NiN2S2 moieties have been used as a unique class of ligand in organometallic chemistry behaving as innocent mono- and bidentate ligands to metals bound via their thiolate sulfur donor atoms. We have established the donor ability of these ligands with respect to conventional ligands, e.g., diphosphines and diimines, by synthesizing a series of (NiN2S2)W(CO)4 complexes and using infrared spectroscopy to obtain the ν(CO) stretching frequencies as a report of the electron density on the metal. In comparison to the analogous tungsten complexes utilizing traditional ligands, the NiN2S2 ligands were found to be far better donors than the diphosphines as evidenced by significantly lower ν(CO) values, and much closer to diimine ligands. Sulfur’s ability to form aggregates is well documented. The metallodithiolate ligands Ni-1 and Ni-1' have been used resulting in numerous molecular constructions, specifically C3 and C4 paddlewheels of the composition M2Nix. Whereas many paddlewheels in the literature employing NiN2S2 ligands were formed largely unintended, a synthetic approach was designed utilizing multiply-bonded dimetal units of various bond orders. These explorations have extended the range of metal-metal distances accommodated by NiN2S2 units in our library from 2.14 Å to 4.35 Å. The complexes discussed in this dissertation are polymetallic clusters with high positive charges associated with them. Electrochemical studies reveal that the redox activity of the NiN2S2 unit can be deconvoluted from the dimetal unit and that sulfur metallation causes the reduction potential of the NiN2S2 ligand (approximately -2.0 V) to become more positive. With each subsequent reduction, the overall positive charge is lessened which causes the corresponding reduction potentials to be more negative. Solvent dependent studies suggest a partial dissociation of the NiN2S2 ligand reminiscent of the mechanism calculated for Acetyl CoA Synthase. Mixed-ligand species proved unstable in any solvent. As rhodium is an intrinsically catalytic metal, investigations were performed to observe if stable complexes could be prepared to serve as models to study industrially relevant processes. The metalloligands Ni-1 and Ni-1' were found to stabilize multiple oxidation states of rhodium resulting in structural forms such as a heterobimetallic (RhI), a C4 paddlewheel (RhII), and tetrametallic analog to Rubpy (RhIII).

The Cassenha Hill copper-gold prospect is situated in the Catabola area, Huambo Province, southwestern Angola. Geologically, the prospect is part of the Angolan Central Eburnean Zone (CEZ) and consists of Paleoproterozoic metasedimentary rock sequences which have been intruded by Eburnean granitoids at ± 2.1 Ga. The prospect itself comprises an area of 180 Km2 and has been intermittently explored since 2005 by Rift Valley Resources (RVR) and its associates. The Cassenha Hill prospect is characterized by the occurrence of partially altered and highly oxidized metasedimentary rocks (meta-mudstone, meta-siltstone, carbonate-rich rock, meta-sandstone, breccia, and quartzite), and altered isolated granitoids. This study represents the first detailed study of the prospect and aims to shed light on the characteristics of the various rock types (i.e., host and barren rocks), their source/provenance, styles of alteration, and the origin and/or type of the fluid responsible for the mineralization. Techniques applied include borehole core logging, petrography, whole-rock geochemistry (XRF and ICP-MS), and stable isotope geochemistry on samples collected on the surface and from exploration boreholes drilled as part of RVR exploration program. Overall, the petrographic and geochemical studies undertaken in the rocks of the Cassenha Hill prospect indicate the following: (1) The rocks are moderately to strongly fractured; (2) The rocks have experienced weak to moderate chemical weathering; (3) The rocks are compositionally immature and originated from felsic provenance; (4) The rocks are sulfur-poor, and lacking