Spectral studies and crystal structures of some transition metal complexes of N4-substituted semicarbazones

The present work is concentrated on the studies of two novel semicarbazones, di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL1) and quinoline-2-carboxaldehyde-N4-phenyl-3-semicarbazone (HL2). The compositions of these semicarbazones were determined by the CHN analyses. For the characterization of these compounds we have used IR, UV and NMR spectral studies. The molecular structure of quinoline-2-carboxaldehyde-N4-phenyl-3- semicarbazone (HL2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Zn(II), Cd(II), Cu(II), Ni(II), Co(II) and Mn(II) complexes of these semicarbazones, HL1 and HL2. These complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some Zn(II) and Cd(II) compounds suitable for X-ray diffraction studies. For other complexes we could not isolate single crystals of good quality for single crystal X-ray diffraction studies.

Geochemistry of transition, non-transition and rare-earth elements in the surficial sediments of continental shelf of Kerala and an annex to the Cochin estuarine system

The metals present in the surface sediments have high demand on a global perspective, and the main reservoir of these elements is believed to be the ocean floor. A lot of studies on metals are going on throughout the world for its quantification and exploitation. Even though, some preliminary attempts have been made in selected areas for the quantitative study of metals in the western continental shelf of India, no comprehensive work has been reported so far. The importance of this study also lies on the fact that there has not been a proper evaluation of the impact of the Great Tsunami of 2004 on the coastal areas of the south India. In View of this, an attempt has been made to address the seasonal distribution, behavior and mechanisms which control the deposition of metals in the sediments of the western continental shelf and Cochin Estuary, an annex to this coastal marine region.Surface sediment samples were collected seasonally from two subenvironemnts of southwest coast of India, (continental shelf of Kerala and Cochin estuarine system), to estimate the seasonal distribution and geochemical behavior of non-transition, transition, rare-earth elements, Th and U. Bottom water samples were also taken from each station, and analysed for temperature, salinity and dissolved oxygen, hence the response of redox sensitive elements to oxygen minimum zone can be addressed. In addition, other sedimentary parameters such as sand, silt, clay fractions, CaCO3 and organic carbon content were also estimated to evaluate the control factors on level of metals present in the sediment. The study used different environmental data analysis techniques to evaluate the distribution and behavior of elements during different seasons. This includes environmental parameters such as elemental normalisation, enrichment factor, element excess, cerium and europium anomalies and authigenic uranium.

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.

Transition metal complexes derived from ketone based N(4)-substituted thiosemicarbazones: Crystal structures and spectral studies

Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

Crystal Structures and Spectral Aspects of Mixed Ligand Transition Metal Chelates Derived from Aldehyde based ONS Donor Thiosemicarbazones

Thiosemicarbazones have emerged as an important class of ligands over a period of time, for a variety of reasons, such as variable donor properties, structural diversity and biological applications. Interesting as the coordination chemistry may be, the driving force for the study of these ligands has undoubtedly been their biological properties and the majority of the 3000 or so publications on thiosemicarbazones since 2000 have alluded to this feature. Thiosemicarbazones with potential donor atoms in their structural skeleton fascinate coordination chemists with their versatile chelating behavior. The thiosemicarbazones of aromatic aldehydes and ketones form stable chelates with transition metal cations by utilizing both their sulfur and azomethine nitrogen as donor atoms. They have been shown to possess a diverse range of biological activities including anticancer, antitumor, antibacterial, antiviral, antimalarial and antifungal properties owing to their ability to diffuse through the semipermeable membrane of the cell lines. The enhanced effect may be attributed to the increased lipophilicity of the metal complexes compared to the ligand alone.

Preparation of transition metal complexes of bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (C7H9CO2H) and X-ray crystal structure of [Cu2?(±)-endo-μ-O2CC7H9?4 (CH3OH)2]·2CH3OH

Metathesis reactions were used to prepare a range of dicopper(II), monocopper(I), diruthenium(II, III), dimolybdenum(II,II) and dirhodium(II,II) complexes of either racemic or resolved forms of endo- and exo-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (C7H9CO2H). The X-ray crystal structure of [Cu2{(±)-endo-μ-O2CC7H9}4(CH3OH)2]·2CH3OH shows the two copper(II) ions bridged by two (+)-endo-bicyclo[2.2.1]hept-5-ene-2-carboxylate anions and two (−)-endo-bicyclo[2.2.1]hept-5-ene-2-carboxylate anions. Methanol molecules occupy the two trans axial sites, and there are also two methanol molecules hydrogen bonded to opposite carboxyl oxygens.

Synthesis and X-ray crystal and molecular structure of tetrakis(2,2-dimethyl-1-phenylethenyl)chromium(IV), the first structurally-characterised homoleptic alkenyl compound of a transition metal

The title compound, the first homoleptic Group 6A metal alkenyl, has been prepared from CrCl3·3(thf), and its properties, including X-ray crystal structure determination, are reported.

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 4. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)-(phenylethynyl)platinum(II) and comments on the relative trans influence of various carbon ligands

The molecular structure of trans-[PtCl(CCPh)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21, with a= 12.359(3), b= 13.015(3), c= 9.031(2)Å, β= 101.65(2)°, and Z= 2. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.046 for 1 877 diffractometric intensity data. The crystals contain discrete molecules in which the platinum coordination is square planar. The phenylethynyl group is non-linear, with a Pt–CC angle of 163(2)°. Selected bond lengths are Pt–Cl 2.407(5) and Pt–C 1.98(2)Å. The structural trans influences of CCPh, CHCH2, and CH2SiMe3 ligands in platinum(II) complexes are compared; there is only a small dependence on hybridization at the ligating carbon atom.

