DNA Interaction and Catalytic Activity Studies of Some New Transition Metal Complexes of Schiff Bases Derived from Quinoxaline

In this thesis we report the synthsis and characterisation of new transition metal complexes of Pd(II),Cu(II),Ru(II) and Ir(III) of Schiff bases derived from quinoxaline-2-carboxaldehyde/3-hydroxyquinoxaline-2-carboxaldehyde and 5-aminoindazole.6-aminoindazole or 8-aminoquinoline.The complexes have been characterised by spectral and analytical data.Pd(II) and Cu(II) form square planar complexes and Ru(III) and Ir(III) form ctahedral complexes with these Schiff bases.The DNA binding properties of theses synthesised complexes have been studied by various methods including electronic absoption spectroscopy,cyclic voltammetry,different pulse voltammetry and circular dichroism spectra were used.Gel electrophoresis experiments were also performed to investigate the DNA cleavage of theses complexes.Furthermore Ru(III) and Ir(III) complexes find application as oxidation and hydogenation catalsts. The studies on catalytic activities has been presented.The metal complexes presented in this thesis assure significance as they contribute to the development of new DNA binding agents and antibacterial and anticancer drugs.

Measurement of thermal diffusivity of some halogeno benzimidazole complexes of cobalt(II), copper (II) and copper(I) using laser induced photoacoustic effect

Cochin University of Science and Technology

Structural Characterization and Non-linear Optical Properties of Metal Complexes of Some Donor-Acceptor Substituted N-salicylidene-N' -aroylhydrazine Ligands

The present work deals with the complexation of Schiff bases of aroylhydrazines with various transition metal ions. The hydrazone systems selected for study have long 7I:-delocalized chain in the ligand molecule itself, which get intensified due to metal-to-ligand or ligand-to-metal charge transfer excitations upon coordination. Complexation with metal ions like copper, nickel, cobalt, manganese, iron, zinc and cadmium are tried. Various spectral techniques are employed for characterization. The structures of some complexes have been well established by single crystal X-ray diffraction studies. The nonIinaer optical studies of the ligands and complexes synthesized have been studied by hyper-Rayleigh scattering technique.The work is presented in seven chapters and the last one deals with summary and conclusion. One of the hydrazone system selected for study proved that it could give rise to polymeric metal complexes. Some of the copper, nickel, zinc and cadmium complexes showed non-linear optical activity. The NLO studies of manganese and iron showed negative result, may be due to the inversion centre of symmetry within the molecular lattice.

Synthesis,characterization and application studies of some polymer supported metal complexes

Polymer supports are efficient reagents,substrates and catalysts and they are extensively used for carrying out reactions at controlled rates.Tailor-made polymer supports are highly versatile which have opened an excellent area of research.Now polymer supported chemistry is being exploited at an amazing rate and it seems to join the routine world of organic synthesis.Polymer supported ligands are found to be efficient complexing agents whose high selectivity enables the analysis and removal of heavy metal ions which are toxic to all the living organisms of land and sea.polymer supported membranes function as ion selective potentiometric sensors which allow the exchange of specific ions among other ions of the same charge.In this investigation three series of polymeric schiff bases and three series of metal complexes have been prepared.An attempt is done to develop optimum conditions for the removal of heavy metal ions using polymeric schiff bases.A novel copper sensor electrode have also been prepared from polymer supported metal complex.

Studies On Some New Transition Metai. Complexes Of The Schiff Bases Derived From Ouinoxaline - 2 - Carboxaldehyde

This thesis deals with the synthesis, characterisation and catalytic activity studies of some new transition metal complexes of the Schiff bases, derived from quinoxaline—2—carboxaldehyde. The model complexes derived from specially designed and synthesised Schiff bases help us to understand the chemistry of biological systems. Schiff bases derived from heterocyclic aldehydes like quinoxaline-2-carboxaldehyde provide great structural diversity during complexation. The Schiff bases synthesised in the present study ' are quinoxaline—2—carboxa.lidene-2-aminophenol (QAP). quinoxaline—2carboxaldehyde semicarbazone (QSC), quinoxaline-2—carboxalidene—o— phenylenediamine (QOD) and quinoxaline-2-carboxalidene-2-furfurylamine (QFA). The elucidation of the structure of these complexes is done using conductance, magnetic susceptibility measurements. infrared, UV—Vis and EPR spectral studies.

