Synthesis and Characterisation of New Transition Metal Complexes of Schiff Bases Derived from 3-hydroxyquinoxaline-2- carboxaldehyde and Application of Some ofthese Complexes as Hydrogenation and Oxidation Catalysts

The thesis deals with studies on the synthesis, characterisation and catalytic applications of some new transition metal complexes of the Schiff bases derived from 3-hydroxyquinoxaline 2-carboxaldehyde.. Schiff bases which are considered as ‘privileged ligands’ have the ability to stabilize different metals in different oxidation states and thus regulate the performance of metals in a large variety of catalytic transformations. The catalytic activity of the Schiff base complexes is highly dependant on the environment about the metal center and their conformational flexibility. Therefore it is to be expected that the introduction of bulky substituents near the coordination sites might lead to low symmetry complexes with enhanced catalytic properties. With this view new transition metal complexes of Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde have been synthesised. These Schiff bases have more basic donor nitrogen atoms and the presence of the quinoxaline ring may be presumed to build a favourable topography and electronic environment in the immediate coordination sphere of the metal. The aldehyde was condensed with amines 1,8-diaminonaphthalene, 2,3-diaminomaleonitrile, 1,2-diaminocyclohexane, 2-aminophenol and 4-aminoantipyrine to give the respective Schiff bases. The oxovanadium(IV), copper(II) and ruthenium(II)complexes of these Schiff bases were synthesised and characterised. All the oxovanadium(IV) complexes have binuclear structure with a square pyramidal geometry. Ruthenium and copper form mononuclear complexes with the Schiff base derived from 4- aminoantipyrine while binuclear square planar complexes are formed with the other Schiff bases. The catalytic activity of the copper complexes was evaluated in the hydroxylation of phenol with hydrogen peroxide as oxidant. Catechol and hydroquinone are the major products. Catalytic properties of the oxovanadium(IV) complexes were evaluated in the oxidation of cyclohexene with hydrogen peroxide as the oxidant. Here allylic oxidation products rather than epoxides are formed as the major products. The ruthenium(II) complexes are found to be effective catalysts for the hydrogenation of benzene and toluene. The kinetics of hydrogenation was studied and a suitable mechanism has been proposed.

Investigations on the preparation of composite polysaccharide films and micro / nanoparticles for novel applications

chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, CSIR

Effect of annealing on the spectral and nonlinear optical characteristics of thin films of nano-ZnO

The annealing effect on the spectral and nonlinear optical NLO characteristics of ZnO thin films deposited on quartz substrates by sol-gel process is investigated. As the annealing temperature increases from 300–1050 °C, there is a decrease in the band gap, which indicates the changes of the interface of ZnO. ZnO is reported to show two emission bands, an ultraviolet UV emission band and another in the green region. The intensity of the UV peak remains the same while the intensity of the visible peak increases with increase in annealing temperature. The role of oxygen in ZnO thin films during the annealing process is important to the change in optical properties. The mechanism of the luminescence suggests that UV luminescence of ZnO thin films is related to the transition from conduction band edge to valence band, and green luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies. The NLO response of these samples is studied using nanosecond laser pulses at off-resonance wavelengths. The nonlinear absorption coefficient increases from 2.9 ×10−6 to 1.0 ×10−4 m/W when the annealing temperature is increased from 300 to 1050 °C, mainly due to the enhancement of interfacial state and exciton oscillator strength. The third order optical susceptibility x(3) increases with increase in annealing temperature (T) within the range of our investigations. In the weak confinement regime, T2.4 dependence of x(3) is obtained for ZnO thin films. The role of annealing temperature on the optical limiting response is also studied.

Nonlinear optical characteristics of self-assembled films of ZnO

In the present work, we have investigated the nonlinear optical properties of self-assembled films formed from ZnO colloidal spheres by z-scan technique. The sign of the nonlinear component of refractive index of the material remains the same; however, a switching from reverse saturable absorption to saturable absorption has been observed as the material changes from colloid to self-assembled film. These different nonlinear characteristics can be mainly attributed to ZnO defect states and electronic effects when the colloidal solution is transformed into self-assembled monolayers. We investigated the intensity, wavelength and size dependence of saturable and reverse saturable absorption of ZnO self-assembled films and colloids. Values of the imaginary part of third-order susceptibility are calculated for particles of size in the range 20–300 nm at different intensity levels ranging from 40 to 325MW/cm2 within the wavelength range of 450–650 nm.

HEAVY METAL TOXICITY IN BIVALVE- HISTOLOGICAL AND HISTOCHEMICAL ENQUIRY

Division of Marine Biology, Microbiology and Biochemistry, School of Marine Sciences, Cochin University of Science and Technology

Photothermal Investigations on certain Organic Molecules and their Plasma polymerized thin Films

Department of Physics, Cochin University of Science and Technology

CuInS2 thin films using chemical methods for the fabrication of CuInS2/CdS solar cells

Dept.of Physics, Cochin University of Science and Technology

Fabrication of thin films and nano columnar structures of Fe-Ni amorphous alloys and modification of its surface properties by thermal annealing and swift heavy ion irradiation for tailoring the magnetic properties

Department of Physics, Cochin University of Science and Technology

Growth and characterization of perovskite oxide ferroelectric thin films and its applications

Department of Physics, Cochin University of Science and Technology

Synthesis and Study of Photophysical and Metal Ion Binding Properties of a Few Novel Semisquaraine and Croconaine Dyes

Photosciences & Photonics, Chemical Sciences & Technology Division, National Institute for Interdisciplinary Science & Technology

Studies on metal complexes with acylhydrazones based on heterocyclic carbonyl compounds

Dept.of Applied Chemistry, Cochin University of Science and Technology

Structural, EPR and Antimicrobial Studies on Some Transition Metal Complexes of Thiosemicarbazones

Department of Applied chemistry, Cochin University of Science and Technology

Structural and biological investigations of metal complexes of some substituted thiosemicarbazones

Department of Applied Chemistry, Cochin University of Science and Technology

Investigations on some Y-Zeolite encapsulated transition metal complexes of Schiff bases

Department of Applied Chemistry, Cochin University of Science and Technology