Thermal diffusivity of some polymer supported halogeno benzimidazole complexes of cobalt(II) and copper(II) - a photoacoustic study

The thermal diffusivities of some polystyrene supported Schiff complexes of Co(II) and Cu(II) were determined by the laser induced photoacoustic technique. The effect of metal as well as the halogen part on thermal diffusivity of polymer supported complexes was studied. The thermal diffusivity of Co complexes increases while it decreases in Cu complexes with Cl, Br and I substitutions, respectively.

Template assisted fabrication of I-D nanostructures of Nickel,Cobalt, Iron Oxide and Carbon nanotubes and a study on their structural, magnetic and nonlinear optical properties for applications

Department of Physics, Cochin University of Science & Technology

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

Transition metal complexes of some bis(thiosemicarbazones) derived from 2,6-diacetylpyridine and N4-substituted thiosemicarbazides:Synthesis, spectral and structural studies

Coordination chemistry of pentadentate 2,6-diacetylpyridine bis(thiosemicarbazone) Schiff base ligands has been intensively studied due to the versatility of the molecular chain in order to obtain very different geometries as well as their broad therapeutic activity. Metal complexes of thiosemicarbazone with aldehydes and ketones have been widely reported. But there have been fewer reports on potential pentadentate bis(thiosemicarbazones) formed from 2,6-diacetylpyridine. Keeping these in view, we have synthesized four bis(thiosemicarbazone) systems with 2,6-diacetylpyridine. In the present work, the chelating behavior of bis(thiosemicarbazones) are studied, with the aim of investigating the influence of coordination exerts on their conformation and or configuration, in connection with the nature of the metal and of the counter ion. The selection of the 2,6-diacetylpyridine as the ketonic part was based on its capability to form polynuclear complexes with different coordination number. The doubled armed bis(thiosemicarbazones) can coordinate to a metal centre as dianionic ligand by losing its amide protons or it can coordinate as monoanionic ligand by losing its amide proton from one of the thiosemicarbazone moiety or it can also be coordinate as neutral ligand. Hence it is interesting to explore the coordinating capabilities of these ligands whether in neutral form or anionic form and to study the structural variations occurring in the ligands during complexation such as change in conformation.

Studies on some new Schiff base complexes of ruthenium and neodymium

In the present study an attempt has been made to synthesize some simple complexes of multidentate ligands. Analogous zeolite encapsulated complexes were also synthesized and characterized. Immobilization on to polymer supports through covalent attachment is expected to solve the problem of decomposition of many complexes during catalytic reaction. Hence the work is also extended to the synthesis and characterization of some polymer supported complexes of Schiff base Iigands. All the three types of synthesized complexes, simple, zeolite encapsulated and polystyrene anchored, were subjected to catalytic activity study towards catechol-oxidation reaction. A selected group of complexes were also screened for their catalytic activity towards phenol-oxidation reaction. Biological screening of the synthesized ligands and neat complexes were done with a view to establish the effect of complexation on biological systems.

Studies on Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Diaminonaphthalene

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.In the present study we have synthesized some new Mn(II),Co(II) and Cu(II) complexes of Schiff bases derived from 1,8-diaminonaphthalene.Even though we could not isolate theses Schiff bases (as they readily cyclise to form the perimidine compounds),we were able to characterize unequivacally the complexes synthesized from these compounds as complexes of Schiff Bases. We Synthesized three perimidine derivatives ,2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine,2-(2,3-dihydro-1H-perimidin-2-yl)-6-methoxyphenol and 4-(2,3-dihyro-1H-perimidin-2-yl)-2-methoxyphenol by the condensation of 1,8-diaminonaphthalene with quinoxaline-2-carboxaldehyde,2- hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively.Theses compounds were used as precursor ligands for the preparation of Schiff base complexes.The complexes were characterized by using elemental analysis ,conductance and magnetic susceptibility measuremets ,infrared and UV-Visible spectroscopy ,thermogravimetric analysis and EPR spectroscopy .We also encapsulated the complexes in zeolite Y matrix and these encapsulated complexes were also characterized. We have also tried theses complexes as catalysts in the oxidation of cyclohexanol and decomposition of hydrogen peroxide.

