Dissertations / Theses on the topic 'Cu(I)'

Atliktas palyginamasis dviejų kompleksinių sistemų - Cu|Cu(II), glicinas ir Cu|Cu(II), maleino rūgštis - elektrocheminių charakteristikų tyrimas. Nustatytos maleino rūgšties tirpalų pusiausvyrinės charakteristikos. Kiekybiniam titravimo kreivių aprašymui išvestos lygtys, kuriose įvertinti medžiagų bei krūvių balansai bei atsižvelgta į praskiedimo efektus. Jų taikymas pH-metrinių duomenų analizei davė tokias maleato anijonų protonizacijos konstantų reikšmes: log = 6,05, log = 7,48. Nustatyta, kad tirpaluose su 0,3 M K2SO4 priedu protonizuotų ligando formų stabilumas sumažėja (log = 5,75, log = 7,30). Cu(II) maleatinių kompleksų stabilumui nustatyti panaudotas spektrofotometrijos metodas ir pasiūlyta duomenų analizės procedūra. Ji remiasi kiekybiniu absorbcijos spektrų aprašymu, taikant lygtis, išplaukiančias iš valdomo harmoninio osciliatoriaus teorijos. Išanalizavus įvairių sudėčių tirpalų absorbcijos maksimumo dydžius, prieita išvados, kad rūgščiose terpėse vyrauja monoligandinis kompleksas, kurio koncentracinė stabilumo konstanta log b1 = 2,2. Atlikta sistemos Cu|Cu(II), maleino rūgštis pusiausvyrų termodinaminė analizė. Nustatyta, kad esant metalinio vario ir tirpalų sąlyčiui, sistemoje galimi gilūs virsmai, kurių metu iki 90 % Cu(II) transformuojasi į Cu(I). Teorines išvadas patvirtina eksperimentiniai duomenys, gauti spektrofotometrijos ir elektrocheminės kvarco kristalo mikrogravimetrijos metodais. Įvertinti Cu korozijos bei fazinių Cu2O sluoksnių susidarymo... [toliau žr. visą tekstą]
A comparative investigation of electrochemical characteristics of two complex systems, viz. Cu|Cu(II), glycine and Cu|Cu(II), maleic acid, was carried out. The equations were obtained for quantitative description of pH-metric and spectrophotometric data, which were used for determination of equilibrium characteristics in Cu(II)-maleic acid solutions. Thermodynamic analysis shows that deep changes are possible in this system resulting in 90 % transform of Cu(II) into Cu(I). The rates of Cu corrosion and Cu2O formation are estimated to be of the same order (nmol cm-2 s-1). Regularities of formal electrochemical kinetics, which account for the mass transport of chemically interacting particles and for step-wise charge transfer process, are suitable for interpretation of voltammetric data of the Cu|Cu(II), glycine system. Kinetic parameters Cu(II) glycinate complex depend on the nature of the supporting electrolyte: the exchange current density decreases and the cathodic charge transfer coefficient increases in the sequence: Li+ - Na+ - K+ - Cs+. To enhance the Cu(I) generation in maleic acid system, the pre-electrolysis procedure was applied. It was found that its effect depends on solution pH. Applied theoretical model describes satisfactorily the steady-state voltammetric characteristics of Cu|Cu(II), maleic acid system, but some contradictory results were obtained in the case of time-dependent processes. Theoretical and experimental problems to be solved are discussed.

A comparative investigation of electrochemical characteristics of two complex systems, viz. Cu|Cu(II), glycine and Cu|Cu(II), maleic acid, was carried out. The equations were obtained for quantitative description of pH-metric and spectrophotometric data, which were used for determination of equilibrium characteristics in Cu(II)-maleic acid solutions. Thermodynamic analysis shows that deep changes are possible in this system resulting in 90 % transform of Cu(II) into Cu(I). The rates of Cu corrosion and Cu2O formation are estimated to be of the same order (nmol cm-2 s-1). Regularities of formal electrochemical kinetics, which account for the mass transport of chemically interacting particles and for step-wise charge transfer process, are suitable for interpretation of voltammetric data of the Cu|Cu(II), glycine system. Kinetic parameters Cu(II) glycinate complex depend on the nature of the supporting electrolyte: the exchange current density decreases and the cathodic charge transfer coefficient increases in the sequence: Li+ - Na+ - K+ - Cs+. To enhance the Cu(I) generation in maleic acid system, the pre-electrolysis procedure was applied. It was found that its effect depends on solution pH. Applied theoretical model describes satisfactorily the steady-state voltammetric characteristics of Cu|Cu(II), maleic acid system, but some contradictory results were obtained in the case of time-dependent processes. Theoretical and experimental problems to be solved are discussed.
Atliktas palyginamasis dviejų kompleksinių sistemų - Cu|Cu(II), glicinas ir Cu|Cu(II), maleino rūgštis - elektrocheminių charakteristikų tyrimas. Nustatytos maleino rūgšties tirpalų pusiausvyrinės charakteristikos. Kiekybiniam titravimo kreivių aprašymui išvestos lygtys, kuriose įvertinti medžiagų bei krūvių balansai bei atsižvelgta į praskiedimo efektus. Jų taikymas pH-metrinių duomenų analizei davė tokias maleato anijonų protonizacijos konstantų reikšmes: log = 6,05, log = 7,48. Nustatyta, kad tirpaluose su 0,3 M K2SO4 priedu protonizuotų ligando formų stabilumas sumažėja (log = 5,75, log = 7,30). Cu(II) maleatinių kompleksų stabilumui nustatyti panaudotas spektrofotometrijos metodas ir pasiūlyta duomenų analizės procedūra. Ji remiasi kiekybiniu absorbcijos spektrų aprašymu, taikant lygtis, išplaukiančias iš valdomo harmoninio osciliatoriaus teorijos. Išanalizavus įvairių sudėčių tirpalų absorbcijos maksimumo dydžius, prieita išvados, kad rūgščiose terpėse vyrauja monoligandinis kompleksas, kurio koncentracinė stabilumo konstanta log b1 = 2,2. Atlikta sistemos Cu|Cu(II), maleino rūgštis pusiausvyrų termodinaminė analizė. Nustatyta, kad esant metalinio vario ir tirpalų sąlyčiui, sistemoje galimi gilūs virsmai, kurių metu iki 90 % Cu(II) transformuojasi į Cu(I). Teorines išvadas patvirtina eksperimentiniai duomenys, gauti spektrofotometrijos ir elektrocheminės kvarco kristalo mikrogravimetrijos metodais. Įvertinti Cu korozijos bei fazinių Cu2O sluoksnių susidarymo... [toliau žr. visą tekstą]

Ce manuscrit décrit en détail la réactivité du précurseur pré-organisé A 1 de formule [Cu 2 (μ 2 - dppm) 2 (CN) 2 ].(PF 6 ) 2 , basé sur des ions de Cu(I) avec différents types de ligands afin de synthétiser de nouveaux assemblages polymétalliques luminescent. Cette réactivité utilise pleinement les concepts de chimie supramoléculaire guidée par la chimie de coordination (CDS), ce qui permet d’obtenir un grand nombre d’assemblages supramoléculaires polymétalliques complexes et variés de l’ion Cu(I). Ils sont obtenus à partir de synthèses simples et présentent une grande variété de caractéristiques structurales. Sur la base de ce résultat, nous sommes intéressés de voir dans quelle mesure il est possible d’étendre l’approche synthétique originale de chimie supramoléculaire adaptative guidée par la coordination développée au laboratoire à l’utilisation de précurseurs présentant des fragments cyano, tels que les fragments K 2 M(CN) 4 (M= Ni, Pd, Pt), K 2 Pt(CN) 6 , K 4 M(CN) 8 (M= Mo et W) et des précurseurs inorganiques anioniques qui ne présentent pas de centre métallique,tels que le KC(CN) 3 , le NaN(CN) 2 et le NaN 3 . Dans le dernier chapitre, le dérivé A 1 a été mis à réagir avec des ligands polytopiques à terminaison pyridine ce qui a permis de caractériser de nouveaux polymères de coordination. Les nouveaux dérivés sont caractérisés en utilisant différentes techniques comme la RMN multinucléaire, des études de diffraction des rayons X sur monocristaux et sur poudre, les spectroscopies UV-Vis et IR. En outre, les propriétés photophysiques (spectre d'émission, mesures des rendements quantiques et des temps de vie des états excités) des matières émissives obtenues ont été étudiées en solution et à l'état solide à température ambiante et à basse température
This manuscript describes in detail the reactivity of the pre-organized precursor A 1 , whose molecular formula is [Cu 2 (μ 2 -dppm) 2 (CN) 2 ](PF 6 ) 2 , based on Cu(I) ions with different types of ligands in order to synthesize new luminescent polymetallic assemblies. Its reactivity makes full use of the concepts of supramolecular chemistry guided by coordination chemistry (CDS), which makes it possible to obtain a large intricate number and varied polymetallic supramolecular assemblies of the Cu(I) ion. They are obtained from simple syntheses and with a wide variety of structural characteristics. Based on this result, we are interested to see how it is possible to extend the original adaptive coordination driven supramolecular approach developed in our group to the use of precursors bearing cyano fragments, such as K 2 M(CN) 4 (M= Ni, Pd, Pt), K 2 Pt(CN) 6 , K 4 M(CN) 8 (M= Mo and W) and also anionic inorganic precursors that do not have a metal centre, such as KC(CN) 3 , NaN(CN) 2 and NaN 3 .In the last chapter, the A 1 derivative has been reacted with pyridine- terminated polytopic ligands, which has made it possible to characterize novel coordination polymers. The new derivatives are characterized using different techniques such as multinuclear NMR, single-crystal and powder X-ray diffraction studies, UV-Vis and IR spectroscopies. In addition, the photophysical properties (emission spectrum, measurements of quantum yields and life times of the excited states) of the emissive materials obtained have been studied in solution and in the solid state at room temperature and at low temperature

