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.

Crystal Structures and Spectral Investigation of Aroylhydrazones and their Mixed Ligand Metal Chelates

Supra molecular architectures of coordination complexes of liydrazones through non covalent interactions have been explored. Molecular self—assernbly driven by weak interactions such as hydrogen— bonding, K '”T[, C-1-I‘ "TE, van der Waals interactions, and so forth are currently of tremendous research interest in the fields of molecule based materials. The directional properties of the hydrogembonding interaction associate discrete molecules into aggregate structures that are sufficiently stable to be considered as independent chemical species. Chemistry can borrow nature’s strategy to utilize hydrogen-bonding as Well as other noncovalent interactions as found in secondary and tertiary structures of proteins such as the double helix folding of DNA, hydrophobic selflorganization of phospholipids in cell membrane etc. In supramolecular chemistry hydrogen bonding plays an important role in forming a variety of architectures. Thus, the wise modulation and tuning of the complementary sites responsible for hydrogen—bond formation have led to its application in supramolecular electronics, host-guest chemistry, self-assembly of molecular capsules, nanotubes etc. The work presented in this thesis describes the synthesis and characterization of metal complexes derived from some substituted aroylhydrazones. The thesis is divided into seven chapters.

Structural studies on some metal complexes of embelin

This thesis deals with the studies on the synthesis and characterisation of the complexes of embelin with manganese (II), cobalt(II), nickel (II), copper (II), zinc (II), cadmium (II), chromium (III), iron (III) lanthanum(III), praseodymium (III) neodymium (III) Samarium (III), gadolinium (III) dysprosium (III), yttrium (III) thorium (IV) and uranium (VI). Elemental analysis as well as spectral, thermal and magnetic data were used to ascertain the composition of the complexes and to establish the structures of the metal complexes. Wherever possible, the electronic spectra and magnetic data were used to predict the stereochemistry of the complexes.The thesis is divided into four chapters.

Spectral, Structural And Biological Studies Of Some Metal Complexes Of ‘Nsubstituted 2-Benzoylpyridine Thiosemicarbazones

Aqua complex ions of metals must have existed since the appearance of water on the earth, and the subsequent appearance of life depended on, and may even have resulted from the interaction of metal ions with organic molecules. Studies on the coordinating ability of metal ions with other molecules and anions culminated in the theories of/\lfred Werner. Thereon the progress in the studies of metal complex chemistry was rapid. Many factors, like the utility and economic importance of metal chemistry, the intrinsic interest _in many of the compounds and the intellectual challenge of the structural problems to be solved, have contributed to this rapid progress. X—ray diffraction studies further accelerated the progress. The work cited in this thesis was carried out by the author in the Department of Applied Chemistry during 2001-2004. The primary aim of these investigations was to synthesise and characterize some transition metal complexes of 2-benzoylpyridine N(4)-substituted thiosemicarbazones and to study the antimicrobial activities of the ligands and their metal complexes. The work is divided into eight chapters

Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

Eight new transition metal complexes of benzaldehyde-N(4)–phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL)2(OAc)2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL)2(OAc)2] in DMF solution at 77K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL)2SO4] complex in frozen DMF, indicate the presence of unpaired electron in the dx2−y2 orbital. The metal ligand bonding parameters evaluated showed strong in-plane bonding and in-plane bonding. The ligand and complexes were screened for their possible antimicrobial activities.

Nonlinear and magneto-optical transmission studies on magnetic nanofluids of non-interacting metallic nickel nanoparticles

Oxide free stable metallic nanofluids have the potential for various applications such as in thermal management and inkjet printing apart from being a candidate system for fundamental studies. A stable suspension of nickel nanoparticles of ∼5 nm size has been realized by a modified two-step synthesis route. Structural characterization by x-ray diffraction and transmission electron microscopy shows that the nanoparticles are metallic and are phase pure. The nanoparticles exhibited superparamagnetic properties. The magneto-optical transmission properties of the nickel nanofluid (Ni-F) were investigated by linear optical dichroism measurements. The magnetic field dependent light transmission studies exhibited a polarization dependent optical absorption, known as optical dichroism, indicating that the nanoparticles suspended in the fluid are non-interacting and superparamagnetic in nature. The nonlinear optical limiting properties of Ni-F under high input optical fluence were then analyzed by an open aperture z-scan technique. The Ni-F exhibits a saturable absorption at moderate laser intensities while effective two-photon absorption is evident at higher intensities. The Ni-F appears to be a unique material for various optical devices such as field modulated gratings and optical switches which can be controlled by an external magnetic field

Near fifty percent sodium substituted lanthanum manganites—A potential magnetic refrigerant for room temperature applications

Nearly half of lanthanum sites in lanthanum manganites were substituted with monovalent ion-sodium and the compound possessed distorted orthorhombic structure. Ferromagnetic ordering at 300K and the magnetic isotherms at different temperature ranges were analyzed for estimating magnetic entropy variation. Magnetic entropy change of 1.5 J kg 1 K 1 was observed near 300 K. An appreciable magnetocaloric effect was also observed for a wide range of temperatures near 300K for small magnetic field variation. Heat capacity was measured for temperatures lower than 300K and the adiabatic temperature change increases with increase in temperature with a maximum of 0.62K at 280 K