Studies on metal complexes of some tridentate acylhydrazones

Studies on transition metal complexes have achieved a great interest due to their versatile applications.The convenient route for synthesis,the nature of ligands and stability of metal complexes has significant contributions in their applications in medicine,biology,catalysis and photonics.The present work deals wth the synthesis and characterization of metal complexes of some tridentate acylhydrazones .Hydrazones are promising ligands in coordination chemistry with interesting binding modes and applications.The acylhydrazones chosen for the current study are capable of forming complexes in different forms through tautomerism.

Loading dependence similarities on the cure time and mechanical properties of rubber ferrite composites containing nickel zinc ferrite

Composite magnetic materials have the unique advantage of property modification for tailoring devices for various applications. Rubber ferrite composites (RFCs) prepared by incorporating ferrites in rubber matrixes have the advantage of easy mouldability and flexibility. RFCs containing various loadings of nickel zinc ferrite (NZF) (Ni1 xZnxFe2O4) in a natural rubber matrix have been prepared. The cure characteristics and the mechanical properties of these composites were evaluated. The effect of loading on the cure characteristics and tensile properties were also evaluated. It is found that the loading dependence on the cure time and mechanical properties exhibit an identical pattern.

Catalysis by Polymer Supported Dendrimers, their Metal Complexes and Nanoparticle Conjugates

The present thesis has described the development of some heterogeneous catalysts based on polymer supported dendrimers. Attachment of dendrimers to crosslinked polymer produced new catalysts with combined benefits of both dendrimers and heterogeneous catalysts. These were used as heterogeneous catalysts in selected reactions. All possible attempts were taken to avoid halogenated and aromatic solvents and toxic reagents. In short the present work has dealt with development of environmental friendly catalysts based on dendrimers.

Synthesis, spectral and structural studies of transition metal complexes of N(4)-substituted semicarbazones

The thesis is an introduction to our attempts to evaluate the coordination behaviour of a few compounds of our interest. Semicarbazones and their metal complexes have been an active area of research during the past years because of the beneficial biological activities of these substances. Tridentate NNO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are well-authenticated compounds in this field and their synthesis and characterization are well desirable. Hence, we decided to develop a research program aimed at the synthesis and characterization of novel semicarbazones derived from 2-benzoylpyridine and 2-acetylpyridine and their transition metal complexes. In addition to various physicochemical methods of analysis, single crystal X—Ray diffraction studies were also used for the characterization of the complexes.

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.

Zeolite encapsulated complexes of ruthenium: synthesis, characterisation and catalytic activity studies

The work presented in this thesis is mainly centered on the synthesis and characterization of some encapsulated transition metal complexes and the catalytic activity of the synthesized complexes in certain organic reactions.thesis deals with the catalytic activity of ruthenium-exchanged zeolite and the zeolite encapsulated complexes of SSC, SOD, SPD, AA, ABA, DMG, PCO, PCP, CPO and CPP in the hydroxylation of phenol using hydrogen peroxide. The products were analyzed with a GC to determine the percentage conversion and the chromatograms indicate the presence of different products like hydroquinone, catechol,benzoquinone, benzophenone etc. The major product formed is hydroquinone. From the screening studies, RuYSSC was found to be the most effective catalyst for phenol hydroxylation with 94.4% conversion and 76% hydroquinone selectivity. The influence of different factors like reaction time, temperature, amount of catalyst, effect of various solvents and oxidant to substrate ratio in the catalytic activity were studied in order to find out the optimum conditions for the hydroxylation reaction. The influence of time on the percentage conversion of phenol was studied by conducting the reactions for different durations varying from one hour to four hours. There is an induction period for all the complexes and the length of the induction period depends on the nature of the active components. Though the conversion of phenol and selectivity for hydroquinone. increases with time, the amount of benzoquinone formed decreases with time. This is probably due to the decomposition of benzoquinone formed during the initial stages of the reaction into other degradation products like benzophenones. The effect of temperature was studied by carrying out the reaction at three different temperatures, 30°C, 50°C and 70°C. Reactions carried at temperatures higher than 70°C result either in the decomposition of the products or in the formation of tarry products. Activity increased with increase in the amount of the catalyst up to a certain level. However further increase in the weight of the catalyst did not have any noticeable effect on the percentage conversion. The catalytic studies indicate that the oxidation reaction increases with increase in the volume of hydrogen peroxide till a certain volume. But further increase in the volume of H202 is detrimental as some dark mass is obtained after four hours of reaction. The catalytic activity is largely dependent on the nature of the solvent and maximum percentage conversion occurred when the solvent used is water. The intactness of the complexes within the zeolite cages enhances their possibility of recycling and the activities of the recycled catalysts show only a slight decrease when compared to the fresh samples .

Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The unusual coordination modes of semicarbazones when bound to metals, the wide applications and structural diversity of metal complexes of semicarbazones provoked us to synthesize and characterize the tridentate ONO and NNO-donor semicarbazones and their transition metal complexes. This work is focused on the studies on complexes of three N4-phenylsemicarbazones synthesized by changing the carbonyl compounds. This work is concerned with the studies of two new semicarbazones, 2- formylpyridine-N4-phenylsemicarbazone (HL1) and 3-ethoxysalicylaldehyde- N4-phenylsemicarbazone (H2L2) and a reported semicarbazone 2-benzoylpyridine-N4-phenylsemicarbazone (HL3) [29]. The compositions of these semicarbazones were determined by the CHN analyses and IR, UV and NMR spectral studies were used for the characterization of these compounds. The molecular structure of 3-ethoxysalicylaldehyde-N4-phenylsemicarbazone (H2L2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Cu(II), Cd(II), Zn(II) and Ni(II) complexes of these three semicarbazones. The complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some complexes of all metals suitable for X-ray diffraction studies. This thesis is divided into six chapters.

Synthesis, Characterization and Application Studies of Some Polymer Supported Metal Complexes

Polymer supports and polymeric complexes are highly versatile and they are successfully employed as efficient reagents, substrates and catalysts. Recently there observed a growing interest in the synthesis of tailor-made polymer supports and functionalized polymers for the preparation of metal complexes for various applications. They have the combination of properties due to the macromolecular structure as well as due to the reactivity of the functional group. An interesting feature of functional polymers is their affinity towards metal ions. Therefore the synthesis, characterization and application of such polymeric complexes have great scientific and analytical importance. In this investigation three series of polymeric complexes of transition metal ions are prepared from three schiff bases. All the complexes and polymeric schiff bases were characterized by analytical, spectral and thermal methods The thesis consist of six chapters. The first chapter contains an introduction and a brief review on application of polymer supports, polymer supported ligands and complexes. The second chapter gives the details of reagents and instruments used and the procedure adopted for the preparation of ligands and complexes. The third chapter explains the methods employed for characterization and the results are also discussed. The fourth chapter gives a detailed study of metal ion removal using ligands whereas the fifth chapter describes the development of the Cu” ion sensor electrode. The sixth chapter is the summary of the thesis and references are presented at the end.

Ligation properties of N4-phenylsemicarbazones towards transition metals: Synthesis and spectral studies

Semicarbazones and their transition metal complexes have been receiving considerable attention because of their biological relevance and applications in the field of analysis and in the field of organic NLO materials. Their structural diversity also attracted inorganic chemists. A good deal of work has been reported on the synthesis and structural investigation of semicarbazones and their complexes. This is due partially to their capability of acting as multidentate, NO, NNO, ONO and ONNO donors with the formation of either mono or bi or polynuclear complexes. Their chemistry and pharmacological applications have been extensively investigated. Appreciable biological applications as well as diverse stereochemistry of their metal complexes prompted us to synthesize two new tridentate ONO donor N4-phenyl semicarbazones derived from 2-hydroxy-4-methoxyacetophenone and 2-hydroxy-4-methoxybenzophenone and their transition metal complexes. These ketones were selected since they can provide a further binding site from phenolic–OH and can thus increase the denticity. Introduction of heterocyclic bases like 1,10-phenanthroline, 2,2′-bipyridine, 4,4′-dimethyl- 2,2′-bipyridine and 4-picoline and some pseudohalides like azide and thiocyanate ion can result in mixed ligand metal chelates with different geometries in coordination compounds In the present study, oxovanadium(IV), manganese(II), cobalt (II/III), nickel(II), copper(II) and zinc(II) complexes of 2-hydroxy-4- methoxyacetophenone-N4-phenylsemicarbazone (H2ASC) and 2-hydroxy-4- methoxybenzophenone-N4-phenylsemicarbazone (H2BSC) were synthesized and characterized.