Triazenido ions are isoelectronic to amidinato anions,[R'N C(R)=NR']- and have a broad versatility in coordination chemistry. Metal complexes including triazenido ligands find applications in various areas of chemistry. Triazenes and complexes including triazole derivatives show extensive applicability as for example in supramolecular chemistry and pharmacological compounds. This work presents deals with the study of new triazene derivatives with triazole substituents resulting from the click reactions, acting as ligands in complexes with Cu(I), Cu(II) and Au(I). The following ligands 1,3-bis(2-azidophenyl)triazene (2), 1-(methyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene-N-oxide (4), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazene (5), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazene (6) and, complexes 1,3-bis(2-azidophenyl)triazenide-κN11- triphenylphosphine-gold(I) (2a), bis-{1-(methyl)-3-[2-(4-phenyl-1,2,3-triazole-κN2)]triazenide-1-oxide-κ2N3,O}copper(II) (4b), 1-(phenyl)-3-(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (5a), 1,3-bis(2-(4-phenyl-1,2,3-triazole)triazenide-κN- triphenylphosphine-κP-gold(I) (6a), bis[1,3-bis(2-(4-phenyl-1,2,3-triazole-κN2)-μ-N3-triazenide]-κN11,κN13 copper(I)κN13,κN11´copper(I) (Cu Cu) (6b) were investigated. The compounds were characterized by IR, UV-Vis and NMR (1H e 13C) spectroscopy, low or high resolution mass spectrometry (EI, ESI, ESI(+)-TOF and ESI(-)-TOF) and X-ray diffraction on single crystal. Triazene (2) and complex (2a) exhibit intramolecular assembling through classical and non-classical hydrogen bonding. Complexes with Au(I), (2a), (5a) e (6a), the metal atom show linear coordination geometry. The metal atom in complex (6b) shows a T distorted coordination geometry, which is extended to a quadratic coordination resulting from d10 d10 interactions between Cu(I) ions. Triazene (6) and its respective complexes (6a) e (6b) exhibit intermolecular interactions of the type C−H···M. Antibacterial activity of triazene (5) and complex (5a) were assayed resulting to be inactive against the bacteria tested.
Os compostos triazenidos são isoeletrônicos a íons amidinatos [R'NH C(R)=NR'], e têm sido usados com sucesso na química de coordenação. A complexação a íons metálicos possibilita a sua aplicação em diversas áreas da química. Assim como os triazenos, os triazóis possuem vasta aplicabilidade, desde a química supramolecular até a área farmacológica. Este trabalho apresenta o estudo inédito de pré-ligantes triazenos contendo substituintes triazóis os quais foram obtidos a partir de reações de Click, e seus respectivos complexos de Cu(I), Cu(II) e Au(I). Foram sintetizados os pré-ligantes 1,3-bis(2-azidofenil)triazeno (2), 1-(metil)-3-(2-(4-fenil-1,2,3-triazol)triazeno-N-óxido (4), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazeno (5), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazeno (6) e os complexos 1,3-bis(2-azidofenil)triazenido-κN11-trifenilfosfina-ouro(I) (2a), bis-{1-(metil)-3-[2-(4-fenil-1,2,3-triazol-κN2)]triazenido-1-óxido-κ2N3,O}cobre(II) (4b), 1-(fenil)-3-(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (5a), 1,3-bis(2-(4-fenil-1,2,3-triazol)triazenido-κN-trifenilfosfina-κP-ouro(I) (6a), bis[1,3-bis(2-(4-fenil-1,2,3-triazol-κN2)-μ-N3-triazenido]-κN11,κN13 - cobre(I)κN13,κN11´cobre(I) (Cu Cu) (6b). Estes foram caracterizados por espectroscopia de IV, UV-Vis e RMN (1H e 13C), espectrometria de massas de baixa ou alta resolução (EI, ESI, ESI(+)-TOF e ESI(-)-TOF) e difração de raios X em monocristal. O triazeno (2) e complexo (2a) apresentam ligações de hidrogênio intermoleculares e intramoleculares do tipo clássica e não-clássica. Os complexos de Au(I), (2a), (5a) e (6a) possuem geometria de coordenação linear. O complexo (6b) apresenta uma geometria T distorcida, a qual é estendida para quadrática pela interação d10 d10 entre os átomos de Cu(I), o triazeno (6) e seus complexos (6a) e (6b) apresentam ainda ligações intermoleculares do tipo C−H···M. Foi testada a atividade antibacteriana do triazeno (5) e o complexo (5a), os quais mostraram-se inativos frente às bactérias testadas.

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O dióxido de carbono, assim como outros gases leves denominados gases estufa, afetam de maneira negativa o sistema de temperatura global, agravando o efeito estufa desde a primeira revolução industrial. Mesmo a concentração nunca ter sido constante, a atividade antropogênica fez com que concentração desses gases na atmosfera aumentar de maneira exponencial. Por essa razão, países adotam estratégias para reduzir a concentração desses gases na atmosfera. O sequestro e captura de gases mostrou-se ser uma medida promissora na redução de gases estufa. O uso de alcanoaminas foi de grande relevância nesse processo, porém seu custo de reciclagem foi se elevando ao ponto de ser um material inviável para a adsorção de gases estufa, em especial o CO₂ devido sua quantidade. A utilização de redes metalorgânicas, materiais híbridos que sua topologia consiste em ligantes orgânicos coordenados a nós metálicos. Esses materiais de alta porosidade e grande área superficial aumentou o interesse em diversos campos de estudo, desde a catalise heterogênea até o transporte controlado de fármacos. Em 1999, Omar Yaghi utilizou esses materiais para a adsorção seletiva de gases, com foco em CO₂. Recentemente, a família SIFSIX se mostrou promissora na captura seletiva de CO₂, utilizando de unidades orgânicas de 1,2-di(piridin-4-il)etino e pilares inorgânicos a base de SiF₆²⁻. Nessa família, as redes metalorgânicas SIFSIX-2-Cu, SIFSIX-2-Cu-i e SIFSIX-3-Cu mostraram-se capazes de realizar a adsorção seletiva de CO₂ com uma alta capacidade em relação as suas concorrentes. A estrutura SIFSIX-3-Cu é a atual recordista de captura seletiva de CO₂. Por isso, o mecanismo de adsorção para gases leves é investigado utilizando-se DFT. A adsorção dos gases CH₄, CO₂, CO, H₂, N₂ e O₂ nas redes metalorgânicas SIFSIX-2-Cu, SIFSIX-2-Cu-i e SIFSIX-3-Cu foi estudada, afim de se entender o processo de adsorção dessa família. Resultados indicam a seletividade do CO₂ ser produto de seu alto momento de quadrupolo, onde o grupo aniônico, SiF₆²⁻, teve um papel importante para a adsorção.

In questo lavoro è presentato l'utilizzo della spettroscopia di assorbimento di raggi X applicata all'indagine inerente il numero e la natura degli atomi vicini di un centro metallico a due diversi stati di ossidazione [Cu(I) e Cu(II)] all'interno di complessi fosfinici e/o azotati. Gli spettri sono stati registrati nella loro completezza, comprendendo sia la soglia sia lo spettro esteso di assorbimento, e le transizioni elettroniche 1s→3d e 1s→4p sono state oggetto d'esame per avere indicazioni circa l'intorno locale del fotoassorbitore (l'atomo centrale). La tecnica più utilizzata, tuttavia, è stata l'analisi EXAFS (Extended X-ray Absorption Fine Structure) che ha permesso di determinare l’effettiva coordinazione di Cu(I) e (II) nel caso dei complessi studiati. Il metodo consiste nella costruzione di un segnale teorico più simile possibile a quello ottenuto sperimentalmente, e l’approccio per raggiungere questo obiettivo consiste nel seguire una procedura di fitting eseguita computazionalmente (tramite il pacchetto software GNXAS), per la quale è necessario un modello strutturale già esistente o creato ex novo da una molecola di partenza molto simile. Sarà presentato lo studio degli esperimenti ottenuti su campioni sia solidi che in soluzione: in questo modo è stato possibile effettuare un confronto tra le due forme dello stesso composto nonché si è potuto osservare i cambiamenti riguardanti l’interazione metallo-solvente a diverse concentrazioni. Come sarà mostrato in seguito, l’analisi sui solidi è risultata più affidabile rispetto a quella riferita alle soluzioni; infatti il basso rapporto segnale/rumore caratterizzante le misure di queste ultime ha limitato le informazioni ottenibili dai relativi spettri di assorbimento di raggi X.

In dieser Arbeit wurde das reaktive Anlassen von dünnen Kupfer-Indium-Schichten in elementarem Schwefel mittels energiedispersiver Röntgenbeugung untersucht. Durch die simultane Aufnahme der Röntgenspektren und der Messung der diffusen Reflexion von Laserlicht der Wellenlänge 635 nm an der Oberfläche der Probe während des Schichtwachstums von CuInS₂ konnte eine Methode zur Prozesskontrolle für ein Herstellungsverfahren von CuInS₂ etabliert werden.

Die Bildung von CuInS₂ aus Kupfer-Indium-Vorläuferschichten wird dominiert von Umwandlungen der intermetallischen Phasen. CuInS₂ wächst innerhalb der Aufheizperiode ab einer Temperatur von ca. 200°C aus der Phase Cu₁₁In₉. Jedoch zerfällt letztere metallische Phase in Cu₁₆In₉ und flüssiges Indium bei einer Temperatur von ca. 310°C. Das flüssige Indium reagiert im Falle von Kupferarmut mit dem Schwefel und führt zu einem zusätzlichen Reaktionspfad über InS zu CuIn₅S₈. Unter Präparationsbedingungen mit Kupferüberschuss wird das Indium in einer intermetallischen Phase gebunden.

Erstmals konnte die Phase Digenite bei Temperaturen über 240°C beobachtet werden. Beim Abkühlen auf Raumtemperatur wandelt sich diese Phase unter dem Verbrauch von Schwefel in Covellite um.

Für Proben mit Kupferüberschuss konnte eine Wachstumskinetik proportional zur Temperatur beobachtet werden. Dieses Verhalten wurde durch eine stress-induzierte Diffusion als dominierenden Reaktionsmechanismus interpretiert. Dabei werden während der Bildung von CuInS₂ durch unterschiedliche Ausdehnungen der metallischen und sulfidischen Schichten eine Spannung in der CuInS₂-Schicht induziert, die nach Überschreiten einer Grenzspannung zu Rissen in der CuInS₂-Schicht führt. Entlang dieser Risse findet ein schneller Transport der Metalle zur Oberfläche, wo diese mit dem Schwefel reagieren können, statt. Die Risse heilen durch die Bildung neuen Sulfids wieder aus.
In this work the reactive annealing of thin copper and indium films in elemental sulphur was investigated by energy dispersive X-ray diffraction. Measuring simultanously laser light diffusively reflected from the growth surface, a simple method for process monitoring could be established. The process monitoring using 635 nm laser light can now independently be used in production.

The growth of CuInS₂ from copper-indium precursors is dominated by transitions between intermetallic phases. CuInS₂ growths in the heat up period above 200 °C from the phase Cu₁₁In₉. However the latter metallic phase decomposes into Cu₁₆In₉ and liquid indium at a temperature of 310 °C. The liquid indium reacts in the case of copper deficiency with sulphur to InS. This leads to an additional reaction path via InS to CuIn₅S₈. Under preparation conditions with copper excess to the contrary, indium is bound in an intermetallic phase.

For the first time the phase Digenite could be observed in a growth experiment at temperatures above 240 °C. During cool down to room temperature this phase transforms to Covellite by consumption of sulphur.

For samples with copper excess a growth kinetic proportional to the temperature was observed. This behaviour is interpreted by a stress induced reaction mechanism: During the formation of CuInS₂, strain in the CuInS₂ thin film is induced due to different expansion coefficients of the metallic and sulphurous phases. After transgression of a certain strain limit, cracks within CuInS₂ are formed. Along these cracks, fast transport of metallic species to the surface can occur. There these species can react with the sulphur. The cracks can heal up by the formation of new sulphides.