in sulfide minerals (5) The rocks are enriched in LREE and LILE elements and depleted in HREE and HFSE elements; (6) The mineralization is associated with chloritization alteration and predominantly occurs within and/or at the edges of quartz/chlorite-rich veins/fractures and is not restricted to any rock type. Two ore stages could be identified, namely, hypogene ore (stage I) consisting of pyrite ± chalcopyrite ± other copper sulfides, and supergene ore (stage II) consisting of malachite ± azurite ± chrysocolla, which represents the prevalent mineralization at the prospect. The δ 18O value of quartz veins range from +12.81 to +13.53‰, while the δD of chlorite minerals range from -51 to -45‰. Therefore, assuming fluid-rock interaction took place at ≈ 350oC, due to the presence of quartz, the fluid had δ 18OH20 values of about +8‰, which are typical of magmatic waters. On the other hand, at a temperature of ≈ 350oC, and with the difference between chlorite and water being -33.5‰, such fluids would have had δDH20 values of about -20‰ (δ 18OH20= -4‰), which are typical of meteoric waters. Although the various mineral phases have yielded different isotopic signatures, this study suggests that water is ultimately of meteoric origin but exchanged with hydrogen-poor magmatic rock, thus maintaining the meteoric signature. The continuous influx of meteoric waters within the fracture system led to the development of copper oxides such as malachite, azurite and chrysocolla, which possibly originated from the insitu oxidation of the hypogene sulfides. This signature, together with other field, petrographic and geochemical observations allows one to, tentatively, suggest that the Cassenha Hill prospect represents an extension of a polymetallic vein-type of porphyry Cu deposit that has been subjected to supergene processes at the weathering profile.

Matrix assisted laser desorption/ionization time-of flight mass spectrometry (MALDI-TOFMS) is used to study several inorganic coordination complexes and a variety of compounds from cyanobacteria. Also presented is a discussion of TOFMS instrumentation and the improvements in resolution and instrument automation that have lead to widespread and diverse applications of MALDI-TOFMS in all areas of science. The feasibility of using direct laser desorption/ionization (LDI) TOFMS to detect trace elements in a variety of glass samples using a lithium borate fusion technique for sample preparation is investigated. The result of the fusion technique is a homogeneous incorporation of the analytical sample into a glass. The fusion technique is investigated as a way to eliminate matrix effects in direct LDI-TOFMS analysis. However, the high concentration and low ionization potential of lithium suppress ionization of the elements of interest. The detection limits of elements in glass samples were not at the trace level. Therefore the technique is not as useful as well-established analytical methods like X-ray fluorescence and inductively coupled plasma mass spectrometry. Direct laser ablation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of four inorganic coordination complexes are discussed. The compounds studied include [Ir(dpp)2Cl2](PF6), {[(bpy)2Ru(dpp)]2RuCl2}(PF6)4, [(tpy)Ru(tpp)Ru(tpp)RhCl3](PF6)4 and {[(bpy)2Ru(dpp)]2IrCl2}(PF6)5 (dpp = 2,3-bis-(2'-pyridyl)-pyrazine, bpy = 2,2'-bipyridine, tpy = 2,2',6',2"-terpyradine, tpp = 2,3,5,6,-tetrakis-(2'-pyridyl)-pyrazine). Spectral intensities and fragmentation patterns are compared and evaluated for several instrument parameters, matrices, and matrix-to-analyte ratios. Direct ablation and MALDI mass spectra of the monometallic complex showed the same ion peaks and differed only in the relative peak intensities. Direct ablation of the trimetallic complexes produced only low-mass fragments containing one metal atom at most. MALDI spectra of the trimetallic complexes exhibited little fragmentation in the high-mass region (>1500 Da) and less fragmentation in the low-mass region compared