Plastic columnar mesomorphism in half-disc-shaped oxovanadium(IV) Schiff base complexes

A new series of non-disc-like oxovanadium(iv) Schiff base complexes of the type [VO((4-C _n H_2n+1O)₂salcn)], where n?=?14, 16 or 18 and salcn is N,N ^′-bis-salicylidene-1,2-cyclohexadiamine, containing 4-substituted alkoxy tails in the side aromatic rings, have been synthesised and their mesogenic properties investigated. The compounds were characterised by FT–IR, ¹H NMR, ¹³C NMR, UV–Vis and FAB mass spectrometry. The mesomorphic behaviour of the compounds was studied using polarised optical microscopy and differential scanning calorimetry. The molecular organisation in the mesophase was determined by X-ray diffraction. It was found that the ligands did not show mesogenic behaviour, but their complexes exhibited a thermally stable enantiotropic highly ordered three-dimensional plastic mesophase with a columnar structure in the extended temperature range 155–166°C. The clearing temperature of the complexes was found to be lower than in the structurally analogous copper complexes. A density functional theory study was carried out using DMol3 at BLYP/DNP level to obtain a stable optimised structure. A square pyramidal geometry for the vanadyl complexes has been proposed.     

Iron(III) metallomesogen of [N2O2] donor Schiff base ligand containing 4-substituted alkoxy chains

Two new square pyramidal iron(III)-complexes of ‘salen’-type Schiff base ligands containing 4-substituted long alkoxy arms on the aromatic rings, [Fe(4-C₁₆H₃₃O)₂salcn)]Cl and [Fe(4-C₁₆H₃₃O)₂salophen)]Cl {salcn = N,N?-cyclohexanebis(salicylideneiminato) and salophen = N,N?-phenylenebis(salicylideneiminato)}, have been successfully synthesised, and their mesomorphic property investigated. The ligands and complexes were characterised by elemental analyses, UV–Vis, FT-IR, ESI–MS, ¹H and ¹³C NMR (for ligands only). The phase behaviour of the iron(III) complexes were ascertained by differential scanning calorimetry, polarising optical microscopy and variable temperature PXRD study. Ligands are non-mesomorphic, however, mesomorphism got induced upon complexation with the iron(III) centre. X-ray diffraction study revealed a layer-like arrangement of the five coordinated mesomorphic iron(III) complexes. The mesophase is stable over a wide range of temperature. The density functional theory calculations were carried out using Gaussian 09 program at B3LYP level using unrestricted 6–31G (d, p) basis set to obtain the optimised geometry of the iron(III) complexes.     

Complexes of cobalt(II), nickel(II), copper(II), zinc(II) and manganese(II) with tridentate Schiff base ligand

Summary A series of metal complexes with new tridentate Schiff base derived from salicylaldehyde and furfuraldehyde with o-phenyldiamine have been prepared and characterised by physical and chemical methods. Electronic spectra, room temperature magnetic moment values, e.p.r. and X-ray photoelectron spectroscopy studies suggest an octahedral geometry for all the complexes, where low molar conductance values are in accord with their non-electrolytic nature. The thermal stability of the complexes is discussed and the ligand-to-metal bonding modes discussed.     

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis,crystal structures,electrochemical and theoretical investigation

In this research, we prepared a new series of the Cu(II) (1) and Ni(II) (2) metal complexes of a tridentate Schiff base ligand, (E)-2-(5-bromo-2-hydroxybenzylideneamino) phenol (H₂L). These complexes were characterized by elemental analysis, FT-IR, UV–Vis, and ¹H-NMR spectroscopy. The crystal structures of (1) and (2) were determined by X-ray diffraction studies. The single crystal X-ray diffraction analyses revealed that copper(II) cation is five-coordinated and the coordination polyhedron is a slightly distorted square pyramid. Nickel(II), on the other hand, is four-coordinated, and has a regular, square planar geometry. Further discussed were the electrochemical reduction of these complexes. We also analyzed the nature of the metal–ligand bond in the complexes through NBO and EDA analysis. Besides, vibrational sample magnetometer (VSM) revealed complex (1) was ferromagnetic.     

Ionic hexagonal columnar metallomesogens derived from tetrabenzo[b,f,j,n] [1,5,9,13]tetraazacyclohexadecine

A series of transition metal (Ni, Cu, Pd) complexes derived from macrocyclic tetrabenzo[b,f,j,n] [1,5,9,13]tetraazacyclohexadecine (TAAB) was synthesized and their mesomorphic properties studied by differential scanning calorimetry, polarized optical microscopy and X-ray powder diffraction (XRD). These compounds have eight alkoxy side chains attached around the central molecular core and form disc-like molecules. All the derivatives exhibited columnar mesophases over a wide range of temperature. The mesomorphic behaviour was found to be dependent on the incorporated metal and the carbon length of the alkoxy side chains. The clearing temperatures decreased in the order M = Ni > Pd > Cu; this decrease was probably due to the size of the metal ions. Some derivatives with shorter side chains (n = 10, 12) were room temperature liquid crystals. All compounds were found to exhibit hexagonal columnar (Col_h) phases which were confirmed by powder XRD.     