Copper is an essential trace element present in all living systems and is important for the function of many cellular enzymes. It ranks third in intracellular abundance behind only zinc and iron and plays a very important role as a catalytic cofactor in various cellular processes such as mitochondrial respiration, iron uptake, and the redox processes of a number of enzymes, including superoxide dismutase, lysyl oxidase, or tyrosinase. Any abnormality in copper trafficking pathways can lead to serious diseases such as Wilsons disease, Menkes syndrome and has been implicated in the neurodegenerative diseases amyotropic lateral sclerosis (ALS) and Alzheimers disease. While free copper in the cytoplasm would prove toxic, there is compelling evidence for the existence of a labile pool of copper that remains kinetically accessible. In order to investigate the existence of such a pool the development of Cu(I) selective probes is necessary. Chapter I provides the background for the role of copper in biology and elucidates the main trafficking pathways discovered to date. This chapter also provides recent developments of fluorescent sensors for selective visualization of biologically relevant metals. Chapter II discusses the exploration of a phenanthroline-based ligand for the selective detection of Cu(I). A series of derivatives incorporating chelating substituents in the 2- and 9-positions to enforce a 1:1 binding stoichiometry were synthesized and the properties of their respective Cu(I) complexes were characterized by x-ray structural analysis, and their photophysical properties were investigated by absorption and emission spectroscopy. Visible light excitation yielded metal-to-ligand charge-transfer (MLCT) excited states with luminescence lifetimes up to 155 ns. Electrochemical measurements further indicate that coordinative rearrangements are involved in nonradiative deactivation of the excited states. According to time-dependent density functional theory calculations (B3LYP/6-31G**), the major MLCT transitions are polarized along the C2 axis of the complex and originate predominantly from the dxz orbital. In chapter III, the development of a ratiometric Cu(I) sensor based on a donor-acceptor functionalized biphenyl fluorophore platform is discussed. The fluorescence emission energy for such fluorophores is highly dependent upon the interannular twist angle and this property was harnessed to provide a ratiometric sensor selective for Cu(I). Coordination of Cu(I) leads to a flattening of the biphenyl backbone and was confirmed by absorbance and emission spectroscopy as well as 2D NOESY experiments. The peak emission energy was shifted by 39 nm towards higher energy upon metal cation binding with a concomitant 7 bathochromic shift in absorption energy. The photophysical data accompanied by 1H NMR analysis confirms a well-defined 1:1 binding stoichiometry between metal and ligand. The findings from this study showed ratiometric behavior for this probe, albeit with a lowered quantum yield. While the quantum yield for the fluorophore discussed in chapter III was low (8.0%), the focus of chapter IV was the elucidation of the fluorescence quenching mechanism. To investigate the possibility of a twisted intramolecular charge transfer (TICT) state a donor-acceptor biphenyl fluorophore was synthesized incorporating a conformationally restricted amine donor group incapable of rotating out of plane in the excited state. Analysis of this derivative, as well as the sensor discussed in chapter III, reveals that fluorescence quenching is most likely due to hydrogen bonding to the acceptor subunit in they excited state. Finally, in chapter V, a pyrazoline fluorophore library with varying numbers of fluorine substituents was synthesized. The photophysical and electrochemical properties of these fluorophores were measured in order to determine if careful tuning of the excited state electron transfer thermodynamics is possible. The compounds cover a broad range of excited state energies and reduction potentials, and the data suggest that selective and differential tuning of both the reduction potential of the acceptor as well as the excited state equilibrium energy. These findings show that the individual parameters involved in excited state electron transfer can be tuned by the modular architecture of the pyrazoline fluorophore.

Les metalotioneïnes (MT) són unes proteïnes de baix pes molecular i elevat contingut en residus de cisteïna que es caracteritzen per la seva extremada habilitat para enllaçar tant cations de metalls essencials, com Zn(II) i Cu(I), com de metalls tòxics (Cd(II), Hg(II)).
En una primera part d'aquest treball s'analitza la utilització del catió Ag(I) com a sonda del catió Cu(I) en l'estudi de les Cu-MT, i en conseqüència es compara detalladament el comportament d'ambdós metalls enfront la isoforma 1 de MT de mamífer. Aquesta proteïna, així com els seus fragments constitutius a i b, s'ha obtingut per enginyeria genètica amb la finalitat d'assegurar al màxim el seu grau de puresa. L'estudi de la capacitat coordinant de MT 1, aMT 1 i bMT 1 enfront Ag(I) s'ha dut a terme mitjançant tècniques d'espectroscòpia electrònica (CD i UV-Vis) i de masses (ESI-MS). Aquesta darrera tècnica ha requerit la incorporació d'un mètode de separació previ a la determinació de la massa, per tal d'eliminar la presència de tampó a la mostra. L'electroforesi capil·lar (CZE) acoblada a l'ESI-MS ha demostrat ser una bona opció.
Amb la finalitat de validar l'acoblament CZE-ESI-MS, en primer lloc s'ha aplicat l'esmentat acoblament a l'estudi del desplaçament del Zn(II) en Zn7-MT 1 per Cd(II) a pH 7, procés ja conegut en les MT de mamífer que procedeix de manera seqüencial i isomorfa. Aquest estudi demostra que la tècnica CZE permet una bona separació del tampó de la solució que conté la proteïna, a la vegada que ofereix una detecció precisa de l'estequiometria de les espècies que coexisteixen en solució. En base a aquests resultats, s'ha seguit en paral·lel -mitjançant CD, UV-Vis i CZE-ESI-MS- la valoració de Zn7-MT 1, Zn4-aMT 1 i Zn3-bMT 1 amb AgClO4 a pH 7.5 i 2.5. Els resultats mostren que al llarg de les valoracions es forma un elevat nombre d'espècies, tant heterometàl·liques AgxZny-MT com homometàl·liques Agx-MT, i que en la majoria dels punts de valoració coexisteixen diverses espècies. També s'ha observat que el zinc exerceix un efecte plantilla en les 3 proteïnes estudiades, ja que el grau d'estructuració d'espècies Ag-MT de la mateixa estequiometria depèn de manera important de que l'espècie inicial sigui Zn-MT o apo-MT. La comparació Ag-Cu permet concloure que els únics casos en què l'ió Ag(I) es podria utilitzar com a substitut de Cu(I) sense causar alteracions estructurals significatives es dóna en les espècies heterometàl·liques M4Zn5-MT i M7Zn3-MT (M= Ag, Cu).
En la segona part del treball s'ha estudiat una nova MT de Drosophila melanogaster, denominada MTO, amb l'objectiu de contribuir a un criteri funcional de classificació de les MT en Zn- o Cu-tioneïna. La proteïna MTO, que disposa de 12 Cys en la seva cadena aminoacídica, es biosintetitza com a Zn4-MTO en medis rics en Zn, mentre que en medis enriquits en Cu s'obté l'espècie Cu9-MTO. El conjunt de resultats, tant in vivo com in vitro, permet classificar la MTO com una Cu-tioneïna, es a dir, amb preferència coordinativa respecte aquest metall en medis fisiològics. També, per primera vegada s'han aportat evidències estructurals sobre la participació dels ions clorur en la coordinació d'ions metàl·lics en MT, concretament en les espècies M4-MTO (M = Zn, Cd).
Metallothioneins (MT) are ubiquitous low molecular weight cysteine-rich metalloproteins, which characterize by their extremely high binding abilities towards essential metal cations, such as Zn(II) and Cu(I), as well as toxic cations like Cd(II) and Hg(II).
In the first stage of this work the use of Ag(I) as a probe for Cu(I) in Cu-MT studies is analysed, and thus, the behaviour of both metal ions when binding to the mammalian MT 1 isoform has been compared. This protein, as well as their constitutive a and b fragments, was obtained by genetic engineering in order to assure the highest purity degree. The binding abilities of Ag(I) to MT 1, aMT 1 and bMT 1 have been studied by using optical spectroscopy (CD, UV-vis) and mass spectrometry (ESI-MS) techniques. The latter required the use of a separation method previous to the mass determination in order to remove the buffer present in the sample.
With the aim of validating the CZE-ESI-MS coupling, we first studied the Zn(II)/Cd(II) replacement in Zn7-MT 1 at pH 7, a well known system in mammalian MT that proceeds by means of a sequential and isomorphous Zn/Cd replacement. This study proves that the previous coupling allow a good separation of the protein from the buffer, while achieving a precise detection of the stoichiometries of the coexisting species in solution. Based on these results, the titrations of Zn7-MT 1, Zn4-aMT 1 and Zn3-bMT 1 with AgClO4 at pH 7.5 and 2.5 were monitored in parallel by CD, UV-vis and CZE-ESI-MS techniques. The results obtained throughout the titration show formation of a high number of heterometallic AgxZny-MT as well as homometallic Agx-MT species. Also, at each titration point, there is coexistence of several species. It has also been shown the Zn template effect in the 3 proteins studied as revealed by the different folding found for the Ag-MT species of the same stoichiometry formed either from Zn-MT or from apo-MT. Comparison of the behaviour of Ag(I) and Cu(I) toward mammalian MT 1 allows us to conclude that the only cases in which the Ag(I) ion can be used as a probe for Cu(I) without causing significant structural alterations are in the heterometallic M4Zn5-MT and M7Zn3-MT (M= Ag, Cu) species.
In the second stage of this work, a new Drosophila melanogaster MT, named MTO, has been studied with the aim of contributing to a new functional criterion of classifying MT as Zn- or Cu-thioneins. The MTO protein, which includes 12 Cys residues in the aminoacidic chain, was biosynthesised as Zn4-MTO in a Zn enriched media, while in a Cu supplemented media the Cu9-MTO species was obtained. The overall results, both in vivo and in vitro, allow us to propose classification of MTO as a Cu-thionein, in agreement with the coordination preference shown by the protein toward this metal ion. Furthermore, unprecedented structural evidences showing the participation of chloride ions as ligands of the metal ions in MT is reported. This was found in the case of M4-MTO (M = Zn, Cd) species.

A plethora of novel scientific phenomena and practical applications, such as solid-state molecular solar cells and other optoelectronic devices for energy harvesting and lighting technologies, have catalyzed us to synthesize novel compounds with tunable properties. Synthetic routes, single crystal structures, and spectral and materials properties are described. Reactions of Ag(I) and Cu(I) precursors with various types of ligands -- including the azolates, diimines, and diiphosphines -- lead to the corresponding complexes in high yield. Varying the metal ions, ligands, synthetic methods, solvents, and/or stoichiometric ratio can change the properties including the molecular geometry or packing structure, reactivity, photophysical and photochemical properties, semiconducting behavior, and/or porosity of the functional coordination polymers obtained. For solar cells purposes, the absorption energy can be extended from the ultraviolet (UV) region, through the entire visible (Vis) region, onto a significant portion of the near-infrared (NIR) portion of the solar spectrum with high absorption coefficients due to the infinite conjugation of Cu(I) with diimine ligands. Twenty-eight crystal structures were obtained by conventional crystal growth methods from organic solvents, whereas their bulk product syntheses also included "green chemistry" approaches that precluded the use of hazardous organic solvents. The resulting products are characterized by powder x-ray diffraction (PXRD), Fouriertransform infrared (FTIR), nuclear magnetic resonance (NMR), UV/Vis/NIR absorption/diffuse reflectance/photoluminescence spectroscopies, and thermogravimetric analysis (TGA). Regarding the scientific phenomena investigated, the highlighting work in this dissertation is the discovery of novel bonding/photophysical/optoelectronic properties of the following materials: a black absorber with absorption from 200- 900 nm, a very stable compound with a bright green luminescence obtained by a solventless reaction, and a novel coordination polymer showing uncommon interaction of Ag(I) with three different types of diimine ligands simultaneously.