to direct laser ablation. Proper matrix selection for MALDI analysis was vital, as was an appropriate matrix-to-analyte ratio. The results demonstrate the applicability of MALDI-TOF mass spectrometry for the structural characterization of labile inorganic coordination complexes. A correlation is made between the gas-phase redox chemistry in the MALDI plume and the solution phase electrochemistry for this series of complexes. MALDI-TOFMS was also used to study compounds isolated from cyanobacteria. A MALDI screening method has been developed to detect the presence of scytonemin, a UV-absorbing pigment. Detection of scytonemin is accomplished by a simple solvent extraction of cyanobacteria in the desiccated state with subsequent MALDI-TOFMS analysis. The method is rapid and semi-quantitative. Cyanobacteria is the only known organism to produce scytonemin, and it is only produced when the organism is subjected to UV stress. Laboratory-grown cultures were subjected to different amounts of UV radiation, and the screening method was used to detect the presence or absence of scytonemin. Cultures grown under ambient conditions (low UV) did not show the presence of scytonemin, while those grown under UV lamps did show the detectable scytonemin. Because scytonemin acts as a biomarker for UV stress, the MALDI screening method could find application in molecular ecology studies of cyanobacteria. Peptide mass fingerprinting is used to monitor the isolation of the water stress protein from N. commune. The protein is produced by recombinant growth in E. coli in order to assess the role of Wsp in the desiccation tolerance of N. commune. The results show that SDS-PAGE and Western blot analysis are not sufficient to detect the presence of Wsp after purification using ion-exchange chromatography. Three E. coli proteins were identified in the same molecular weight range as Wsp and one of them cross-reacts with the series of antibodies used for the Western blot. The presence of contaminating proteins that cross-react with the immuno assay make it difficult to determine which fractions contained Wsp. Peptide mass fingerprints were obtained for a series of fractions collected after ion-exchange chromatography to pinpoint the location of Wsp. Peptide mass fingerprinting was also used to monitor the stability of the clone and results show that the clone is modified over a six month period. / Ph. D.

A series of bimetallic (Ru^II, Pt<sup>II</sup) complexes were synthesized with the general formula [(tpy)RuCl(BL)PtCl₂](PF₆) (tpy = 2,2':6',2"-terpyridine and BL = bridging ligand) and their spectroscopic, electrochemical, and DNA binding properties studied. The bridging ligands used in these complexes were 2,3-bis(2'-pyridyl)pyrazine (dpp), 2,3-bis(2'-pyridyl)quinoxaline (dpq) and 2,3-bis(2'-pyridyl)benzoquinoxaline (dpb). These complexes combine light-absorbing Ru^II-polypyridyl chromophores and a cis-PtCl₂ structural motif known to bind DNA. The Ru-bound chloride may be substituted, enabling further modification of the spectroscopic properties. The synthesis of [(tpy)RuCl(BL)PtCl₂](PF₆) utilizes a building block approach that allows modifications to the series of complexes within the general synthetic scheme. This illustrates the applicability of this scheme to the development of new series of complexes. The lowest-energy absorption for the three complexes is assigned to a Ru(dπ) → BL(π*) charge transfer transition. This transition shifts to lower energy as the ligand is varied from dpp to dpq to dpb. The first and second reductions are BL^0/- and BL^-/2- based and shift to more positive potentials from dpp to dpq to dpb. The Ru^II/III redox couple remains at a nearly constant potential for the series. All three compounds show DNA binding when incubated with linearized plasmid DNA. Adduct formation was assessed by agarose gel electrophoresis as a retardation of band migration. / Master of Science

