Raw and normalized X-ray fluorescence (XRF) scannings of IODP Expedition 321, Site U1338

We used X-ray fluorescence (XRF) scanning on Site U1338 sediments from Integrated Ocean Drilling Program Expedition 321 to measure sediment geochemical compositions at 2.5 cm resolution for the 450 m of the Site U1338 spliced sediment column. This spatial resolution is equivalent to ~2 k.y. age sampling in the 0-5 Ma section and ~1 k.y. resolution from 5 to 17 Ma. Here we report the data and describe data acquisition conditions to measure Al, Si, K, Ca, Ti, Fe, Mn, and Ba in the solid phase. We also describe a method to convert the data from volume-based raw XRF scan data to a normalized mass measurement ready for calibration by other geochemical methods. Both the raw and normalized data are reported along the Site U1338 splice.

Mineralogy, geochemistry and elemental ratios of ODP Core 171B-1049C-8X

Inorganic geochemistry and mineralogy of Core 171B-1049C-8X, containing a Cretaceous/Tertiary boundary section, was investigated by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The ages of samples analyzed stretched from the latest Maastrichtian into the Danian. XRD measurements were made using the peak height method. A reduction in low-magnesium calcite and an increase in quartz were found above the spherule layer. Substantial amounts of dolomite were noted just above the spherule layer. XRF analyses were performed using the RHSMALL program to measure the abundance of major and minor elements. Replicate analyses for each technique were performed to assess the precision of the results. The section above the spherule bed was found to be characterized by peaks in many elements, including Si, Al, Fe, and Mg, as well as the following elemental ratios: Fe/Al, Ni/Al, Zr/Rb, and Rb/Sr'. Above the spherule bed, there were significant reductions in Ca, Sr/Ca, Ti/Al, K/Al, Rb/Al, Cr/Al, Ba/Al, biogenic Ba, and excess P.

Experimental data from column and batch samples

The presented thesis was written in the frame of a project called 'seepage water prognosis'. It was funded by the Federal Ministry for Education and Science (BMBF). 41 German institutions among them research institutes of universities, public authorities and engineering companies were financed for three years respectively. The aim was to work out the scientific basis that is needed to carry out a seepage water prognosis (Oberacker und Eberle, 2002). According to the Federal German Soil Protection Act (Federal Bulletin, 1998) a seepage water prognosis is required in order to avoid future soil impacts from the application of recycling products. The participants focused on the development of either methods to determine the source strength of the materials investigated, which is defined as the total mass flow caused by natural leaching or on models to predict the contaminants transport through the underlying soil. Annual meetings of all participants as well as separate meetings of the two subprojects were held. The department of Geosciences in Bremen participated with two subprojects. The aim of the subproject that resulted in this thesis was the development of easily applicable, valid, and generally accepted laboratory methods for the determination of the source strength. In the scope of the second subproject my colleague Veith Becker developed a computer model for the transport prognosis with the source strength as the main input parameter.

Element concentrations of bulk sediment from the Southern Cape Basin

High-resolution records of Ca and Sr were obtained from shipboard XRF analyses of bulk sediments in five gravity cores from the southern Cape Basin, South Atlantic Ocean. Sr/Ca ratios display regular glacial/interglacial variations of 14-40% and reveal a close correlation with the SPECMAP record, minimum Sr/Ca ratios appearing during glacial (delta18 O) maxima, distinct increases during periods of deglaciation, and highest ratios in interstadials. Shifts in carbonate-producing phytoplankton and/or zooplankton assemblages over glacial/interglacial cycles are suggested to be the main cause for the observed variations in Sr/Ca patterns. Quick assessment of the relationship between Sr/Ca ratios and the SPECMAP record made it possible to easily transfer an age model to the newly collected cores already during the cruise.