Quoique les premiers complexes métalliques contenant les ligands cyclométallés PCP de type pinceur (Figure 1a) furent reportés il y a plus de 30 ans, ce sujet, recouvrant tous les aspects de la chimie (mécanistique, structurale, catalytique, synthétique, théorique et de coordination), reste toujours d'actualité et est promis à un développement rapide. Les complexes métalliques à ligands de type pinceur possèdent cette propriété unique d’associer stabilité et réactivité, qui peuvent être contrôlées par des modifications des ligands et par la variation du centre métallique. De nombreux complexes métalliques avec des ligands de type pinceur NHC (Figure 1b) ont été reportés et bien caractérisés (avec p. Ex. Avec les atomes donneurs CCC ou CNC). Principalement lié au fait que les ligands NHC ont moins tendance à se dissocier du centre métallique que les phosphines, leurs complexes présentent des avantages par rapport à ceux formés avec des phosphines, tels que leur stabilité thermique et à l'air, ce qui représente un atout important en chimie organométallique et en catalyse homogène. Le but de ce travail de thèse consiste à concevoir et à synthétiser des analogues NHC aux fragments PCP, qui peuvent conduire à des ligands de type pinceur CCP, CCOP et CCC. Dans le cadre de ce travail, parmi les métaux de transition, nous avons choisi l'argent et l'iridium pour différentes raisons (i) les ligands NHC liés à Ag(I) peuvent généralement être transférés à un autre métal et (ii) les complexes de l'iridium sont de bons candidats pour les réactions d'activation Csp3-H et de transfert d'hydrogène. Trois types différents de ligands ont pu être synthétisés: 1) un sel bis-imidazolium avec un groupe méthylène faisant la jonction entre un cycle aromatique et deux hétérocycles en position meta l’un par rapport à l’autre; 2) un sel hybride phosphine-imidazolium avec un méthylène entre le cycle aromatique et d'une part un cycle imidazole et d'autre part un groupement phosphine; 3) un sel hybride phosphinite-imidazolium où les atomes d'oxygène et d'azote correspondants sont directement liés au cycle aromatique, toujours en position mutuellement méta. Les complexes métal-carbène correspondants furent préparés in situ à partir de ces précurseurs imidazolium en présence de la base faible Cs2CO3 puis isolés. Le ligand bis-NHCDeux positions méta du cycle aromatique sont bloquées avec des groupements méthylène pour éviter une possible activation ortho- C-H du cycle, dans le but de former uniquement les complexes de type pinceur. Les contre-ions bromures sont remplacés par des ions PF6 non-coordinants, ce qui a pour effet de supprimer le charactère hautement hygroscopique de ces sels. Une première étude de chimie de coordination du ligand 1, avec une base faible Ag2O a été réalisée. Cependant, sans doute du fait de possibles liaisons hydrogène entre les entités NCHN et un atome de fluor de PF6, Ag2O n'est pas capable de déprotoner l'imidazolium pour engendrer le complexe d'argent NHC. Cependant, le complexe de Cu(I) correspondant a pu être synthétisé par traitement du sel d'imidazolium avec [Cu(NCMe)4]PF6 en présence de Cs2CO3 dans l'acétonitrile à 60 °C. Etonnamment, on observe une réaction de transmétallation entre le complexe 4 et AgOTF qui conduit au complexe Ag(I) 5 souhaité. Cette réaction est remarquable, étant donné que les réactions de transmétallation de carbènes observées jusqu’alors se font toujours de l'argent vers le cuivre. Les courtes distances entre le métal et les cycles aromatiques observées par diffraction des rayons X nous amènent à examiner quelle est la meilleure description pour les centres métalliques d10; une forme T/Y tricoordinée ou une forme linéaire dicoordinée. Les résultats d'une étude DFT détaillée suggèrent l'absence de liaison chimique entre le Cu(I) ou l'Ag(I) et la partie proche du cycle aromatique. La proximité observée expérimentalement, entre les carbones aromatiques et le métal, résulte donc d'effets combinés de la structure du ligand chélatant et de la géometrie de coordination préférentielle du métal. Dans le cas des complexes de l'iridium, la nature des précurseurs métalliques joue un rôle important. Dans le complexe 7, le ligand cod est préféretiellement chélaté au centre Ir et les deux ligands CNHC^CH^CNHC pontants sont liés au centre Ir(I) de telle manière que chaque métal soit lié à deux donneurs cis carbène, ce qui conduit à un dimétallacycle dicationique à 20 chaînons. Etant donné que le cyclooctène (coe) est plus labile que le 1,5-cyclooctadiène (cod), il était aisé de le remplacer par une molécule de solvent (MeCN), qui, dans le complexes 6, se coordine au centre métallique par l'atome d'azote. La réduction du temps de réaction a pu être illustrée dans le cas d'un complexe à haute labilité résultant de la coordination du ligand coe plus labile comparé à celle de cod. Au contraire de la situation rencontrée dans le complexe 7 qui a une structure en forme de huit, le cycle aromatique est métallé dans le complexe 6, suite à la formation de liaisons Ir-C et Ir-H. Un mélange de solvants est utilisé pour augmenter la solubilité du ligand 1 (soluble dans le MeCN) et celle du complexe [Ir(coe)2(µ-Cl)]2 (soluble dans le THF). Il est intéressant de noter que MeCN semble stabliliser l'hydure d'Ir(III) de type pinceur, vu que dans le traitement du dibromure bis-imidazolium, soluble dans le THF, dans les mêmes conditions, mais en l'absence de MeCN, on observe uniquement la décomposition du précurseur Ir. Le ligand hybride phosphine-NHCDans le but de limiter les possibles problèmes associés à la sensibilité des phosphines libres, nous introduisons la phosphine dans l'étape finale de la préparation. Le diethylether est utilisé comme solvant dans la première étape pour favoriser la précipitation du dérivé mono-substitué, ce qui permet de s'affranchir d'autres substitutions bien que le 1,3-bis(chlorométhyl)benzène soit présent en large excès. Le chlorure d'imidazolium, extrêmement hygroscopique, est traité avec KPF6 pour conduire au sel phosphine-imidazolium 2 associé à l'anion non-coordinant hexafluorophosphate. En faisant réagir le sel de phosphine-imidazolium avec 0. 5 equiv. D'Ag2O dans le dichlorométhane à température ambiante et à l'abri de la lumière, on observe un précipité blanc du complexe Ag(I). Il est intéressant de comparer la structure du complexe 8 avec celles d'autres complexes Ag(I) contenant des ligands semblables phosphores/NHC. [. . . ]
Although the first metal complexes with the cyclometalated PCP pincer ligands (Figure 1a) were reported about 30 years ago, it is still a hot and fast developing topic covering all aspects of chemistry: mechanistic, structural, catalytic, synthetic, theoretical, and coordination studies. Pincer-based metal complexes possess a unique balance of stability and reactivity that can be controlled by systematic ligand modifications and variation of the metal centre. Numerous metal complexes with related pincer-type NHC ligands (Figure 1b) have been reported and well characterized (with e. G. CCC or CNC donor sets). Largely because the NHC ligands have a lesser tendency to dissociate from the metal centre than phosphines, their complexes exhibit advantages over phosphine metal complexes, such as improved air and thermal stability, which are highly desirable in e. G. Organometallic chemistry and homogeneous catalysis. The aim of this thesis was to design and synthesize partial/full NHC analogues to the PCP framework, which may result in CCP, CCOP and CCC pincer ligands. Among the transition metals, silver and iridium are at the focus of our work because (i) NHC ligands bound to Ag(I) can generally be transferred to another metal and (ii) Ir complexes are good candidates for the challenging Csp3-H bond activation and hydrogen transfer reactions. Three different types of ligand precursors have been successfully synthesized: 1) bis-imidazolium salts with a methylene bridge connecting the aromatic ring to each of the two imidazole rings; 2) hybrid phosphino-imidazolium salts with a methylene bridge connecting the aromatic ring to the imidazole ring and to the phosphine group; 3) hybrid phosphinito-imidazolium salts where the corresponding oxygen and nitrogen atoms, respectively, are directly connected to the aromatic ring. The corresponding metal carbene complexes were prepared in situ from these imidazolium precursors in the presence of the weak base Cs2CO3 and isolated. The bis-NHC ligandTwo mutually meta positions of the aromatic ring were blocked with methyl groups to avoid possible ortho-C-H activation on the ring so that only pincer-type complexes would form if metalation was to occur on the aromatic ring. The bromides in the imidazolium dibromide salt were replaced with non-coordinating counterions PF6 to suppress their high hygroscopic character. An initial coordination chemistry study was performed by reaction of 1 with Ag2O as a weak base. However, owing to possible H-bonding between the NCHN units and a fluorine atom of PF6, Ag2O was not able to deprotonate the imidazolium to generate the silver NHC complex. However, the corresponding Cu(I) complex was obtained by treating the imidazolium salt with [Cu(NCMe)4]PF6 and Cs2CO3 in MeCN at 60 _C. Surprisingly, a transmetalation reaction between 4 and AgOTF afforded the desired Ag(I) complex 5. This reaction is particularly noteworthy since carbene transmetalation reactions always feature the opposite reaction (from Ag to Cu). The short distances observed by X-ray diffraction for 4 and 5 between the metal and the aromatic rings led us to examine whether these d10 metal centers are better described as T/Y-shaped tri-coordinated or linearly di-coordinated, and the results of detailed DFT calculations suggested the absence of a chemical bond between the Cu(I) or Ag(I) center and parts of the aromatic ring. The proximity observed experimentally between the aromatic carbon and the metals thus results from the combined effects of a chelating ligand structure and the metal preferred coordination geometry. In the cases of iridium complexes, the nature of the metal precursors played an important role. In complex 7, the cod ligand was preferably chelated to the Ir center and the two bridging CNHC^CH^CNHC ligands connect the Ir(I) centres in such a way that each metal is bonded to two mutually cis carbene donors, resulting in a dicationic 20-membered dimetallacycle. While cyclooctene (coe) is more labile than 1,5-cyclooctadiene (cod), it was easily replaced by the solvent molecule MeCN which coordinates to the Ir center through its nitrogen in complex 6. The requirement for shorter reacting times (compared with the reaction using [Ir(cod)(µ-Cl)]2) also showed the higher lability of the complex resulting from a more weakly bound coe ligand compared to cod. Unlike the situation found in the figure-of-eight complex 7, the aromatic ring was metalated, resulting in the formation of an Ir-C and an Ir-H bond. Mixtures of solvents were used to increase the solubility of the ligand (soluble in MeCN) and [Ir(coe)2(µ-Cl)]2 (soluble in THF). It is worth mentioning that MeCN seemed to have stabilized the pincer-type Ir(III) hydride because when bis-imidazolium dibromide, which is soluble in THF, was treated under the same conditions but in the absence of MeCN, only decomposition of the Ir precursor was observed. Hybrid phosphino-NHC ligandIn order to limit possible problems associated with the sensitivity of uncoordinated phosphine groups, we introduced the P-donor moiety in the final step of the preparation. Diethyl ether was used as the solvent in the first step to precipitate the mono-substituted derivative, thus preventing further substitution eventhough 1,3-bis(chloromethyl)benzene was present in large excess. [. . . ]

Copper homeostasis in Escherichia coli is mediated in part by a copper sensing system (the Cus system) that includes a tripartite protein complex, CusCBA, which spans both the inner and outer membranes of E. coli. The inner membrane protein, CusA, belongs to the RND superfamily of protein transporters and couples the export of copper ions with an influx of protons. CusB, the membrane fusion protein, is a soluble protein that forms a complex with CusA and is believed to interact with CusC, the outer membrane factor protein. CusF, the fourth component of this system, is a small periplasmic metallochaperone that delivers metal to the CusCBA pump. The research presented in this work describes the elucidation of protein-protein interactions and metal transfer between components of the Cus system. Chemical cross-linking and mass spectrometry reveal that CusF and CusB interact at their metal-binding sites. The N-terminal region of CusB, which includes the metal-binding site, is characterized utilizing a variety of biochemical and molecular tools and demonstrates metal-binding and metal transfer with CusF. Cross-linking experiments and XAS preliminary results reveal a novel interaction between CusF and CusA, which supports our theory that CusA acquires metal from CusF rather than CusB. Together, these findings aid in our understanding of the mechanism of metal transport and the molecular details involved in protein-protein interactions within CusCFBA.