High tilt antiferroelectric esters bearing a perfluorobutanoyloxy terminal chain: the influence of lateral fluoro substituents on mesomorphic behaviour,tilt angle,and spontaneous polarization

Novel liquid crystalline esters have been synthesized with a perfluorocarbonyloxy terminal chain and lateral fluoro substituents in order to determine their influence on mesomorphic behaviour, tilt angle and spontaneous polarization. Certain locations of lateral fluoro substituents provide for very low melting points and reasonably wide temperature ranges of the antiferroelectric phase, and can generate enhanced tilt angles of up to 45°, although spontaneous polarization is always lower than for the parent system without lateral fluoro substituents. Thus, these novel materials, particularly as components in mixtures, should be useful in high tilt antiferroelectric (orthoconic) applications.     

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes

Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)～5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level.     

The chiral helical structure of a copper(II) complex with a tridentate Schiff base ligand

In the title salt, catena‐poly[[[aquacopper(II)]‐μ‐3‐(2‐pyridylmethyleneamino)propanoato‐κ⁴N,N′,O:O′] perchlorate], {[Cu(C₉H₉N₂O₂)(H₂O)]ClO₄}_n, the monomeric unit contains a square‐based pyramidal Cu^II centre. The four basal positions are occupied by a tridentate anionic Schiff base ligand which furnishes an NNO‐donor set, with the fourth basal position being occupied by an O‐donor atom from the carboxylate group of an adjacent Schiff base ligand. The coordination sphere is completed by a water molecule at the apical position. Interestingly, each carboxylate group in the ligand forms a syn–anti‐configured bridge between two Cu^II centres, leading to left‐handed chiral helicity. The framework also exhibits O—H...O hydrogen bonds involving the water molecules and an O atom of the perchlorate anion.     

Molecular photochromic systems: a theoretical and experimental investigation on zinc(II) dithizonate

Zinc(II)‐dithizone based molecular systems [Zn(HDz)₂] are intriguing candidates for the development of optical devices thanks to their interesting photochromic and nonlinear optical properties. In the present work, the behavior of Zn(HDz)₂ in different solvents was investigated by a combined theoretical and experimental approach. In particular, solutions of both dithizone (H₂Dz) and Zn(HDz)₂ were analyzed by optical absorption spectroscopy and nuclear magnetic resonance (NMR) techniques, with particular attention to structure–properties relationships. Density functional and time‐dependent density functional calculations were performed on the stable and the activated forms of the complex, obtaining information on the energetics of their interconversion, as well as on the nature of their electronic excitations. Copyright © 2007 John Wiley & Sons, Ltd.     

Spectral,thermal, electrochemical,biological and DFT studies on nanocrystalline Co(II), Ni(II), Cu(II) and Zn(II) complexes with a tridentate ONO donor Schiff base ligand

Co(II), Ni(II), Cu(II) and Zn(II) Schiff base complexes derived from 3-hydrazinoquionoxaline-2-one and 1,2-diphenylethane-1,2-dione were synthesized. The compounds were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV–vis, ¹H NMR, ¹³C NMR, ESR, and mass spectral studies. Thermal studies of the ligand and its metal complexes were also carried out to determine their thermal stability. Octahedral geometry has been assigned for Co(II), Ni(II), and Zn(II) complexes, while Cu(II) complex has distorted octahedral geometry. Powder XRD study was carried out to determine the grain size of ligand and its metal complexes. The electrochemical behavior of the synthesized compounds was investigated by cyclic voltammetry. For all complexes, a 2 : 1 ligand-to-metal ratio is observed. The ligand and its metal complexes were screened for their activity against bacterial species such as E. coli, P. aeruginosa, and S. aureus and fungal species such as A. niger, C. albicans, and A. flavus by disk diffusion method. The DNA-binding of the ligand and its metal complexes were investigated by electronic absorption titration and viscosity measurement studies. Agarose gel electrophoresis was employed to determine the DNA-cleavage activity of the synthesized compounds. Density functional theory was used to optimize the structure of the ligand and its Zn(II) complex.     