Core scans and lithologic analysis of Subglacial Lake Whillans sediment cores

The hydrologic system beneath the Antarctic Ice Sheet is thought to influence both the dynamics and distribution of fast flowing ice streams, which discharge most of the ice lost by the ice sheet. Despite considerable interest in understanding this subglacial network and its affect on ice flow, in situ observations from the ice sheet bed are exceedingly rare. Here we describe the first sediment cores recovered from an active subglacial lake. The lake, known as Subglacial Lake Whillans, is part of a broader, dynamic hydrologic network beneath the Whillans Ice Stream in West Antarctica. Even though "floods" pass through the lake, the lake floor shows no evidence of erosion or deposition by flowing water. By inference, these floods must have insufficient energy to erode or transport significant volumes of sediment coarser than silt. Consequently, water flow beneath the region is probably incapable of incising continuous channels into the bed and instead follows preexisting subglacial topography and surface slope. Sediment on the lake floor consists of till deposited during intermittent grounding of the ice stream following flood events. The fabrics within the till are weaker than those thought to develop in thick deforming beds suggesting subglacial sediment fluxes across the ice plain are currently low and unlikely to have a large stabilizing effect on the ice stream's grounding zone.

Chemical composition of ocean manganese nodules from the Pacific Ocean using different techniques

Mineralogical and chemical analyses performed on 67 ferromanganese nodules from widely varying locations and depths within the marine environment of the Pacific Ocean indicate that the minor element composition is controlled by the mineralogy and that the formation of the mineral phases is depth dependent. The pressure effect upon the thermodynamics or kinetics of mineral formation is suggested as the governing agent in the depth dependence of the mineralogy. The minor elements, Pb and Co, appear concentrated in the dMnO2 phase, whereas Cu and Ni are more or less excluded from this phase. In the manganites, Pb and Co are relatively low in concentration, whereas Cu and Ni are spread over a wide range of values. The oxidation of Pb and Co from divalent forms in sea water to higher states can explain their concentration in the dMnO2 phase.

High performance cobalt-free Cu_1.4Mn_1.6O₄ spinel oxide as an intermediate temperature solid oxide fuel cell cathode

<p>In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78��S��cm^���1 is achieved at 800����C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10��mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143������cm² at 800����C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076��mW��cm^���2 at 800����C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.</p>

Surface modifications of nanocrystalline diamond films and their functionalization with phthalocyanines

Boron-doped diamond is a promising electrode material for a number of applications providing efficient carrier transport, a high stability of the electrolytic performance with time, a possibility for dye-sensitizing with photosensitive molecules, etc. It can be functionalized with electron donor molecules, like phthalocyanines or porphyrins, for the development of light energy conversion systems. For effective attachment of such molecules, the diamond surface has to be modified by plasma- or photo-chemical processes in order to achieve a desired surface termination. In the present work, the surface modifications of undoped and boron-doped nanocrystalline diamond (NCD) films and their functionalization with various phthalocyanines (Pcs) were investigated. The NCD films have been prepared by hot filament chemical vapor deposition (HFCVD) on silicon substrates and were thereafter subjected to modifications with O2 or NH3 plasmas or UV/O3 treatments for exchange of the H-termination of the as-grown surface. The effectiveness of the modifications and their stability with time during storage under different ambients were studied by contact angle measurements and X-ray photoelectron spectroscopy (XPS). Furthermore, the surface roughness after the modifications was investigated with atomic force microscopy (AFM) and compared to that of as-grown samples in order to establish the appearance of etching of the surface during the treatment. The as-grown and the modified NCD surfaces were exposed to phthalocyanines with different metal centers (Ti, Cu, Mn) or with different side chains. The results of the Pc grafting were investigated by XPS and Raman spectroscopy. XPS revealed the presence of nitrogen stemming from the Pc molecules and traces of the respective metal atoms with ratios close to those in the applied Pc. In a next step Raman spectra of Ti-Pc, Cu-Pc and Mn-Pc were obtained with two different excitation wavelengths (488 and 785 nm) from droplet samples on Si after evaporation of the solvent in order to establish their Raman fingerprints. The major differences in the spectra were assigned to the effect of the size of the metal ion on the structure of the phthalocyanine ring. The spectra obtained were used as references for the Raman spectra of NCD surfaces grafted with Pc. Finally, selected boron doped NCD samples were used after their surface modification and functionalization with Pc for the preparation of electrodes which were tested in a photoelectrochemical cell with a Pt counter electrode and an Ag/AgCl reference electrode. The light sources and electrolytes were varied to establish their influence on the performance of the dye-sensitized diamond electrodes. Cyclic voltammetry measurements revealed broad electrochemical potential window and high stability of the electrodes after several cycles. The open circuit potential (OCP) measurements performed in dark and after illumination showed fast responses of the electrodes to the illumination resulting in photocurrent generation.