In this work, three mononuclear and five binuclear heteroleptic copper(I) complexes based on quinolin-yl-1H-1,2,3-triazole as diimine chelating ligand and DPEPhos as chelating diphosphine were successful synthesised, these compounds may be good alternative to more expensive photosensitizer based on ruthenium complexes. They show good absorption in visible region and good luminescence in solution at room temperature with long-lived excited states. The most promising complexes, which show adequate photophysical characteristics, such as high PLQY and long-lived luminescence lifetimes will be used to prove their activity in the photocatalytic reduction of CO2.

Thesis (M.S.)--University of Missouri-Columbia, 2007.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed Oct. 26, 2007). Vita. Includes bibliographical references.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Triazenides ligands, strategically substituted by aril groups [ N=N N(H) ] chains and containing NO2, CF3 e F groups in different positions were evaluated in relation to the occurrence of intermolecular interactions through secondary non-covalent bonding. The research is based on the single crystal X-ray diffraction to analysis of arrangements performed in the solid state. This work presents the synthesis and the investigation of the crystalline and molecular structure of twelve new molecules in the literature: the pró-ligands 1-(3-nitrophenyl)-3-(2-fluorophenyl)triazene,1-(3-trifluorometilphenyl)-3-(3nitrophenyl)triazeno and 1,3-bis(3-trifluorometilphenyl)triazene, and the mononuclear complexes de Cu(I), Cu(II), Ni(II) e Pd(II), trans-bis[1-(3-nitrophenyl)-3-(2-fluorophenyl)triazenide]bis(amin) Copper(II) (1), trans-{bis[1(3-nitrophenyl)-3-(2-fluorophenyl)triazenide]bis(pyridina)Copper(II)}.Pyridina (2), bis[1,3-bis(3-trifluorometilphenyl)triazenide]bis(pyridina)Copper(II) (3), trans-{bis[1-(3-trifluorometilphenyl)-3-(3-nitrophenyl)triazenide]bis(pyridina)Copper(II)} (4), trans-{bis[1-(2-fluorophenyl)-3-(3-trifluorometilphenyl)triazenide]bis(pyridina)Copper(II)} (5), {[1,3-bis(3-nitrophenyl)triazenido] bis-(triphenylfosfine) Copper(I)}.THF (6), trans-bis[1(3-nitrophenyl)-3-(2-fluorophenyl) triazenide]bis(pyridina)Nickel(II) (7), bis[1,3-bis(4-fluorometil- phenyl)triazenide]bis(pyridina)Nickel(II) (8) e trans-bis[1-(3-nitrophenyl)-3-(2-fluorophenyl) triazenide] bis(pyridina)Palladium(II) (9). Beside the structural analysis the compounds were characterized by melting point and infrared spectroscopy. Additionally, all pre-ligands were characterized by nuclear magnetic resonance and ultraviolet-visible spectroscopies. The complex (1) by electronic paramagnetic resonance. Specifically the complex (7) and (8) were analyzed for their UV-visible electronic spectra, molecular modeling and semi-empirical calculations for the correlation of spectra.
Ligantes triazenidos estrategicamente substituídos por grupos arilas terminais na cadeia diazoamínica [ N=N N(H) ] contendo os substituintes NO2, CF3 e F em diferentes posições foram avaliados quanto à ocorrência de interações intermoleculares através de ligações secundárias não covalentes. A investigação baseou-se principalmente na difração de raios-X em monocristal para analisar estruturalmente a formação de arranjos supramoleculares no estado sólido. Este trabalho apresenta a síntese e a investigação da estrutura cristalina e molecular de doze moléculas inéditas na literatura: os pré-ligantes 1-(3-nitrofenil)-3-(2-fluorofenil)triazeno, 1-(3-trifluorometilfenil)-3-(3-nitrofenil)triazeno e 1,3-bis(3-trifluorometilfenil)triazeno, e os complexos mononucleares de Cu(I), Cu(II), Ni(II) e Pd(II), trans-bis[1-(3-nitrofenil)-3-(2-fluorofenil)triazeni-do]bis(amin)Cobre(II)(1), trans-{bis[1(3-nitro- fenil)-3-(2-fluorofenil)triazenido]bis(piridina)Cobre(II)}.Piridina (2), bis[1,3-bis(3-trifluorometil- fenil)triazenido]bis(piridina)Cobre(II) (3), trans-{bis[1-(3-trifluorometilfenil)-3-(3-nitrofenil) triazenido]bis(piridina)Cobre(II)}(4), trans-{bis[1-(2-fluorofenil)-3-(3-trifluorometilfenil)triazeni- do]bis(piridina)Cobre(II)} (5), {[1,3-bis(3-nitrofenil)triazenido]bis-(trifenilfosfina) Cobre(I)}.THF (6), trans-bis[1(3-nitrofenil)-3-(2-fluorofenil)triazenido]bis(piridina)Níquel(II) (7), bis[1,3-bis(4-fluorometilfenil)triazenido]bis(piridina)Níquel(II) (8) e trans-bis[1-(3-nitrofenil)-3-(2-fluorofenil) triazenido] bis(piridina)paládio(II) (9). Além da análise estrutural cristalina e molecular por difração de raios-X em monocristal, os compostos foram caracterizados pelo ponto de fusão e a espectroscopia de infravermelho. Adicionalmente, todos os pré-ligantes foram caracterizados por ressonância magnética nuclear H1 e por espectroscopia do ultravioleta visível. O complexo (1) por ressonância paramagnética eletrônica. Especificamente os complexos (7) e (8) foram analisados quanto aos seus espectros eletrônicos ultravioleta-visível, modelagem molecular e cálculos semiempíricos para a correlação de espectros.

· S'ha preparat i caracteritzat una família de complexos de Cu(III) contenint lligands triazamacrocíclics, estudiant-se les seves propietats estructurals, espectroscòpiques i redox. Aquesta àmplia família de complexos tenen un gran interès perquè permeten descriure les propietats dels complexos de Cu en un estat d'oxidació poc habitual i a més ens han permès mesurar de manera quantitativa l'efecte Meyerstein.
· Una nova família de complexos de Cu(I) amb els lligands triazamacrocíclics es sintetitzada i caracteritzada per tècniques espectroscòpiques i estructurals, demostrant que aquests complexos presenten diferents estructures a l'estat sòlid i en dissolució. Així doncs, mentre que en dissolució es demostra per RMN que es tracta d'una espècie monomèrica, la determinació estructural per difracció de raigs X d'aquests complexos de Cu(I), ens confirma la formació d'espècies polimèriques. Per altra banda, s'ha estudiat la seva reactivitat; a) la seva implicació en la formació de lligands deuterats mitjançant l'intercanvi H/D en condicions suaus i b) la formació de complexos bisfenoxo a partir de la reactivitat entre els corresponents complexos de Cu(I) i oxigen molecular. De la mateixa manera, s'ha preparat el corresponent anàleg de Ag(I) en estat sòlid, obtenint la formació d'un polímer de Ag(I), el qual presenta a l'estat sòlid una estructura en forma de ziga-zaga, diferent a l'estructura del polímer de Cu(I), que és lineal.
· S'ha determinat i proposat el mecanisme que té lloc en l'activació de l'enllaç C-H i posterior reacció de transferència per tal d'estabilitzar els productes finals mitjançant una reacció de desproporció. El seguiment de la reacció té lloc mitjançant tècniques espectroscòpiques com UV-vis. Dit seguiment, ens permet determinar les diferents influències electròniques sobre la reacció de formació dels complexos organometàl·lics de Cu(III). A més a més, el seguiment de la reacció a baixa temperatura ens permet determinar espectroscòpica i teòricament la formació d'un intermedi de Cu(II), i mitjançant la determinació dels paràmetres cinètics i termodinàmics es proposa un mecanisme de reacció. Posteriorment, s'ha assajat la reactivitat d'una sal de Cu(II) amb un lligand macrocíclic que conté un grup metil en el carboni orientat cap al centre del macrocicle, implicant la formació d'un intermedi agòstic. De la determinació estructural d'aquest intermedi de CuII i del lligand protonat, s'extreuen una sèrie de conclusions molt interessants, com són la demostració estructural de l'activació de l'enllaç C-C en la primera etapa de formació i de manera anàloga poder comparar-ho amb els sistemes macrocíclics HL2-HL6, demostrant la possible formació d'un intermedi agòstic, on es produeix l'activació de l'enllaç C-H. Aquesta similitud estaria d'acord amb els sistemes HL2-HL6, els quals espectroscòpica i teòricament s'havia detectat la presència d'un intermedi de característiques similars. Degut a l'acidesa d'aquest protó, i gràcies a la presència d'una base com és el propi lligand, aquest podia ésser extret donant lloc a la formació dels corresponents organometàl·lics de Cu(III). Dita estructura també representa un dels pocs exemples d'un organometàl·lic de CuII, un estat d'oxidació poc conegut dins d'aquest camp.
· S'ha descrit la reactivitat dels nous complexos organometàl·lics de Cu(III), els quals sota medi pròtic i en condicions àcides o neutres són espècies totalment estables, però en condicions bàsiques o reductores aquestes espècies reaccionen donant lloc a la formació de noves espècies de tipus bisfenoxo, on el Cu es troba en estat d'oxidació +2. S'han caracteritzat mitjançant difracció de RX, on es s'observa l'entorn químic del Cu, la geometria del complex bisfenoxo i l'hidroxilació de l'anell aromàtic.
· Finalment, s'ha descrit per primera vegada la síntesi i caracterització d'uns nous complexos organometàl·lics de Ni. Aquests són sintetitzats en base als càlculs teòrics realitzats sobre els nostres sistemes macrocíclics. Per aquests complexos hem investigat l'efecte del metall, canviant el coure per altres metalls de la primera sèrie de transició (Mn, Fe, Co, Ni, Cu, Zn) i de la segona sèrie de transició (Ru, Rh, Pd, Ag). Els resultats demostren que el Ni(II), és el metall que presenta una major capacitat de l'activació de l'enllaç C-H en aquests sistemes aromàtics. Aquests compostos s'oxiden lentament cap a complexos de Ni(III). Per altra banda, l'addició d'una sal de clor sobre una solució d'un complex de Ni(II) permet aïllar el corresponent complex de Ni(III), caracteritzat per ressonància de spin electrònic
· A family of Cu(III) complexes containing triaza macrocyclic ligands has been described and their structural, spectroscopic and redox properties thoroughly investigated. This family is of interest because it allows studying the properties of Cu complexes in the very unusual oxidation state III and furthermore it allows measuring the so called Meyerstein effect in a quantitative manner.
· A new family of Cu(I) complexes containing triaza macrocyclic ligands has been synthesized and characterized both in the solid state and in solution by spectroscopic and structural techniques. NMR spectroscopy demonstrates that the complexes adopt monomeric structures in solution. However, X-ray diffraction analyses demonstrate a polymeric nature in the solid state. On the other hand, the reactivity of these complexes in H/D exchange reactions has been studied, demonstrating that these systems are capable of activating the C-H bond of the aromatic ring in deuterated acetone. On the other hand, the Cu(I) complexes are capable of activating O2, leading to intramolecular aromatic hydroxylation, thus generates complexes with the general formula [(CuII2(m-OLi)2]2+. Finally, we have prepared the corresponding Ag(I) compound. X ray analysis shows that the complex adopts a lineal zigzag polymeric structure.
· We propose the mechanism for the activation C-H bond by a Cu(II) complex, coupled to a disproportionation reaction. The monitoring of this reaction has been performed at room and at low temperatures, determinating the different electronic influences of the ligand on the organometallic Cu(III) formation reaction. The monitoring at low temperatures allows to observe and spectroscopically characterize a Cu(II) intermediate. Determination of the kinetic and thermodynamic parameters leads us to propose a mechanism for the reaction.
By replacing the H with a Me group, we have crystallography characterized the first example of a Cu(II) C-C agostic intermediate. This specie bears spectroscopic resemblance with the Cu(II) species formed in the aromatic C-H bond activation, and thus we propose it to be the analogous Cu(II) intermediate.
Both Cu(I) and Cu(III) complexes are known in organocopper chemistry, but a stable Cu(II) complex is seldom reported. Furthermore, this specie constitutes the second example of a Cu(II) organometallic compound reported in the literature.
· We have studied the reactivity of organocopper(III) complexes under different conditions to synthesize new bisphenoxo Cu(II) complexes. These bisphenoxo complexes have been characterized by X-ray diffraction.
· A new family of Ni(II) complexes containing triaza macrocyclic ligands have been described and their structural and spectroscopic properties thoroughly investigated. In this case, the C-H bond activation is proposed to occur via acid-base reaction. Moreover, a theoretical study of the activation of the C-H bond in aromatic systems by several transition metals has been carried out. For these specific ligands we have investigated the effect of the metal, changing the copper ion by other first (Mn, Fe, Co, Ni, Cu, Zn) and second transition series metals (Ru, Rh, Pd, Ag). The results demonstrate that the Ni(II) is the ion that presents the highest capacity for activating the C-H bond in the aromatic system of the ligand. On the other hand, the addition of a chloride salt to the Ni(II) complex solution allows the formation of a new and extremely rare organometallic Ni(III) complex.