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 3. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)(vinyl)platinum(II)

The molecular structure of trans-[PtCl(CHCH2)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are orthorhombic, space group Pbcn, with a= 10.686(2), b= 13.832(4), c= 16.129(4)Å, and Z= 4. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.044 for 1 420 diffractometric intensity data. The crystals contain discrete molecules in which the platinum co-ordination is square planar. The Pt–Cl bond vector coincides with a crystallographic diad axis about which the atoms of the vinyl group are disordered. Selected bond lengths (Å) are Pt–Cl 2.398(4), Pt–P 2.295(3), and Pt–C 2.03(2). The Pt–CC angle is 127(2)°. From a survey of the available structural data it is concluded that there is little, if any, back donation from platinum to carbon in platinum–alkenyl linkages.

Influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite

In this work we report results on the influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite. A series of Fe(2.85)RE(0.15)O(4) (RE = Gd, Dy, Ho, Tm and Yb) samples have been prepared by high energy ball milling. Structure/microstructure investigations of two selected samples Fe(2.85)Gd(0.15)O(4) and Fe(2.85)Tm(0.15)O(4), represent an extension of the previously published results on Fe(3)O(4)/gamma-Fe(2)O(3), Fe(2.85)Y(0.15)O(4) and Fe(2.55)In(0.45)O(4) [Z. Cvejic, S. Rakic, A. Kremenovic, B. Antic, C. Jovalekic. Ph. Colomban, Sol. State Sciences 8 (2006) 908], while magnetic characterization has been done for all the samples. Crystallite/particle size and strain determined by X-ray diffractometry and Transmission electron microscopy (TEM) confirmed the nanostructured nature of the mechanosynthesized materials. X-ray powder diffraction was used to analyze anisotropic line broadening effects through the Rietveld method. The size anisotropy was found to be small while strain anisotropy was large, indicating nonuniform distribution of deffects in the presence of Gd and Tm in the crystal structure. Superparamagnetic(SPM) behavior at room temperature was observed for all samples studied. The Y-substituted Fe(3)O(4) had the largest He and the lowest M(S). We discuss the changes in magnetic properties in relation to their magnetic anisotropy and microstructure. High field irreversibility (H>20kOe) in ZFC/FC magnetization versus temperature indicates the existence of high magnetocrystalline and/or strain induced anisotropy. (C) 2008 Elsevier B.V. All rights reserved.

Structure and properties of intermetallic ternary rare earth compounds

The so called material science is an always growing field in modern research. For the development of new materials not only the experimental characterization but also theoretical calculation of the electronic structure plays an important role. A class of compounds that has attracted a great deal of attention in recent years is known as REME compounds. These compounds are often referred to with RE designating rare earth, actinide or an element from group 1 - 4, M representing a late transition metal from groups 8 - 12, and E belonging to groups 13 - 15. There are more than 2000 compounds with 1:1:1 stoichiometry belonging to this class of compounds and they offer a broad variety of different structure types. Although many REME compounds are know to exist, mainly only structure and magnetism has been determined for these compounds. In particular, in the field of electronic and transport properties relatively few efforts have been made. The main focus in this study is on compounds crystallizing in MgAgAs and LiGaGe structure. Both structures can only be found among 18 valence electron compounds. The f electrons are localized and therefor not count as valence electrons. A special focus here was also on the magnetoresistance effects and spintronic properties found among the REME compounds. An examination of the following compounds was made: GdAuE (E = In, Cd, Mg), GdPdSb, GdNiSb, REAuSn (RE = Gd, Er, Tm) and RENiBi (RE = Pr, Sm, Gd - Tm, Lu). The experimental results were compared with theoretic band structure calculations. The first half metallic ferromagnet with LiGaGe structure (GdPdSb) was found. All semiconducting REME compounds with MgAgAs structure show giant magnetoresistance (GMR) at low temperatures. The GMR is related to a metal-insulator transition, and the value of the GMR depends on the value of the spin-orbit coupling. Inhomogeneous DyNiBi samples show a small positive MR at low temperature that depends on the amount of metallic impurities. At higher fields the samples show a negative GMR. Inhomogeneous nonmagnetic LuNiBi samples show no negative GMR, but a large positive MR of 27.5% at room temperature, which is interesting for application.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Crystal Structures, Magnetic Structures and Photophysics in Supramolecular Transition-Metal Oxalate Compounds

Polymeric two- and three-dimensional, homo- and heterometallic oxalatebridged coordination compounds offer exciting opportunities, mainly in the fields of molecular magnetism and photophysics. Given that a large variety of magnetic phenomena have been reported so far from these molecular magnets, very limited experience is gained from elastic neutron scattering experiments. Therefore, with two examples, we will address the topic of the elucidation of magnetic structures by means of the neutron scattering technique. In addition, due to the possibility of the variation of different metal ions in varying oxidation states, interesting photophysical processes can be observed within the extended three-dimensional host/guest systems.