Applicazione della Tomografia con raggi X per la lettura virtuale di antichi manoscritti veneziani

Questo lavoro di tesi si inserisce in un progetto di ricerca internazionale denominato ���Venice Time Machine��� dove collaborano fianco a fianco l���Ecole Polytechnique Fe��de��rale de Lausanne e l���Universita�� Ca�� Foscari di Venezia. Grazie al coinvolgimento dell���Archivio di Stato di Venezia, decine di chilometri di documenti verranno digitalizzati e indicizzati, al fine di creare un database open access da utilizzare per la ricerca e l���istruzione. Molti di questi documenti tuttavia sono particolarmente fragili oppure, come nel caso di diversi testamenti, non sono mai stati aperti, per cui le tecniche tradizionali di digitalizzazione non sono applicabili. Di qui deriva l���interesse per sperimentare nuove tecniche non invasive al fine di digitalizzare e quindi rendere fruibili al pubblico anche questi documenti altrimenti inaccessibili. Lo scopo dell���analisi tomografica e�� quello di creare un modello 3D del documento, su cui effettuare successive elaborazioni al fine di ottenere una separazione virtuale delle pagine e quindi permetterne la lettura anche se il manoscritto e�� chiuso e non puo�� essere aperto. In particolare in questo lavoro di tesi sono stati analizzati due testamenti: un testamento del 1679, usato come campione di prova per verificare la migliore sorgente di raggi X ai fini della ricostruzione tomografica e anche per valutare l���efficacia della tecnica, e il testamento Alchier-Spiera (dai nomi dei testatori), datato 1634, di maggiore interesse poiche�� ancora chiuso. I risultati ottenuti sono molto soddisfacenti, poiche�� elaborando le ricostruzioni tomografiche e�� possibile la lettura virtuale sia di parole che di intere frasi. Questo risultato porta nuova linfa al progetto che, di base, si pone l���obiettivo di convertire in formato digitale decine di km di testi conservati in Archivio, ma che ha trovato, in questo tipo di testamenti chiusi, un ostacolo molto difficile da superare.

Studio delle propriet�� in banda X degli AGN a z > 5.5

Si �� effettuato lo studio pi�� completo e uniforme delle propriet�� X degli AGN ad alto redshift (z>5.5) mai realizzato. Questo studio vuole anche essere un lavoro preliminare per le survey che verranno effettuate con eROSITA e, su tempi pi�� lunghi, con Athena.

Determina����o de cobre, cromo e ars��nio em madeira preservada (Eucalyptus sp.) pelas espectrometrias de fluoresc��ncias de raios X

Disserta����o (Mestrado em Tecnologia Nuclear)

Aroylhydrazone Cu(II) complexes in keto form: structural characterization and catalytic cctivity towards cyclohexane oxidation

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with a copper(II) salt of a base of a strong acid, i.e., nitrate, chloride or sulphate, yielded the mononuclear complexes [Cu(H2L)(NO3)(H2O)] (1), [Cu(H2L)Cl]center dot 2MeOH (2) and the binuclear complex [{Cu(H2L)}(2)(mu-SO4)]center dot 2MeOH (3), respectively, with H2L- in the keto form. Compounds 1-3 were characterized by elemental analysis, Infrared (IR) spectroscopy, Electrospray Ionisation-Mass Spectrometry (ESI-MS) and single crystal X-ray crystallography. All compounds act as efficient catalysts towards the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, under mild conditions. In the presence of an acid promoter, overall yields (based on the alkane) up to 25% and a turnover number (TON) of 250 (TOF of 42 h(-1)) after 6 h, were achieved.