Copper(II) complexes derived from di-2-pyridyl ketone-N4-phenyl-3-semicarbazone: Synthesis and spectral studies

Five copper(II) complexes [CuLCl]2·CuCl2·4H2O (1), [CuLOAc] (2), [CuLNO3]2 (3), [CuLN3] (4) and [CuLNCS]·3/2H2O (5) of di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL) were synthesized and characterized by elemental analyses and electronic, infrared and EPR spectral techniques. In all these complexes the semicarbazone undergoes deprotonation and coordinates through enolate oxygen, azomethine and pyridyl nitrogen atoms. All the complexes are EPR active due to the presence of an unpaired electron. EPR spectra of all the complexes in DMF at 77K suggest axial symmetry and the presence of half field signals for the complexes 1 and 3 indicates dimeric structures

Preparation, magnetic and EPR spectral studies of copper(II) complexes of an anticancer drug analogue

Ten new copper(II) complexes of five potential bisthiocarbohydrazone and biscarbohydrazone ligands were synthesized and physico-chemically characterized. The spectral and magnetic studies of compounds are consistent with the formation of asymmetric di-, tri- or tetranuclear copper(II) complexes of deprotonated forms of respective ligands. The variable temperature magnetic susceptibility measurements of all complexes showantiferromagnetic interactions between the Cu(II) centers, in agreement with very broad powder EPR spectra. However, frozen solution EPR spectral studies are found in contradiction with the solid-state magnetic studies and indicate that the complexes are not very stable in solutions; the possible fragmentations of complexes are found in agreement with MALDI MS results. The EPR spectral simulation of most of the compounds is in agreement with the presence of two uncoupled Cu(II) species in solution.

Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone

An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2] H2O (1), [CuLNCS] ½H2O (2), [CuLNO3] ½H2O (3), [Cu(HL)Cl2] H2O (4), [Cu2(HL)2(SO4)2] 4H2O (5), [CuLClO4] ½H2O (6), [CuLBr] 2H2O (7), [CuL2] H2O (8) and [CuLN3] CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2 y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure

Syntheses, EPR spectral studies and crystal structures of manganese(II) complexes of neutral N,N donor bidentate Schiff bases and azide/thiocyanate as coligand

Four manganese(II) complexes Mn2(paa)2(N3)4 (1), [Mn(paa)2(NCS)2] 3/2H2O (2), Mn(papea)2(NCS)2 (3), [Mn(dpka)2(NCS)2] 1/2H2O(4) of three neutral N,N donor bidentate Schiff bases were synthesized and physico- chemically characterized by means of partial elemental analyses, electronic, infrared and EPR spectral studies. Compounds 3 and 4 were obtained as single crystals suitable for X-ray diffraction. Compound 4 recrystallized as Mn(dpka)2(NCS)2. Both the compounds crystallized in the monoclinic space groups P21 for 3 and C2/c for 4. Manganese(II) is found to be in a distorted octahedral geometry in both the monomeric complexes with thiocyanate anion as a terminal ligand coordinating through the nitrogen atom. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines and the zero field splitting parameters (D and E) were calculated.

Synthesis, Spectral Characterization, Structural Studies and Biological Investigations of Transition Metal Complexes of Some Acid Hydrazones

This study concentrates the chemical properties of hydrazones due to its chelating capability and their pharmacological applications. Studies cover the preparation of different acid hydrazones and their structural studies and studies on their antimicrobial activity, synthesis and spectral characterization of different complexes of copper oxovanadium, manganese, nickel etc. Effect of incorporation of heterocyclic bases to the coordination sphere, change in the biological activity of acid hydrazones upon coordination, development of X-ray quality single crystals and its X-ray diffraction studies, studies on the redox behavior of the coordinated metal ions and correlation between the stereochemistry and biological activities.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.