Synthesis,structure, and biological properties of a Co(II) complex with tridentate Schiff base ligand

A new Co(II) complex of general formula [Co(L)₂] has been synthesized from a NNO tridentate Schiff base ligand, 2-[(piperidin-2-ylmethylimino)-methyl]-phenol (L). The title complex is characterized by elemental, spectroscopic, antibacterial, and single crystal X-ray structural studies. X-Ray crystallography reveals that the complex shows a distorted octahedral geometry around the Co(II) ion. The complex was tested against several bacteria and shows good antibacterial activities against almost all of the bacteria. The interactions of the title complex with calf thymus deoxyribonucleic acid (CT-DNA) have been investigated by electronic absorption and fluorescence spectroscopy, showing that the complex interacts with CT-DNA via partial intercalation. Thermogravimetric analysis (TGA) of the complex has also been reported and the result shows that the complex is thermally stable up to 134 °C.     

Theoretical investigation on molecular structure of a new mononuclear copper(II) thiocyanato complex with tridentate Schiff base ligand

An asymmetrical Schiff base ligand, 4-bromo-2-(2-pyridylmethyliminomethyl)phenol (HL), and its copper(II) complex, [Cu(L)SCN] (1), have been synthesized. Complex 1 is experimentally characterized by elemental analysis, FT-IR and UV–vis spectroscopic techniques, and cyclic voltammetry. The structure of the complex has been established by single-crystal X-ray diffraction studies, which reveal a square planar geometry of the central copper(II) ion in 1. The neighboring molecules of the complex connect each other by π–π stacking interactions with centroid-to-centroid ring distance 3.653 Å. The ligand can display two possible tautomeric forms; therefore, 1 can have an alternate molecular structure. DFT calculations have been employed to investigate the structure and relative stabilities of the suggested tautomeric forms of the ligand and its corresponding copper(II) complex.     

Ether formation on the tridentate Schiff base ligands of copper(II) complexes

A series of copper(II) complexes, CuL·imidazole, where L^2? are tridentate Schiff base ligands formed by condensation of salicylaldehyde with a series of amino acids, have been synthesized. Visible spectral data indicate that copper(II) in these complexes are five coordinate in the solid state and in solution. Electrospray mass spectrometry has been used to show how these complexes react in alcohol/NaOH solutions with and without the presence of d-galactose. In the absence of d-galactose where the amino acid in the ligand is serine, the alcohol group on the ligand is converted to its alkyl ether after sonication of the solution for up to 4?h. In the presence of d-galactose, an alkoxy group is added to the ligands except for the ligand containing serine after sonication of the solutions for up to 4?h. At the same time, d-galactose is oxidized to its aldehyde. Where the ligand contains methionine, oxygen is also added to the ligand, most likely to the thioether sulfur.     

Alkyl chain length effect on construction of copper(II) complexes with tridentate Schiff base ligand and DNA interaction

Two tridentate Schiff base ligands were synthesized by condensation of equimolar amounts of benzoylacetone and 2-amino-1-ethanol or 3-amino-1-propanol, H₂L¹ and H₂L², respectively. The reaction of the Schiff base ligands with Cu(CH₃COO)₂ in methanol leads to (CuL¹)₄, 1 and (CuL²)₂, 2. In the tetranuclear cubane species, the tridentate H₂L has both a chelating and a bridging mode, after double deprotonation of the enolic OH groups. The copper(II) centers are five-coordinate with a NO₄ donor set from the ligands. The coordination geometry around each copper ion is essentially square pyramidal with one nitrogen and two oxygens from one ligand and two oxygens of adjacent ligands from the next unit of the cubane. In dinuclear 2, H₂L² has chelating and bridging modes after double deprotonation of the enolic OH groups. The dianionic form of the Schiff base coordinates forming a six-membered chelate ring with Cu(II). Two such monomeric CuL² entities are eventually linked through the alkoxo bridges to produce dinuclear 2. The absorption spectra strongly suggest that 2 interacts with CT-DNA. Both 1 and 2 appear to be more efficient than the parent compound in DNA cleavage.     

Organotin(IV) complexes of dibasic tridentate Schiff bases containing ONO donor atoms

Organotin(IV) Schiff base complexes of the type (L)SnR₂ [where R?CH₃, C₆H₅ or CH₂CH₂CO₂ CH₃], (LH)Sn(C₆H₅)₃ and (L)SnCl(CH₂CH₂CO₂ CH₃) [where LH₂?2-N-salicylideneimino-2-methyl-1-propanol, derived from the condensation of salicylaldehyde and 2-amino-2-methyl-1-propanol] have been prepared and characterized on the basis of their elemental analyses, IR, ¹H, ¹³C and ¹¹⁹Sn NMR studies. In these mononuclear complexes the Schiff base acts either as a dianionic tridentate or as a monobasic bidentate moiety by coordinating through an alkoxy group, an azomethine nitrogen and a phenoxide ion to tin. Sulphur dioxide inserts in the tin–methyl/–phenyl bond in the above Schiff base complexes to give tin–O–sulphinates of formulae (L)RSn(SO₂R) and (LH)(C₆H₅)₂Sn(SO₂C₆H₅).     