Estudo do aerossol (poeira do Sara) na regi��o de Cabo Verde

No ��mbito do projeto CV-DUST foi desenvolvida uma campanha de medi����o do aerossol atmosf��rico na Cidade da Praia (14�� 55��� N, 23��29��� W), de janeiro de 2011 a janeiro de 2012. A concentra����o do aerossol foi determinada com base no m��todo gravim��trico, com a amostragem feita em termos de PM10 e em fra����es granulom��tricas, usando impactores. Complementarmente, foi usado um contador ��tico de part��culas que permite a monitoriza����o em cont��nuo e a classifica����o do n��mero de part��culas em 31 fra����es de tamanho na gama entre 0,25 e 32 ��m. A composi����o qu��mica do aerossol foi determinada com incid��ncia nos seguintes componentes: i��es inorg��nicos sol��veis em ��gua (Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+ e Ca2+), carbonato total, elementos maiorit��rios da crosta (Si, Na, Al, Fe, Ca, Mg, K, Ti e Mn) e elementos vestigiais (Ba, Zn, Zr, Pb, Cu, Ce, Ni, Cr, V, Co, Sc, As, Sm e Sb), assim como a fra����o carbon��cea (carbono elementar ��� EC e o carbono org��nico - OC). Durante a campanha, a concentra����o de PM10 apresentou uma grande variabilidade temporal, com valores m��dios (�� escala di��ria) situados entre 10 ��g/m3 e 507 ��g/m3, sendo a concentra����o m��dia anual estimada em cerca de 59 ��g/m3. As concentra����es mais elevadas (tipicamente acima dos 100 ��g/m3) foram registadas durante os eventos de poeira proveniente do Norte de ��frica, sendo os mais intensos observados nos meses de janeiro, fevereiro e dezembro de 2011. Os registos do contador ��tico, feitos em intervalos de 5 min, revelaram que durante os eventos de poeira as concentra����es m��dias hor��rias das part��culas PM10 e PM2.5 podem ultrapassar os 700 ��g/m3 e 200 ��g/m3, respetivamente. Com base nos resultados do m��todo ��tico, as contribui����es das fra����es granulom��tricas PM1, PM(1-2.5) e PM(2.5-10) para a massa de PM10 foram estimadas em cerca de 11 %, 28 % e 61 %, respetivamente. A composi����o qu��mica do aerossol varia consideravelmente ao longo do ano e revela a predomin��ncia das part��culas minerais e do sal marinho. Com base em c��lculos do balan��o m��ssico das esp��cies qu��micas, as contribui����es dos dois constituintes maiorit��rios para a massa de PM10 foram estimadas em cerca de 47 % (part��culas minerais) e 17 % (sal marinho). O aerossol secund��rio (NO3-, NH4+ e fra����o n��o marinha do SO42) e o aerossol carbon��ceo (EC + OC) contribuem cada um com cerca de 4 % e 3 %, respetivamente. A fra����o m��ssica restante (cerca de 29 %), corresponde aos constituintes n��o analisados, podendo a ��gua ser a mais importante neste grupo. A an��lise qu��mica das amostras segregadas por tamanho revela a seguinte composi����o para as part��culas PM1, PM(1-2.5) e PM(2.5-10): 5,2, 11,8 e 20,7 % (constituintes do sal marinho); 8,6, 3,7 e 3,1 % (i��es secund��rios); 8,9, 1,5 e 1,3 % (EC + OC).

Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9��50���N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18��54���N, 155��15���W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9��50���N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and ��74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (��74/70Ge fluid-basalt up to 1.15 ��� at EPR 9��50���N and 1.64 ��� at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 �� 0.6 ��� (2sd), and a maximum value of -3.6 �� 0.6 ��� (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9��50���N also demonstrates that Ge isotopes are fractionated by approximately -5.6 �� 0.6 ��� (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the ���missing Ge sink���, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and ��74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

Synth��ses et propri��t��s thermiques et photophysiques de nouveaux polym��res de coordination �� base de CuX (X = Cl, Br, I) et de ligands mono- ou dithio��thers