Abstract Polymetallic (Pb-Zn-Cu-Ag-Au-Sb-As-Bi-Cd-Te-Se-Ge…) quartz veins occur in an area from Eidsvoll in southeastern Norway to west of LakeVänern in southwestern Sweden. They most likely formed during the waning stage of the c. 1 Ga Sveconorwegian orogeny. In Värmskog parish, Värmland county, several mineralized quartz veins of different types are known. Of these, three of the larger vein deposits, Vegerbol, Karlsbol and Södra Gärdsjön, have been investigated. Despite a history of mining activities (mostly for silver) and exploration from the mid-1800s up until the present day, details about their ore mineralogy have remained essentially unknown. In order to classify and characterize them better, the present study was undertaken. The main ore minerals in the veins are galena, sphalerite, chalcopyrite, tetrahedrite sensu lato and pyrite. Additionally, this investigation showed the occurrence of an array of silver-bearing phases such as argentian tetrahedrite to freibergite, native silver, polybasite, pyrargyrite, jalpaite, aguilarite, cervelleite, hessite and matildite. These are the main and accessory silver carriers in the studied deposits. Gold (argentiferous) was also found, as well as the nickel-cobalt sulphide siegenite.    The silver contents of the tetrahedrites may vary within one deposit, ranging from tetrahedrite sensu stricto to freibergite. A weak positive correlation occurs between silver and iron in the tetrahedrites. Cadmium was found both in the tetrahedrites and in the sphalerites. Many sphalerites, however, are very pure ZnS. The complex accessory ore mineralogy, including native gold as well as tellurium and selenium-bearing phases (Vegerbol), makes these vein deposits comparable to mineralized veins to the west and southwest of the Värmskog area.    Combining mineralogical and textural observations with previous studies, the vein mineralizations most likely formed during a change in tectonic regime, in recurrently active brittle structures, at temperatures ranging from c. 350 down to below 100°C. The occurrence of pyrite and hematite and the lack of pyrrhotite and magnetite points to an oxidizing ore-forming environment with relatively high sulphur activity.    Finally, in order to assess the possibility of connecting two of the mined vein systems, VLF (Very Low Frequency) electromagnetic measurements were performed across the strike of a possible continuation between the Vegerbol and Karlsbol deposits. The VLF survey showed a significant anomaly where such a continuation was to be expected, thus indicating an overall strike length of at least 1 km for that vein system.
Sammanfattning Polymetalliska (Pb-Zn-Cu-Ag-Au-Sb-As-Bi-Cd-Te-Se-Ge…) kvartsgångar förekom­mer inom ett område från Eidsvoll, Norge i norr, till sydväst om Vänern i Sverige. De tros ha bildats under den svekonorvegiska orogenesens (ca 1 Ga) slutskede. I Värmskogs socken, Värmland, förekommer mineraliserade kvartsgångar av flera olika typer. Bland dessa har tre undersökts med avseende på malmmineralogi. Dessa kallas för Vegerbol, Karlsbol och Södra Gärdsjön, och de har brutits i huvudsak på silver. Trots att brytning och prospekteringsarbeten pågått från 1800-talet fram till i dag har det saknats detaljerade mineralogiska beskrivningar över fyndigheterna. Denna studie har genomförts för att bättre kunna karakterisera och klassificera dessa mineralis­eringar. Huvudmalmmineral vid dessa förekomster är blyglans, zinkblände, koppar­kis, pyrit och för Södra Gärdsjön även tetraedrit. Denna undersökning har påvisat förekomsten av silverförande faser som silverhaltig tetraedrit till freibergit, gediget silver, polybasit, jalpait, aguilarit, cervelleit, hessit och matildit, vilka utgör både huvudsakliga och accessoriska silverbärare i de undersökta förekomsterna. Guld (silverhaltigt) har också hittats, samt ett Ni-Co-förande mineral, siegenit.    Silverinnehållet i tetraedriterna varierar inom en och samma förekomst, några analyser har givit freibergitsammansättningar. En svag positiv korrelation finns mellan silver och järnhalt i tetraedrit. Kadmium förekommer både i tetraedrit och i zinkblände. Många zinkbländen består dock av rent ZnS. Förekomsten av relativt komplexa accessoriska mineral inklusive guld och Se-Te-faser (Vegerbol) visar att dessa gångar är jämförbara med liknande förekomster väster och sydväst om Värmskogs­området.    Genom att sammanföra data från denna undersökning med sådana från tidigare studier gjorda på gångarna kan man anta att de bildats vid vid en förändring av den tektoniska miljön, i upprepat aktiva spröda strukturer och vid temperaturer mellan ungefär 350 till under 100 °C. Förekomsten av pyrit och hematit samt avsaknad av magnetkis och magnetit tyder på att malmbildningen skett under oxiderade förhållan­den och relativt hög svavelaktivitet.      Elektromagnetiska mätningar i VLF-bandet (Very Low Frequency) utfördes tvärs över den förmodade strykningsriktningen för en möjlig fortsättning av gången mellan Karlsbol och Vegerbol. Mätningarna gav en tydlig anomali där en sådan fortsättning kan förväntas vilket skulle kunna betyda att det finns en sammanhängande mineralisering med ca 1 kilometers längd.

This Thesis presents the synthesis of novel 1D, 2D, and 3D Ag(I) and Cu(II) nanostructures and their use as sacrificial templates to make functional nanomaterials. New soft template methods were developed for the synthesis of AgCN and Cu(OH)2 nanostructures. Polymeric organic nanotubes were successfully used to synthesize AgCN nanowires, while the precipitation of Cu(OH)2 nanofibers was templated in water microdroplets. Both methods benefit from the versatility of soft templates and allows for a control of both the size and the morphology of the nanostructures produced. The conversion of these precursors into metallic and semi-conductive nanomaterials was achieved via chemical and electrochemical reduction, and thermolysis. Chemical reduction of the AgCN nanowires leads to the fabrication of conductive arrays on nylon filter substrates, while the thermolysis of the Cu(OH)2 spherical assemblies yields photoresponsive semi-conductive porous CuO spheres. The electrochemical reduction of the native Ag(I) and Cu(II) one-dimensional nanostructures was investigated in aqueous solution at gold/glass/gold junctions. The solid-solid conversion involved in the electrochemical reduction process was studied via cyclic voltammetry, chronoamperometry, and electronic microscopy. The strong influence of the reduction potential on the nanomaterials produced allowed for the fabrication of a range of Ag(0) nanostructures, including nanoparticles, nanoprisms, nanofibers and porous networks. Electrochemical reduction of Au/Mz+/Au junctions leads to the formation of an excellent electrical contact between the two gold electrodes. This technique was expanded to include ionically-conductive Ag2S nanowires which form metallic/ionic-conductor heterojunctions.Keywords: nanostructure, nanowire, template, emulsion, electrochemistry, silver, cyanide, copper, oxide, heterojunction, sacrificial template
Cette Thèse présente la synthèse de nouvelles nanostructures d'argent(I) et de cuivre(II) utilisées comme structures sacrificielles dans la fabrication de matériaux fonctionnels. De nouvelles méthodes basées sur des « template » souples ont été développées pour la synthèse de nanostructures de cyanure d'argent et d'hydroxyde de cuivre. Des nanotubes de polymères organiques ont été utilisés avec succès pour synthétiser des nanofils de AgCN, tandis que la précipitation de Cu(OH)2 a été confinée dans des microgouttes d'eau pour produire des aggrégats sphériques de nanofibres de Cu(OH)2. Ces deux méthodes bénéficient de la versatilité des « template » souples en permettant de contrôler la taille et la morphologie des nanostructures produites. La conversion de ces précurseurs en nanomatériaux métalliques ou semi-conducteurs a été réalisée par réduction chimique et électrochimique, ainsi que par thermolyse. La réduction chimique des nanofils de cyanure d'argent a permis la fabrication de nanostructures conductrices ordonnées à la surface de filtres de nylon. La thermolyse des sphères de Cu(OH)2 a produit des sphères poreuses et semi-conductrices composées de CuO, qui sont sensibles à la lumière. La réduction électrochimique des structures unidimensionnelles de Ag(I) et de Cu(II) a été réalisée en milieu aqueux sur des jonctions or/verre/or. La conversion solide-solide opérée durant la réduction électrochimique a été étudiée par voltammétrie cyclique, chronoamperométrie et microscopie électronique. La grande influence du potentiel de réduction sur les nanomatériaux ainsi produits a permis la fabrication d'un grand nombre de nanostructures d'argent(0), dont : des nanoparticules, des nanoprismes, des nanofibres et des réseaux poreux. La réduction électrochimique de jonctions Au/Mz+/Au conduit à la formation d'excellents contacts électriques entre les deux électrodes d'or. Cette technique a été appliquée à des nanofils conducteurs d'ions pour former des hétérojonctions.