Deep sea polymetallic nodules are concretions of manganese and iron oxides formed around a nucleus. They accrete either hydrogenetically - metals precipitate from the seawater - or diagenetically - metals precipitate from the sediment pore water. The accretion process affects both the nodules morphology and geochemistry. In this study, fourteen polymetallic nodules from four ocean regions, namely the Clarion-Clippertone Zone (Northeast Pacific Ocean), the Central Indian Basin (Central Indian Ocean), the Mascarene Basin (West Indian Ocean), and the Rio Grande Rise (Southwest Atlantic Ocean), were used to compare morphological and geochemical aspects between the different oceanic regions. Computed Tomography (CT) was applied to study the nodules internal structure. Scanning Electron Microscopy (SEM) was used to describe the micro layers within the nodules. Chemical composition of growth layers and nuclei was determined by both Micro X-ray Fluoscence (&#956;-XRF) and Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS). Finally, X-ray Absorption Near Edge Spectroscopy (XANES) was performed in order to determine the speciation (i.e., the oxidation state) of Mn and Fe. Polymetallic nodules from the Central Indian Basin are diagenetic and the ones from the Mascarene Basin and the Rio Grande Rise are hydrogenetic, while nodules from the Clarion-Clippertone Zone are of mixed type. However, the dominant accretion process varies across the nodules resulting in inhomogeneous layer textures and chemical composition. Strong Mn and Fe fractionation occurs in the diagenetic and mixed type nodules accompanied by fractionation of the trace elements Ni, Cu, Co and Ti. Mn and Fe are present in the nodules mainly as oxidized species Mn4+ and Fe3+, independently of the degree of fractionation. Schematic models of the nodules environment of formation are proposed, in which and the fractionation of Mn and Fe is possibly the result of the variation of the redox front depth through time. / Nódulos polimetálicos de mar profundo são concreções de óxidos de manganês e de ferro ao redor de um núcleo. Os nódulos crescem através da precipitação hidrogenética - precipitação de metais da água do mar - ou diagenética - precipitação de metais da água intersticial do sedimento. O processo de acreção reflete na morfologia e geoquímica dos nódulos. Neste trabalho, quatorze nódulos polimetálicos provenientes de quatro regiões oceânicas - Clarion-Clippertone Zone (Oceano Pacífico Nordeste), Bacia Central do Índico (Oceano Índico Central), Bacia Mascarene (Oceano Índico Oeste) e Elevação de Rio Grande (Oceano Atlântico Sudoeste) - foram usados a fim de se comparar os aspectos morfológicos e geoquímicos dos nódulos entre regiões diferentes. A estrutura interna dos nódulos foi avaliada através da Tomografia Computadorizada por Raios-X (CT). Microscopia Eletrônica de Varredura (SEM) foi usada para descrever as micro camadas. A composição química foi determinada por Micro Fluorescência de Raios-X (&#956;-XRF) e por ablação a laser acoplada a espectrometria de massa com plasma indutivamente acoplado (LA-ICP-MS). Por fim, a Espectroscopia de Absorção de Raios-X próximo à borda (XANES) foi realizada a fim de se determinar a especiação (i.e., o número de oxidação) do Mn e do Fe. Os nódulos polimetálicos da Bacia Central do Índico são diagenéticos e os da Bacia Mascarene e Elevação do Rio Grande são hidrogênicos, enquanto que os da Clarion-Clippertone Zone são do tipo misto. Entretanto, o processo de acreção varia ao longo dos nódulos, resultando em textura das camadas e composição química heterogênea. Forte fracionamento entre Mn e Fe ocorre nos nódulos diagenéticos e do tipo misto, assim como entre os metais traço Ni, Cu, Co e Ti. O Mn e o Fe estão presentes nos nódulos principalmente na forma de espécies oxidadas Mn4+ e Fe3+, independentemente do efeito de fracionamento entre eles. Modelos esquemáticos do ambiente de formação dos nódulos são propostos e sugere-se que variações da profundidade da frente redox no sedimento ao longo do tempo são responsáveis pelo efeito de fracionamento entre o Mn e o Fe.