La recherche sur la conception de nouveaux mat��riaux, dits intelligents, est en constant progr��s depuis plus de 30 ans. Historiquement, les premiers mat��riaux utilis��s et transform��s par l���homme ��taient le bois, les min��raux et ses d��riv��s (pierre, m��taux, etc.). C���est �� la fin du 19e si��cle que la synth��se des polym��res organiques et inorganiques ainsi que leurs utilisations se d��velopp��rent. Ce progr��s continue de nos jours. Ainsi, c���est dans cette direction que cette th��se fut r��dig��e, l�����tude de polym��res de coordination bas��s sur le cuivre(I). Elle s���orchestra en six principales sections de recherche. La premi��re section, i.e. le chapitre 2 traite de la coordination de diff��rents ligands monothio��thers sur du CuX (X = I, Br) pour former plusieurs types de polym��res de coordination (CPs). Ainsi, le CP 1D [(Me[indice inf��rieur 2]S)[indice inf��rieur 3]{Cu[indice inf��rieur 2]([mu]-I)[indice inf��rieur 2}][indice inf��rieur n] est obtenu quand CuI et Sme[indice inf��rieur 2] r��agissent ensemble dans le n-heptane, alors qu���ils entrainent la formation du CP 2D [(Me[indice inf��rieur 2]S) [indice inf��rieur 3] {Cu[indice inf��rieur 4]([mu]-I) [indice inf��rieur 4]}] [indice inf��rieur n] dans le MeCN. Ce dernier contient des unit��s de construction secondaire (SBU���; Secondary Building Units en anglais) en forme de cluster Cu[indice inf��rieur 4]I[indice inf��rieur 4] �� cubane partiellement ouvert ��. En faisant r��agir le MeSEt avec du CuI, le CP 2D [(MeSEt) [indice inf��rieur 2]{Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 2] ([mu][indice inf��rieur 2]-I) [indice inf��rieur 2]}(MeCN) [indice inf��rieur 2]] [indice inf��rieur n] contenant des SBUs de type Cu[indice inf��rieur 4]I[indice inf��rieur 4] �� cubanes en escalier �� a ��t�� isol�� dans MeCN, alors qu���ils entrainent l���obtention du polym��re 1D [(MeSEt) [indice inf��rieur 3]{Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 4]}] [indice inf��rieur n] dans le n-heptane contenant quant �� lui des clusters de types Cu[indice inf��rieur 4]I[indice inf��rieur 4] �� cubanes ferm��s ��. Alors que le traitement de MeSPr avec du CuI forme le CP 1D [(MeSPr) [indice inf��rieur 3]{Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 4]}] [indice inf��rieur n], les compos��s [(L) [indice inf��rieur 4]{Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 4]}] (L = EtSPr, Pr[indice inf��rieur 2]S) sont respectivement obtenus avec le EtSPr et le Pr[indice inf��rieur 2]S. �� partir du [indice sup��rieur i]Pr[indice inf��rieur 2]S et de CuI, le cluster [([indice sup��rieur i]Pr[indice inf��rieur 2]S) [indice inf��rieur 6]{Cu[indice inf��rieur 8] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 3]}([mu][indice inf��rieur 4]-I) [indice inf��rieur 2]}] est obtenu alors que l���on forme un CP 2D [(Cu[indice inf��rieur 3]Br[indice inf��rieur 3])(MeSEt) [indice inf��rieur 3]] [indice inf��rieur n] �� partir de CuBr et MeSEt dans l���heptane. Ce dernier incorpore �� la fois des Cu([mu][indice inf��rieur 2]-Br) [indice inf��rieur 2]Cu rhombo��driques et des SBUs de type Cu[indice inf��rieur 4]Br[indice inf��rieur 4] �� cubanes ouverts ��. Le MeSPr forme, quant �� lui avec le CuBr dans l���heptane, le CP 1D [(Cu[indice inf��rieur 3]Br[indice inf��rieur 3])(MeSPr) [indice inf��rieur 3]] [indice inf��rieur n] qui, apr��s recristallisation dans