U disertaciji su opisane sinteze i fizičko-hemijske karakterizacije 32 kompleksa kobalta(III), nikla(II) i bakra(II) sa ligandima S-metilizotiosemikarbazonom 2-acetilpiridina (HL¹), bis(S-metilizotiosemikarbazonom) 2,6-diacetilpiridina (H₂L²), tiosemikarbazonom-S-metilizotiosemikarbazonom 2,6-diacetilpiridina (HL³), 1-adamantoilhidrazonom 2-acetilpiridina (HL⁴) i 1-adamantoilhidrazonom di(2-piridil)-ketona (HL⁵).Kako ligandi HL³, HL⁴ i HL⁵ do sada nisu bili sintetisani, dobijeni rezultati ujedno predstavljaju i prve iz njihove koordinacione hemije. Iako je sa S-metilizotiosemikarbazonom 2-acetilpiridina poznato nekoliko kompleksa, do sada nijedan od njih nije strukturno okarakterisan, tako da su rezultati prikazani u ovoj disertaciji dali jasnu sliku o načinima koordinacije HL¹. Takođe, kako je sa H₂L² poznat vrlo malo broj kompleksa, dobijeni rezultati su dali značajan doprinos razumevanju koordinacione hemije ovog liganda.Gotovo svi sintetisani kompleksi (njih 27 od 32) su strukturno okarakterisani metodom rendgenske kristalografije. Odabrana jedinjenja su ispitana metodama termičke analize, a utvrđena je njihova antimikrobna i citotoksična aktivnost. 
This thesis describes syntheses and physico-chemical characterizations of 32 complexes of cobalt(III), nickel(II) and copper(II), with ligands 2-acetylpyridine S-methylisothiosemicarbazone (HL¹), 2,6-dicetylpyridine bis(S-methylisothiosemicarbazone) (H₂L²), thiosemicarbazone-S-methylisothiosemicarbazone 2,6-dicetylpyridine (HL³), 2-acetylpyridine 1-adamantoylhydrazone (HL⁴), and di(2-pyridil)-ketone 1-adamantoylhydrazone (HL⁵).Since the ligands HL³, HL⁴, and HL⁵ were not synthetized hitherto, the obtained results are the first regarding their coordination chemistry as well. Even though there are several complexes reported with 2-acetylpyridine S-methylisothiosemicarbazone as a ligand, none of them was structurally characterized. Therefore, here presented results gave clear insight into coordination modes of the HL¹. Moreover, since there is limited number of complexes with H₂L² reported hitherto, the obtained results gave significant contribution to understanding of its coordination chemistry.Almost each synthetized complex (27 out of 32) was structurally characterized by means of single crystal X-ray crystallography. The selected compounds were characterized by thermal analysis, and their antimicrobial and cytotoxic activity were determined.

Ligand-isotope labelling studies were performed on Zeise’s salt derivatives with pyridine N-oxide and quinoline N-oxide, their perdeuterated and O-18 isotopomers, C₂D₄ and ¹³CO, and the results of the vibrational analyses are reported. The isotopomers are modelled utilizing DFT calculations at the B3LYP level with the 6-31 G** basis set, and a pseudopotential level for the Pt atom. The calculated and observed structure and vibrational spectra correlate well. The crystal structures of [Pt(C₂2H₄)(pyO)Cl₂] and [Pt(CO)(quinO)Br₂] are reported. The frequency for the νPt-O vibration, ambiguously assigned in the literature, is here assigned unequivocally at 400 cm⁻¹. Previously observed, but inadequately described phenomena are addressed: the νN-O vibration in substituted quinoline N-oxides has been assigned previously at significantly different frequencies, depending on the nature of the substituent. This suggests that there is no specific mid-ir band associated with a high N-O character. A suitable explanation is presented for this phenomenon, showing that in low symmetry systems (eg. quinO) the N-O stretch is dispersed among several modes, whereas in high symmetry systems (eg. pyO) only a few limited modes have a high N-O character. A theoretical study of Cu(I) carbonyl compounds with macrocyclic ligands is presented. Local and global HSAB parameters applied to the donor and Cu atoms are used to explain the observed reactivities and the available spectroscopic data. Extended to [Cu(CO){H₂N(CH₂)[subscript n]NH(CH₂)[subscript m] NH₂}] BPh₄ (where n = 2, m = 2, 3 and n =3, m = 3, 4) and their -d₅ and ¹³CO isotopomers, subtle differences obtained experimentally for the CO stretching frequency in this series have been reproduced in the DFT calculations at the B3LYP level, using the 6-31 G* and 6-31 G** basis sets. Several properties (ligand pK[subscript a] values, νCO frequencies, etc.) correlate with some HSAB descriptors. Vibrational analyses are presented of Cu(I) carbonyl Schiff-base derivatives of N-Benzylidene-N’-[2-(benzyilidene-amino)-ethyl]-ethane-1,2-diamine, {2,2N3(C₆H₄R)₂}, and their -d₅ and ¹³CO isotopomers. The crystal structure of [Cu(CO){2,2N3(C₆H₅)₂}]BPh₄ is reported. From geometry optimizations and the HSAB descriptors, spectroscopic trends ([n]Cu-N and [nu]CO) are related to calculated global hardness and the Hammett substituent parameters, and are discussed in terms of σ-donation and π-backbonding of Cu- CO.

The present work is part of a research project that involves the study of new copper based complexes to be employed as photosensitizer in carbon dioxide photoreduction reaction. My research project is focused on the synthesis and characterization of 1,2,3 triazoles with a quinoline or pyridine in the lateral chain, which have been successively utilized to synthesize heteroleptic Cu(I) complexes. Redox potential and photophysic properties have been studied.

The atomic layer deposition (ALD) of copper oxide films from [(ⁿBu₃P)₂Cu(acac)] and wet oxygen on SiO₂ and TaN has been studied in detail by spectroscopic ellipsometry and atomic force microscopy. The results suggest island growth on SiO₂, along with a strong variation of the optical properties of the films in the early stages of the growth and signs of quantum confinement, typical for nanocrystals. In addition, differences both in growth behavior and film properties appear on dry and wet thermal SiO₂. Electron diffraction together with transmission electron microscopy shows that nanocrystalline Cu₂O with crystallites < 5 nm is formed, while upon prolonged electron irradiation the films decompose and metallic copper crystallites of approximately 10 nm precipitate. On TaN, the films grow in a linear, layer-by-layer manner, reproducing the initial substrate roughness. Saturated growth obtained at 120°C on TaN as well as dry and wet SiO₂ indicates well-established ALD growth regimes.
© 2009 The Electrochemical Society. All rights reserved.

Södra Cell Mörrum is one of the five paper pulp plants that are included in Södra Cell, and the paper pulp that is produced here is not only sold to Swedish paper mills. Most of the paper pulp is exported to different countries in Europe. In the manufacturing process the plant needs different kind of process water and there are guideline values for how much copper, iron and sodium this water is allowed to contain. Analyzes of this water is in the current situation done with an atomic absorption spectrometric instrument (AAS-instrument) with a flame.

 

Measurements done with flame-AAS of samples that have concentrations near the guideline values for copper, iron and sodium, are not reliable. The reason for not being reliable is that the quantitation limits of these metals are higher than the limit values. An alternative method that should give more reliable values is to analyze with an AAS- instrument with a graphite furnace. The purpose of this project was to perform a method validation of the graphite furnace of the AAS-instrument in the analysis of Cu, Fe and Na. The focus of the project was to find the detection limits for each metal, study the variation and to see if it is possible to analyze these water samples with this technique.

 

The concentrations of the calibration solutions is between 1-10 µg/l for Na, 5-25 µg/l for Cu and 2-20 µg/l for Fe.The detection limits for all metals were slightly below 1 µg/l and during the present circumstances in the laboratory; it would be difficult to get even lower detection limits. There are improvements that can be done to get to the even lower detection limits. The results from this work show that the variation in each sampling cup is very small but if you look at different sampling cups the variation could be large if the cups are not treated in the right way. Further validation analyzes like variation in between days needs to be done.

It is possible to analyze these low concentrations of copper, iron and sodium in the water samples with the AAS- graphite furnace, but it is difficult because there are many factors that affect the results. Examples of such factors are the environment where the instrument is placed in the laboratory and the human factor. Further analyzes needs to be done to get a better view of how these factors affect the result.