Porphyry copper deposits represent one of the largest copper reserves on Earth. They typically contain large, low-grade reserves of primary ore and higher-grade, supergene enrichment blankets of sulfide and oxide ores. Understanding the mineralogy of porphyry copper ores and ores related to porphyry copper systems is exceedingly important for several reasons, foremost of which are the information provided by ore mineral parageneses, assemblages, and mineral chemistry on evolution of these magmatic-hydrothermal systems, and information on mineral processing characteristics of the ores. The focus of this work is to better understand the mineralogy of supergene copper sulfides in porphyry copper systems and hypogene base metal lodes related to porphyry copper systems, and use this mineralogical knowledge to improve our understanding of the processes responsible for ore formation. The objectives of this study are accomplished by two means: focusing on the crystallography and crystal chemistry of minerals, and then applying this mineralogical knowledge to a supergene sulfide enrichment blanket and hypogene massive sulfides from base metal lodes in southeastern Arizona. The discovery of a new mineral, natropalermoite, NaSr2Al4(PO4)4(OH)4, provided the opportunity to use single-crystal X-ray diffraction to solve a crystal structure, and electron-probe microanalysis (EPMA) to study the crystal chemistry of natropalermoite and how the accommodation of Na in the structure changes lengthens the unit cell along [010] and shortens it along [100] and [001] compared to its lithium analogue, palermoite. Solution of the crystal structure of the mineral nickelskutterudite, (Ni,Co,Fe)As3, allowed for the investigation of anion deficiency in minerals of the skutterudite group, a problem whose solution has eluded researchers for nearly 100 years. Two skutterudite (CoAs3) and two nickelskutterudite samples were analyzed using single-crystal X-ray diffraction, EPMA, and procrystal electron density. The results showed fully-occupied anion sites and a cation surplus, which was accommodated in the icosahedral site, proving that minerals of the skutterudite group are not anion deficient. This mineralogical knowledge was applied to the supergene enrichment blanket in the Western Copper section of the Morenci mine, Greenlee County, and hypogene massive sulfide deposits associated with a porphyry copper deposit at Bisbee, Cochise County, Arizona. This is one of very few studies of supergene sulfide blankets ever completed. One drill hole through the supergene blanket at Western Copper was examined using ore microscopy and EPMA. Results showed dominant (Cu+Fe):S ratios of 1.80 ± 0.05, 1.92 ± 0.03, and 1.10 ± 0.10, with higher (Cu+Fe):S dominant high in the blanket and low ratios dominant near the base of the blanket. These values were interpreted to be controlled by activity of Cu2+, Fe2+, and Fe3+ in solution. Massive sulfide deposits at Bisbee were investigated using ore microscopy and EPMA in order to correct the previous conflicting reports of the mineralogy and paragenesis of this famous district and interpret constraints on conditions of ore-forming fluids. Results show four types of ore: chalcopyrite-rich with hematite and/or pyrite, bornite-rich, chalcocite-rich, and a Zn-Pb association. Chalcopyrite-rich ores formed first, followed by bornite-rich and chalcocite-rich ores. All ores were formed at relatively shallow depths from oxidized, moderately sulfur-rich fluids; early fluids were higher temperature and later fluids were lower temperature and considerably more sulfidized. Zinc-lead ores formed early and were continuously dissolved and reprecipitated distal to Cu-mineralization. These patterns are similar to many other base-metal lode districts worldwide, however Bisbee contains more Zn-Pb ore than other districts with hematite-containing ores and less than those without hematite.