le MeCN, est converti en un CP 2D [(Cu[indice inf��rieur 5]Br[indice inf��rieur 5])([mu][indice inf��rieur 2]-MeSPr) [indice inf��rieur 3]] [indice inf��rieur n] incorporant des SBUs [(Cu[indice inf��rieur 5] ([mu][indice inf��rieur 4]-Br)([mu][indice inf��rieur 2]-Br)]. Les propri��t��s de stabilit��s thermiques et photophysiques de ces mat��riaux ont aussi ��t�� report��es. ��� Dans la section 2, i.e. au chapitre 3, les r��actions entre des ligands dithio��therbutanes (1,4-bis(ph��nylthio)butane et 1,4-bis(cyclohexylthio)butane) avec CuX (X = Br, I) ont ��t�� ��tudi��es. En faisant r��agir les CuX avec le 1,4-bis(cyclohexylthio)butane, dans le ratio (1:1), les CPs 1D, peu luminescents, isostructuraux [(Cu[indice inf��rieur 2]X[indice inf��rieur 2])([mu]-CyS(CH[indice inf��rieur 2]) [indice inf��rieur 4])SCy) [indice inf��rieur 2]] [indice inf��rieur n] (X = Br, I) sont obtenus. Inversement, quand CuI r��agit avec 1,4-bis(ph��nylthio)butane, dans le ratio (2:1), il se forme le pr��alablement report�� CP 2D [(Cu[indice inf��rieur 4]I[indice inf��rieur 4])([mu]- PhS(CH[indice inf��rieur 2]) [indice inf��rieur 4])SPh) [indice inf��rieur 2]] [indice inf��rieur n], alors qu���avec le CyS(CH[indice inf��rieur 2]) [indice inf��rieur 4])SCy, un nouveau compos�� luminescent est obtenu, mais sa structure n���a pas pu ��tre r��solue.(1) Les caract��risations habituelles en photophysique et en stabilit�� thermique ont ��t�� men��es sur ces mat��riaux. Dans la troisi��me section, i.e. dans le chapitre 4, les r��actions de coordination de CuX (Br, I) sur les ligands dithio��therbut��nes E-���et Z-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh, E-���et Z-pTolS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])S-pTol ont ��t�� compar��es. Quand les sels CuX r��agissent avec E-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh les CP 2D [Cu[indice inf��rieur 2]X[indice inf��rieur 2]{[mu]-E-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh}[indice inf��rieur 2]] [indice inf��rieur n] (X = I, Br), compos��s isostructuraux, sont obtenus. Incorporant une structure sans-pr��c��dente, ces r��seaux sont form��s �� partir de couches 2D en alternance ABAB, contenants des SBUs Cu[indice inf��rieur 2] ([mu][indice inf��rieur 2]-X) [indice inf��rieur 2] rhombo��driques. Inversement, quand l���isom��re Z-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh r��agit avec des sels de CuX, deux structures diff��rentes sont obtenues : le CP 2D [Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 4] ([mu]-Z-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh}[indice inf��rieur 2]] [indice inf��rieur n] contenant des SBUs de type �� cubane ferm�� �� et le complexe 0D [Cu[indice inf��rieur 2]Br[indice inf��rieur 2]{[mu]-Z-PhS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])SPh}[indice inf��rieur 2]]. De par la r��action de E-pTolS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])S-pTol avec CuI, le CP 2D [{Cu([mu][indice inf��rieur 3]-I)} [indice inf��rieur 2] ([mu]-E-pTolS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])S-pTol)]n contenant des rubans parall��les en escalier est obtenu, alors que la structure issue de CuBr n���a pas pu ��tre r��solue. Finalement, quand CuX r��agit avec Z-pTolS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])S-pTol, les CPs 2D iso-structuraux [Cu[indice inf��rieur 2]X[indice inf��rieur 