studies of some lanthanide metallomesogens with Schiff's base ligands

Low angle X-ray scattering studies have been used to identify the mesophase of some calamitic lanthanide mesogens as smectic A, while magnetic birefringence studies have shown a huge magnetic anisotropy for these complexes.     

Electrochemical behaviour of the complexes of copper(II) with a Schiff base compartmental ligand

Summary The ethylenediamine Schiff base derivative ofo-acetoacetylphenol, H₄aapen, is a ligand able to form both mononuclear and dinuclear complexes with copper(II) ion. Mononuclear positional isomers can be obtained, having the copper in the O₂O₂ site and in the N₂O₂ site. The electrochemistry of these copper(II) complexes in dimethylsulfoxide shows that the two positional isomers are reduced at different potentials through an e.c.e. mechanism, in which a chemical reaction is coupled between two one-electron transfers, the N₂O₂ isomer being the less reducible. They also undergo complicated oxidation processes at high potentials, less significant in distinguishing the two isomers. The electrochemical behaviour of the dinuclear copper(II) complex parallels that of the two mononuclear isomers.     

Spectroscopic studies on copper(II)triphenylarsine oxide square planar complexes

Electronic and ESR spectra of the complexes [Cu(II)(tpa_so)₄][Cu(I)Cl₂]₂,[Cu(tpa_so)₄](NO₃)₂ and [Cu(tpa_so)₄](ClO