Photofunctional supramolecular solution systems of chiral Schiff base nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzenes

Preparations, crystal structures, electronic and CD spectra are reported for new chiral Schiff base complexes, bis(N-R-1-naphthylethyl-3,5-dichlorosalicydenaminato)nickel(II), copper(II), and zinc(II). Nickel(II) and copper(II) complexes adopt a square planar trans-[MN₂O₂] coordination geometry with Δ(R,R) configuration. While zinc(II) complex adopts a compressed tetrahedral trans-[MN₂O₂] one with Δ(R,R) configuration and exhibits an emission band around 21 000 cm⁻¹ (λ_ex = 27 000 cm⁻¹). Absorption and CD spectra were recorded in N,N′-dimethylformamide, acetone, methanol, chloroform, and toluene solutions to discuss relationships between spectral shifts of d–d and π–π^∗ bands by structural changes of the complexes and physical properties of the solvents. Moreover, we have attempted to investigate conformational changes of the complexes induced by photoisomerization of azobenzene, 4-hydroxyazobenzene, or 4-aminoazobenzene, in various solutions under different conditions. Weak intermolecular interactions between complexes and azobenzenes are important for the phenomenon by conformational changes of bulky π-conjugated moieties of the ligands.     

Crystal Structure of the Bis[zinc(II)-hydroxide-(μ-perchlorate)-triaqua] Complex

Colorless single crystals of the title compound were accidentally obtained by a reaction of p-sulfophenylalanine with zinc perchlorate. The crystal structure (monoclinic, P2₁/c, Z = 4, a = 5.9031(7), b = 13.5404(16), c = 9.7932(8) Å, β = 126.438(5)°, V = 629.74(12) ų, R₁[I>2σ(I)] = 0.0276, wR₂(all) = 0.0844) reveals a discrete dinuclear [Zn(OH)(μ-ClO₄)(H₂O)₃]₂ in which each perchlorate anion acts as a bidentate bridging linker to bind two Zn atoms whereas the hydroxy group is a terminal group. Thus, the local surrounding around the zinc atom can be best described as a slightly distorted octahedron.     

Tetrazolate bridged dinuclear photo-luminescent zinc(II) Schiff base complex prepared via 1,3-dipolar cycloaddition at ambient condition

A bis(μ-NN′-tetrazolate)-bridged centrosymmetric dinuclear zinc(II) Schiff base complex, [Zn₂(L)₂(PZTZ)₂] (HL is a tridentate Schiff base, 2-(2-(dimethylamino)ethyliminomethyl)-6-ethoxyphenol and HPZTZ is 2-pyrazinyltetrazole), has been synthesized via [3 + 2] cycloaddition of 2-cyanopyrazine and sodium azide in the presence of zinc(II) acetate dihydrate and HL. The structure of the complex is confirmed by single-crystal X-ray diffraction analysis. The complex shows fluorescence.     

Synthesis of novel zirconium complexes bearing mono‐Cp and tridentate Schiff base [ONO] ligands and their catalytic activities for olefin polymerization

A series of novel zirconium complexes {R²Cp[2‐R¹‐6‐(2‐CH₃OC₆H₄N?CH)C₆H₃O]ZrCl₂ ( 1 , R¹ = H, R² = H, 2 : R¹ = CH₃, R² = H; 3 , R¹ = ^tBu, R² = H; 4 , R¹ = H, R² = CH₃; 5 , R¹ = H, R² = n‐Bu)} bearing mono‐Cp and tridentate Schiff base [ONO] ligands are prepared by the reaction of corresponding lithium salt of Schiff base ligands with R²CpZrCl₃·DME. All complexes were well characterized by ¹H NMR, MS, IR and elemental analysis. The molecular structure of complex 1 was further confirmed by X‐ray diffraction study, where the bond angle of Cl? Zr? Cl is extremely wide [151.71(3)°]. A nine‐membered zirconoxacycle complex Cp(O? 2? C₆H₄N?CHC₆H₄‐2? O)ZrCl₂ ( 6 ) can be obtained by an intramolecular elimination of CH₃Cl from complex 1 or by the reaction of CpZrCl₃·DME with dilithium salt of ligand. When activated by excess methylaluminoxane (MAO), complexes 1–6 exhibit high catalytic activities for ethylene polymerization. The influence of polymerization temperature on the activities of ethylene polymerization is investigated, and these complexes show high thermal stability. Complex 6 is also active for the copolymerization of ethylene and 1‐hexene with low 1‐hexene incorporation ability (1.10%). Copyright © 2006 John Wiley & Sons, Ltd.