2]{[mu]-Z-pTolS(CH[indice inf��rieur 2]CH=CHCH[indice inf��rieur 2])S-pTol}[indice inf��rieur 2]] (X = I, Br) sont form��s. Dans ce cas, contrairement, aux premi��res structures obtenues, les couches de ces CPs sont compos��es de grilles incorporant des SBUs rhombo��driques Cu[indice inf��rieur 2] ([mu][indice inf��rieur 2]-X) [indice inf��rieur 2] dont les distances Cu������Cu sont identiques d���une couche �� l���autre. Les caract��risations habituelles en photophysique et en stabilit��s thermiques ont ��t�� men��es sur ces mat��riaux. De plus, des calculs th��oriques ont ��t�� r��alis��s afin de mieux comprendre les propri��t��s photophysiques de ces compos��s. La quatri��me section, i.e. le chapitre 5, traite des r��actions de CuX (Br, I, Cl) sur des ligands dithio��therbutynes (1,4-bis(pTolthio)but-2-yne et 1,4-bis(benzylthio)but-2-yne. Quand CuBr r��agit avec 1,4-bis(pTolthio)but-2-yne, le CP 1D [{Cu([mu][indice inf��rieur 2]-Br) [indice inf��rieur 2]Cu}([mu]-pTolSCH[indice inf��rieur 2]C���CCH[indice inf��rieur 2]S-pTol) [indice inf��rieur 2]] [indice inf��rieur n] est obtenu, alors que le CP 2D [{Cu[indice inf��rieur 4] ([mu][indice inf��rieur 3]-I) [indice inf��rieur 4]}([mu]-pTolSCH[indice inf��rieur 2]C���CCH[indice inf��rieur 2]S-pTol) [indice inf��rieur 2]] [indice inf��rieur n], pr��alablement report��, est form��.(2) La r��action des sels CuI et CuCl avec 1,4-bis(benzylthio)but-2-yne engendre la formation de complexes isomorphes 0D [{Cu([mu][indice inf��rieur 2]-X) [indice inf��rieur 2]Cu}([mu]-PhCH[indice inf��rieur 2]SCH[indice inf��rieur 2]C���CCH[indice inf��rieur 2]SCH[indice inf��rieur 2]Ph) [indice inf��rieur 2]] (X = I, Br). Contrairement �� l���utilisation de CuCl, qui avec PhCH[indice inf��rieur 2]SCH[indice inf��rieur 2]C���CCH[indice inf��rieur 2]SCH[indice inf��rieur 2]Ph forme le CP 2D [{Cu[indice inf��rieur 2] ([mu][indice inf��rieur 2]-Cl)([mu] [indice inf��rieur 3]-Cl)}([mu]-PhCH[indice inf��rieur 2]SCH[indice inf��rieur 2]C���CCH[indice inf��rieur 2]SCH[indice inf��rieur 2]Ph)] [indice inf��rieur n]. Notons que ce CP pr��sente des propri��t��s de photophysique peu communes pour un d��riv�� chlor��, car il ��met de la lumi��re autour de 600 nm. La cinqui��me section, i.e. le chapitre 6, traite des r��actions de CuI avec PhS(CH[indice inf��rieur 2]) [indice inf��rieur 8]SPh et pTolS(CH[indice inf��rieur 2]) [indice inf��rieur 8]S-pTol qui g��n��rent respectivement les CPs luminescents 1D [Cu[indice inf��rieur 4]I[indice inf��rieur 4]{[mu][indice inf��rieur 2]-PhS(CH[indice inf��rieur 2]) [indice inf��rieur 8]SPh}[indice inf��rieur 2]] [indice inf��rieur n] et 2D [Cu8I8{[mu]2-pTolS(CH2)8S-pTol}3(MeCN)2]n. Le CP 2D [Cu8I8{[mu]2-pTolS(CH2)8S-pTol}3 (MeCN)2]n pr��sente un r��seau qui n���avait jamais ��t�� rencontr�� dans la litt��rature auparavant, c.-��-d., des couches de polym��re construites �� partir de deux cubanes ferm��s pont��s ensemble par un rhombo��dre comme SBUs. Leurs propri��t��s physiques et de stabilit��s thermiques ont ��t�� ��tudi��es et pr��sentent quelques diff��rences notables. La sixi��me section, i.e. le chapitre 7, traite des r��actions entre CuI avec le ligand flexible pTolS(CH[indice inf��rieur 2]) [indice inf��rieur 8]S-pTol dans le MeCN ou EtCN et p-[indice sup��rieur t]BuC[indice inf��rieur 6]H[indice inf��rieur 4]S(CH[indice inf��rieur 2]) [indice inf��rieur 8]SC[indice inf��rieur 