Deep sea polymetallic nodules are concretions of manganese and iron oxides formed around a nucleus. They accrete either hydrogenetically - metals precipitate from the seawater - or diagenetically - metals precipitate from the sediment pore water. The accretion process affects both the nodules morphology and geochemistry. In this study, fourteen polymetallic nodules from four ocean regions, namely the Clarion-Clippertone Zone (Northeast Pacific Ocean), the Central Indian Basin (Central Indian Ocean), the Mascarene Basin (West Indian Ocean), and the Rio Grande Rise (Southwest Atlantic Ocean), were used to compare morphological and geochemical aspects between the different oceanic regions. Computed Tomography (CT) was applied to study the nodules internal structure. Scanning Electron Microscopy (SEM) was used to describe the micro layers within the nodules. Chemical composition of growth layers and nuclei was determined by both Micro X-ray Fluoscence (&#956;-XRF) and Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS). Finally, X-ray Absorption Near Edge Spectroscopy (XANES) was performed in order to determine the speciation (i.e., the oxidation state) of Mn and Fe. Polymetallic nodules from the Central Indian Basin are diagenetic and the ones from the Mascarene Basin and the Rio Grande Rise are hydrogenetic, while nodules from the Clarion-Clippertone Zone are of mixed type. However, the dominant accretion process varies across the nodules resulting in inhomogeneous layer textures and chemical composition. Strong Mn and Fe fractionation occurs in the diagenetic and mixed type nodules accompanied by fractionation of the trace elements Ni, Cu, Co and Ti. Mn and Fe are present in the nodules mainly as oxidized species Mn4+ and Fe3+, independently of the degree of fractionation. Schematic models of the nodules environment of formation are proposed, in which and the fractionation of Mn and Fe is possibly the result of the variation of the redox front depth through time. / Nódulos polimetálicos de mar profundo são concreções de óxidos de manganês e de ferro ao redor de um núcleo. Os nódulos crescem através da precipitação hidrogenética - precipitação de metais da água do mar - ou diagenética - precipitação de metais da água intersticial do sedimento. O processo de acreção reflete na morfologia e geoquímica dos nódulos. Neste trabalho, quatorze nódulos polimetálicos provenientes de quatro regiões oceânicas - Clarion-Clippertone Zone (Oceano Pacífico Nordeste), Bacia Central do Índico (Oceano Índico Central), Bacia Mascarene (Oceano Índico Oeste) e Elevação de Rio Grande (Oceano Atlântico Sudoeste) - foram usados a fim de se comparar os aspectos morfológicos e geoquímicos dos nódulos entre regiões diferentes. A estrutura interna dos nódulos foi avaliada através da Tomografia Computadorizada por Raios-X (CT). Microscopia Eletrônica de Varredura (SEM) foi usada para descrever as micro camadas. A composição química foi determinada por Micro Fluorescência de Raios-X (&#956;-XRF) e por ablação a laser acoplada a espectrometria de massa com plasma indutivamente acoplado (LA-ICP-MS). Por fim, a Espectroscopia de Absorção de Raios-X próximo à borda (XANES) foi realizada a fim de se determinar a especiação (i.e., o número de oxidação) do Mn e do Fe. Os nódulos polimetálicos da Bacia Central do Índico são diagenéticos e os da Bacia Mascarene e Elevação do Rio Grande são hidrogênicos, enquanto que os da Clarion-Clippertone Zone são do tipo misto. Entretanto, o processo de acreção varia ao longo dos nódulos, resultando em textura das camadas e composição química heterogênea. Forte fracionamento entre Mn e Fe ocorre nos nódulos diagenéticos e do tipo misto, assim como entre os metais traço Ni, Cu, Co e Ti. O Mn e o Fe estão presentes nos nódulos principalmente na forma de espécies oxidadas Mn4+ e Fe3+, independentemente do efeito de fracionamento entre eles. Modelos esquemáticos do ambiente de formação dos nódulos são propostos e sugere-se que variações da profundidade da frente redox no sedimento ao longo do tempo são responsáveis pelo efeito de fracionamento entre o Mn e o Fe.

La construction de complexes polymétalliques de lanthanides préprogrammés et sophistiqués, de taille nanométrique, pour le développement de matériaux luminescents présentant des propriétés photophysiques nouvelles ou améliorées (double émission, transfert d'énergie intermétallique, etc.) est un des sujets de la chimie supramoléculaire des lanthanides suscitant énormément d'intérêt. La compréhension, le contrôle et la programmation de l'auto-assemblage de complexes de lanthanides est un défi majeur en raison de la difficulté à contrôler l'environnement de coordination de ces ions qui se caractérise par des nombres de coordinations importants et variables et peu de préférences stéréochimiques. Ainsi, la plupart des complexes