6]H[indice inf��rieur 4]-p-[indice sup��rieur t]Bu L2 dans EtCN. Les synth��ses issues de pTolS(CH[indice inf��rieur 2]) [indice inf��rieur 8]S-pTol permettent l���obtention de CPs 2D [Cu[indice inf��rieur 8]I[indice inf��rieur 8]{pTolS(CH[indice inf��rieur 2]) [indice inf��rieur 8]S-pTol}[indice inf��rieur 3] (solvant) [indice inf��rieur 2]] [indice inf��rieur n] (1���MeCN et 1���EtCN) contenant des n��uds de connexion de type Cu[indice inf��rieur 8]I[indice inf��rieur 8]. Par opposition, l���utilisation du ligand p-[indice sup��rieur t]BuC[indice inf��rieur 6]H[indice inf��rieur 4]S(CH[indice inf��rieur 2]) [indice inf��rieur 8]SC[indice inf��rieur 6]H[indice inf��rieur 4]-p-[indice sup��rieur t]Bu dans EtCN entraine la formation d���un CP 1D [Cu[indice inf��rieur 4]I[indice inf��rieur 4]{p-[indice sup��rieur t]BuC[indice inf��rieur 6]H[indice inf��rieur 4]S(CH[indice inf��rieur 2]) [indice inf��rieur 8]SC[indice inf��rieur 6]H[indice inf��rieur 4]-p-[indice sup��rieur t]Bu}[indice inf��rieur 2] (EtCN) [indice inf��rieur 2]] [indice inf��rieur n] incorporant les SBUs de type cubane ferm��. Les CPs 2D 1���MeCN et 1���EtCN, contrairement �� 2���EtCN, pr��sentent l���habilit�� de pouvoir perdre le solvant initialement incorpor�� dans leur structure sous vide et de le readsorber ou d���adsorber un autre solvant, chose qui peut ��tre suivie �� l���aide de la variation de la luminescence, la stabilit�� thermique, ou encore par diffraction des rayons X sur poudre. La septi��me section, i.e. le chapitre 8 traite des r��actions, une fois encore, entre un ligand dithio��ther, contenant un pont flexible butane (EtS(CH[indice inf��rieur 2]) [indice inf��rieur 4]SEt) et les sels CuX (X = I, Br). Dans ce cas, il se forme avec le CuI un CP luminescent 2D [Cu[indice inf��rieur 4]I[indice inf��rieur 4]{[mu]-EtS(CH[indice inf��rieur 2]) [indice inf��rieur 4]SEt}[indice inf��rieur 2]] [indice inf��rieur n], alors qu���il g��n��re avec CuBr, le CP 3D [(Cu[indice inf��rieur 2]Br[indice inf��rieur 2]){[mu]-EtS(CH[indice inf��rieur 2]) [indice inf��rieur 4]SEt}][indice inf��rieur n] faiblement luminescent, construit sur des couches en parall��le pont��es par les soufres doublement n-donneurs. Il est int��ressant de remarquer qu���une migration de l�����nergie d���excitation se produit dans le CP 3D (d��riv�� brom��) contrairement au CP 2D (d��riv�� iod��) sous excitation de haute intensit��. Tr��s peu d���exemples pr��sentent ce type de processus parmi tous les CPs ( < 10). Pour conclure, les r��actions entre les sels CuX (X = Cl, Br, I) avec des ligands thio��thers de types diff��rents (mono-, di-thio, rigide ou flexible) peuvent offrir des mat��riaux de structures variables (CP 0D, 1D, 2D, 3D avec et sans cavit��s) pr��sentant leurs propres sp��cificit��s (luminescence, stabilit�� thermique, adsorption de gaz, solvatochromisme, etc.). Le r��sultat le plus important �� noter, en comparaison avec la litt��rature est, qu���il est tr��s difficile, voire impossible, de pouvoir pr��dire la dimensionnalit��, la structure et les propri��t��s dont r��sultera la coordination des ligands thio��thers sur des sels de CuX (X = Cl, Br, I). Par cons��quent, de nombreuses combinaisons et ��tudes restent encore �� ��tre men��es pour mieux comprendre ces mat��riaux et trouver la, ou les meilleures combinaisons possibles pour concevoir des MOFs luminescents �� partir de CuX.