polynucléaires de lanthanides décrits dans la littérature sont formés de façon fortuite plutôt que par conception rationnelle. Afin d'inclure les ions lanthanides dans des architectures polymétalliques de haute nucléarité tout en améliorant leurs propriétés photophysiques, nous nous sommes concentrés sur des études de complexation de ligands dissymétriques (tridentates anioniques, tétradentates chiraux) permettant de promouvoir la formation des assemblages. Nous avons par ailleurs commencé à explorer le potentiel d'une méthode synthétique originale de clusters oxo par réactivité redox de complexes divalents de lanthanides. Nous présentons ici la synthèse et les propriétés photophysiques de complexes stables émettant dans le proche infrarouge basés sur des ligands anioniques hydroxyquinoléine fonctionnalisé par des groupes carboxylates ou tétrazolates. En outre, nous pouvons montrer que l'utilisation de ligands chiraux possédant un groupement oxazoline favorise l'auto-assemblage diastéréosélectif de complexes de lanthanides homo- et hétéro-polymétalliques énantiopures émettant dans le visible et le proche infrarouge. Un complexe trinucléaire d'europium énantiopure a été caractérisé par cristallographie, celui-ci présentant une forte activité en polarisation circulaire de luminescence (CPL). Le ligand chiral oxazoline a permis d'obtenir une roue heptanucléaire d'europiums, le plus important assemblage polymétallique énantiopure. Enfin, nous avons pu préparer et caractériser des complexes de lanthanides divalents hautement réactifs basés sur un ligand tripode neutre possédant des groupements pyridine (tpa). Des résultats préliminaires montrent que ces complexes peuvent être des précurseurs très utiles pour isoler des clusters oxo polymétalliques. En particulier, la réaction d'un complexe de néodyme hautement réactif a conduit à isoler un cluster oxo volumineux et très intéressant par clivage de THF en présence de tpa. / The construction of preprogrammed, sophisticated and nanoscopic polymetallic lanthanide complexes for the development of luminescent materials that possess new or improved photophysical properties (dual emission, intermetallic energy transfer, etc.) is one of the hot topics in the lanthanide supramolecular chemistry. Understanding, controlling and programming self assembly of lanthanide complexes is a key challenge due to the difficulty in controlling the coordination environment of these ions which display high and variable coordination numbers with little stereochemical preferences. As a result of this, most of the polynuclear lanthanide complexes reported in literature are formed by serendipity rather than rational design. In order to include lanthanide ions in discrete high nuclearity polymetallic architectures with improved photophysical properties we have concentrated on complexation studies with dissymmetric chelating ligands (tridentate anionic ligands, tetradentate chiral ligand) with possibility of promoting assembly formation, and we started to investigate the potential of an original synthetic method using the redox reactivity of divalent lanthanides complexes for the synthesis of oxo clusters. Here we present the synthesis and photophysical properties of NIR emissive stable complexes obtained with hydroxyquinoline based tridentate dianionic ligands functionalised with carboxylic acid and tetrazole groups. Moreover we show that the use of a chiral tetradentate ligand possessing oxazoline ring promotes the diastereoselective self assembly of enantiopure homo- and hetero-polymetallic lanthanide complexes emitting in the visible and NIR range. An original enantiopure trinuclear europium complex was crystallographically characterised and we found that it displays a high circularly polarized luminescence (CPL) activity. The chiral oxazoline based ligand also led to the synthesis of the largest enantiopure polymetallic assembly of europium, a heptanuclear wheel. Finally we were able to prepare and characterize highly reactive complexes of divalent lanthanides with a neutral tripodal pyridine based ligand and very preliminary results show that these complexes can be useful precursors for the isolation of polymetallic oxoclusters. Notably, the reaction of the highly reactive neodymium complex led to the isolation of a very interesting large neodymium oxo cluster by cleavage of THF in the presence of the ligand tpa.

Le magnétisme moléculaire est une discipline qui regroupe le magnétisme de molécules relativement simples mais aussi celui de systèmes très complexes : molécules à haut spin, aimants à base moléculaire, molécules-aimants… Le travail présenté ici se place dans ce contexte et abord la synthèse et l’étude détaillée des structures cristallines et des propriétés magnétiques de complexes polymétalliques à base de métaux 3d et 4f. L’une des préoccupations majeure de ce travail concerne la compréhension des relations magnéto-structurales dans ces systèmes. Dans le premier chapitre nous donnons quelques éléments de magnétisme moléculaire et les principaux résultats dans le domaine des matériaux à base moléculaire. Dans le deuxième chapitre de ce travail nous présentons les résultats variés obtenus grâce à l’association d’un ligand simple, la 2-hydrosypyridine, avec des ions de CuII et LnIII. Les synthèses réalisées ont permis d’obtenir deux séries différentes de composés : hexanucléaires de type [Cu4Ln2] et décanucléaires de type [Cu8Ln2]. Dans le troisième chapitre nous avons focalisé notre étude sur la synthèse et caractérisation d’un complexe à valence mixte de manganèse comportant le cation [MnII(MnII3MnIII3)L12]5+, ou L = 2-hydroxybenzimidazole. Dans le dernier chapitre nous présentons les résultats de l’étude théorique et expérimentale des interactions antiferromagnétiques et de l’anisotropie dans un composé dinucléaire de CoII à partir de mesures effectuées sur des monocristaux de grande taille. Cette étude a été complétée par une étude par diffraction de neutrons polarisés selon les trois directions cristallographiques a, b et c d’un monocristal / Molecular magnetism is a field which gathers the magnetism of the simplest molecules but also that of very complex systems : high-spin molecules, molecular-based magnets, single molecule magnets, magnetic supramolecular buildings. Coordination chemistry is one way to obtain compounds with specific magnetic properties : ferromagnetic exchange interactions, uniaxial anisotropy, slow relaxation and quantum tunnelling of magnetization. In this context, the work presented here reports the synthesis and the detailed study of the crystal structures and interest of this study is the understanding of the magneto-structural relationships. In the fist chapter we give some elements of molecular magnetism. In the second chapter we present the results obtained by the association of 2-hydroxypyridine lignad, with cuII et LnIII ions. The syntheses lead to two different series of compounds : [Tu4Ln2] and [Cu8Ln2]. In the third chapiter we foaclized our attention on synthesis and study of new heptanuclear mixed-valence manganese complex with 2-OHBzIm ligand (2-hydroxybenzimidazole). The structure is formed by [Mn7(L]12]5+ core, consisting in a nearly planar Mn7 unit comprising a central Mn held within a Mn6 hexagon. The magnetic properties of this compound show a single molecule magnet behaviour. In the last chapter we report the results of the theoretical and experimental study of the antiferromagnetic exchange interactions ad the anisotropy in a dinuclear CoII complex from measurements made on large size single crystal. This study was completed with a polarized neutron diffraction study

L’extraction de l’uranium a eu pour conséquence une remobilisation de cet actinide au niveau des écosystèmes avoisinants les mines. L’utilisation de sels métalliques lors de la réhabilitation des sites miniers et la présence naturelle de métaux ont accentué les niveaux de la contamination métallique dans les hydrosystèmes soumis aux rejets miniers uranifères.Des expériences in situ ont été conduites au niveau de deux anciens sites miniers uranifères français. L’encagement de l’épinoche à trois épines a été employé pour connaître les effets sublétaux de ce mélange métallique, ainsi que sur la susceptibilité de ce poisson envers un stress biologique.Cette pollution, caractérisée par de plus importantes concentrations métalliques (notamment en uranium), a entraîné un stress oxydant chez l’épinoche visible sur plusieurs biomarqueurs, ainsi que d’autres effets dépendants du site d’exposition.La contamination polymétallique a occasionné une augmentation de la susceptibilité des épinoches au stress biologique, en empêchant leurs réponses phagocytaire antioxydante à ce stress. Ces travaux ont permis de renforcer l’intérêt de la technique d’encagement lors d’une étude environnementale, et celui des immunomarqueurs au sein d’une approche multi-biomarqueurs. / Uranium extraction has resulted in a remobilisation of this actinide into mine surrounding ecosystems. Uses of metal salts during mining site rehabilitation, and the natural presence of metals have increased the metal contamination in hydrosystems submitted to mine tailings.In situ experiments were conducted in two former French uranium mining sites. Three-spined stickleback caging was used to determine the sublethal effects of this metal mixture on this freshwater fish, as well as its effects on fish susceptibility to a sudden biological stress.This pollution, characterised by higher metal concentrations (especially for uranium), has led to an oxidative stress in sticklebacks visible through several biomarkers, and other effects dependent on the study site. The polymetallic contamination has modified the stickleback responses to the biological stress, by preventing their phagocytic and antioxidant responses. This work has reinforced the interest of the caging technique during environmental studies and that of immunomarkers in a multi-biomarker approach.