Les metal·lotioneïnes (MTs) són unes metal·loproteïnes de baix pes molecular i un elevat contingut en residus de cisteïna que els confereixen una gran capacitat per coordinar i intercanviar ions metàl·lics pesants. A més dels residus de cisteïna, existeixen altres lligands no proteics, com els lligands sulfur àcid-làbils, que també poden participar en la coordinació metàl·lica. L’estudi de les capacitats coordinants de les MTs ha permès classificar-les segons la seva preferència metàl·lica en Zn-tioneïnes i Cu-tioneïnes, així com demostrar l’existència d’una gradació entre aquests dos tipus extrems de MTs, donant lloc a un conjunt de proteïnes amb característiques intermèdies que podrien comportar-se com Cu-tioneïnes o Zn-tioneïnes depenent de les necessitats específiques de la cèl·lula. En els mamífers es troben 4 isoformes de metal·lotioneïna (MT1, MT2, MT3 i MT4). Aquestes 4 isoformes tenen 20 cisteïnes conservades en la seva seqüència proteica, i s’accepta que al unir-se a metalls divalents formen una estructura en dos dominis, β i α, que uneixen 3 i 4 ions divalents respectivament. MT1 i MT4 ja han estat estudiades per el nostre equip de recerca i han estat classificades com a Zn-tioneïna i Cu-tioneïna respectivament, així com els seus dominis. Amb l’objectiu d’ampliar el coneixement actual d’aquestes proteïnes, en aquesta Tesi Doctoral s’ha estudiat la capacitat coordinant respecte als metalls zinc, cadmi i coure de les dues isoformes restants de MT de mamífer, MT2 i MT3. Aquest estudi té com objectiu diferenciar la preferència metàl·lica de MT2, comparant-la amb MT1 (considerades fins ara equivalents), determinar les característiques de coordinació metàl·lica de MT3 i relacionar-les amb la seva funció biològica i, finalment, integrar les MTs de mamífer en la classificació global de les metal·lotioneïnes. Per això, s’han sintetitzat mitjançant enginyeria genètica aquestes isoformes i els seus dominis per separat a partir de cultius bacterians suplementats amb Zn, Cd o Cu. Els complexos metàl·lics així obtinguts s’han caracteritzat químicament mitjançant tècniques espectroscòpiques i espectromètriques (ESI-MS, ICP-AES, CD i UV-Vis). Els treballs realitzats amb la isoforma MT2 de mamífer i els seus dos dominis han permès conèixer les diferències de preferència metàl·lica respecta a MT1. Així, mentre que MT1 ha estat classificada com una Zn-tioneïna, MT2 presenta certes característiques de Cu-tioneïna, amb un domini β clarament Cu-tioneïna i un domini α Zn-tioneïna, que situa la isoforma en una pla intermedi en la classificació de les MTs. S’ha demostrat la relació entre les diferencies de seqüència entre les isoformes MT1 i MT2 i les seves preferències de coordinació metàl·lica, per la qual cosa es proposa que siguin considerades separadament, i no de manera conjunta com s’ha fet tradicionalment. Per altra banda, MT3 és clarament una Cu-tioneïna, amb els dos dominis Cu-tioneïna. De fer, s’ha revelat com una MT de caràcter Cu-tioneïna més accentuat que la mateixa MT4. Finalment, en aquesta Tesi Doctoral, s’ha pogut establir definitivament la gradació de preferència metàl·lica de totes les MTs de mamífer des de Zn-tioneïna a Cu-tioneïna tal i com segueix: MT1 > MT2 > MT4 > MT3, per posteriorment incloure aquestes isoformes en la classificació global de les MTs.
Las metalotioneínas (MTs) son unas metaloproteínas de bajo peso molecular y un elevado contenido en residuos de cisteína que les confieren gran capacidad de coordinar e intercambiar iones metálicos pesados. Además de los residuos de cisteína existen otros ligandos no proteicos, como los ligandos sulfuro ácido-lábiles, que también pueden participar en la coordinación metálica. El estudio de las capacidades coordinantes de las MTs ha permitido clasificarlas según su preferencia metálica en Zn-tioneínas y Cu-tioneínas así como demostrar la existencia de una gradación entre estos dos tipos extremos de MTs, dando lugar a un conjunto de proteínas con características intermedias que podrían comportarse como Cu-tioneínas o Zn-tioneínas dependiendo de las necesidades específicas de la célula. En mamífero se encuentran 4 isoformas de metalotioneína (MT1, MT2, MT3 y MT4). Estas 4 isoformas tienen 20 cisteínas conservadas en su secuencia proteica y, se acepta que al unirse a metales divalentes forman una estructura en dos dominios, β y α, que unen 3 y 4 iones divalentes respectivamente. MT1 y MT4 ya han sido estudiadas por nuestro equipo de investigación y clasificadas como Zn-tioneína y Cu-tioneína respectivamente, así como sus dominios. Con el objetivo de ampliar el conocimiento actual sobre estas proteínas, en esta Tesis Doctoral se ha estudiado la capacidad coordinante respecto a los metales zinc, cadmio y cobre de las dos isoformas restantes de MT de mamífero, MT2 y MT3. Este estudio tiene como objetivo diferenciar la preferencia metálica de MT2, comparándola con MT1 (consideradas hasta el momento como equivalentes), determinar las características de coordinación de MT3 y relacionarlas con su función biológica y, finalmente, integrar las MTs de mamífero en la clasificación global de las metalotioneínas. Para ello, se han sintetizado mediante ingeniería genética estas isoformas y sus dominios por separado a partir de cultivos bacterianos suplementados con Zn, Cd o Cu. Los complejos metálicos así obtenidos, se han caracterizado químicamente mediante técnicas espectroscópicas y espectrométricas (ESI-MS, ICP-AES, CD y UV-Vis). Los trabajos realizados con la isoforma MT2 de mamífero y sus dos dominios han permitido conocer las diferencias de preferencia metálica respecto a MT1. Así pues, mientras MT1 se había clasificado como Zn-tioneína, MT2 exhibe ciertas características de Cu-tioneína, con un dominio β claramente Cu-tioneína y un dominio α Zn-tioneína, que sitúan la isoforma en un plano intermedio en la clasificación de las MTs. Se ha demostrado la relación entre las diferencias de secuencia entre las isoformas MT1 y MT2 y sus preferencias de coordinación metálica, por lo que se propone la consideración separada de estas dos isoformas, y no conjunta como se ha hecho tradicionalmente. Por otra parte, MT3 es claramente una Cu-tioneína, con ambos dominios Cu-tioneína. De hecho se ha revelado como una MT de carácter Cu-tioneína más acentuado que la propia MT4. Finalmente, en esta Tesis Doctoral, se ha podido establecer definitivamente la gradación de preferencia metálica de todas las MTs de mamífero desde Zn-tioneína a Cu-tioneína como sigue: MT1 > MT2 > MT4 > MT3, para posteriormente incluir las isoformas en la clasificación global de las MTs.
Metallothioneins (MTs) are low molecular weight proteins with a high cysteine content, which confers them the ability to bind heavy metal ions. As well as the Cys residues, other kind of non-proteic ligands (such as acid labile sulfide) exist in MTs that also could participate in metal coordination. The study of the MT’s coordinative abilities has allowed classifying them following their metallic preferences as Zn- and Cu-thioneins, and to demonstrate the existence of a gradation between these two extreme MT’s types. These proteins with intermediate features could thus behave as Cu-thionein or Zn-thionein depending on the specific requirements of cell. In mammals, 4 isoforms of MT were found (MT1, MT2, MT3 and MT4). These 4 isoforms show 20 preserved Cys, and it’s accepted that in the union with divalent metals, they form a 2-domain structure (β and α) with 3 and 4 divalent ions, respectively. Our research team has already studied MT1 and MT4 and their domains, and classified them as Zn-thionein and Cu-thionein, respectively. With the objective of increasing the actual knowledge about these proteins, the Zn(II), Cd(II) and Cu(I) coordinative abilities of the 2 other mammal’s MT isoforms, MT2 and MT3 were studied. The goal of this PhD was to differentiate the metallic preferences of MT2 and MT1 (which were formerly considered as equal), to determinate the metallic coordinative characteristics of MT3 with respect to their biological function and finally, to integrate the mammal’s MT into the global MT classification. Using genetic engineering, these isoforms and their individual domains were synthetized from bacterial cultures in presence of Zn, Cd or Cu. The metal complex was chemically characterized using spectroscopy and spectrometry technics (ESI-MS, ICP-AES, CD i UV-Vis). These experiments showed different metallic preferences between MT2 and MT1. MT1 was identified as a Zn-thionein, whereas MT2 displays some characteristics of Cu-thioneins. The β domain of MT2 is a Cu-thionein and the α domain is a Zn-thionein, classifying MT2 as an intermediate MT into the global MT classification. The relationship between the sequence differences of MT1 and MT2, and their metallic coordinative preferences were demonstrated. These results suggest that MT1 and MT2 should be considered separately and not together as it was traditionally studied. On the other hand, MT3 is clearly a Cu-thionein, with 2 Cu-thionein domains, with a stronger Cu-thionein characteristic than MT4. Finally, this work has determined a gradation of metallic preferences of all mammal’s MTs, from Zn-thionein to Cu-thionein, as follow: MT1 > MT2 > MT4 > MT3. These isoforms were included into the global MT classification.

This thesis is organized in seven independent chapters: I) a description of the structure and reactivity of the metalloproteins of copper and iron which deal with the oxygen processing into living organisms; II) an study of the catalytic ability of different copper(I) complexes to activate H2O2 or tBuOOH; III) a mechanistic study on the Gif systems; IV) a study of the catalytic ability of FEpy4Cl2 to perform the catalytic oxidation of aromatic amines using H2O2 or tBuOOH as an oxidant; V) a mechanistic sudy of the reaction mechanism between LCu(I) and O2 in acetone, L = tris[4-tButyl(2-methylpyridil)] amine; VI) synthesis, structure and characterization of dinuclear zinc and cooper complexes, using hexaazamacrociclic ligands; VII) conclusions
Tesis organitzada en set capítols independents: I) activació d’O2, HOOH i t-BuOOH amb complexos de Cu i Fe per a l’oxidació de substrats orgànics i inorgànics; II) activació de dioxigen catalitzada per Cu(I) per a l’oxidació de substrats orgànics amb condicions suaus; III) la funcionalització d’hidrocarburs saturats. Noves evidències del paper de l’enllaç Fe-C en Química Gif; IV) transformació d’amines aromàtiques amb HOOH catalitzada amb Fepy4CI2+; V) mecanisme de reacció de LCu(I)CIO4, L = tris[(3-t-butil)-piridil] amina, amb oxigen en acetona; VI) complexos dinuclears de Cu i Zn amb lligands hexaazamacrocíclics

This Thesis aimed the synthesis of new metal complexes with triazenido ligands and triazenes chains directly linked to ferrocene fragment by a new synthesis methodology. The complex bis-[1,3-bis(2-biphenyl)triazenido-κN1]mercury(II) was synthesized, melting point 222–224 °C and yield 82 %, characterized by IR, UV-Vis, 1H e 13C RMN, elemental analysis, mass spectrometry by ESI(+)TOF, single crystal x-ray diffraction. The triazenes 1,1’-bis[1-phenyl-3(H)triazene]ferrocene (Compound 1) and 1,1’-bis(benzo-1,2,3-triazol-1-phenyltriazene)ferrocene (Compound 6) were synthesized by ferrocene metalation with BuLi and substitution by correspondent azide, with yields higher than 70 %, melting points 151 and 160 °C, respectively, were characterized by UV-Vis (Compound 1), 1H and 13C NMR, elemental analysis, IE-MS (Compound 1) ESI(+)TOF (Compound 6), single crystal x-ray diffraction (Compoound 1), powder x-ray diffraction, scanning electron microscopy (SEM) and thermogravimetric analysis. Starting from Compound 1 the following heterobimetallic complexes were sinthesized: {[Fe(C5H4NNNH5C6)]2Ni2} (Compound 2), {[Fe(C5H4NNN(H)H5C6)]2Cl2Cu2} (Compound 3 with protonated triazene), {[Fe(C5H4NNNH5C6)]2[Cu(PPh3)2]2} (Compound 4), {[Fe(C5H4NNN(H)H5C6)]2Cu4} (Compound 5). Compounds 6 and 7 didn’t yields suitable single crystals for X-ray diffraction, but based on the MS-ESI(+)TOF and 1H NMR analysis the respective structures based on 1,1’-bis[1-phenyl-3(H)triazene]ferrocene could be predicted. The new triazenes synthesis by methodology under study showed good yields and can be done in two steps. The compounds purification is simple by only extraction with organic solvent and water precipitation followed by filtration enabling the development of further new triazenes including other metallocenes and other azides.
O objetivo desta tese foi a síntese de novos complexos metálicos envolvendo ligantes triazenidos e triazenos diretamente ligados ao ferroceno. Foi sintetizado o complexo bis-[1,3-bis(2-bifenil)triazenido-κN1]mercúrio(II) com ponto de fusão 222–224 °C e rendimento de 82 %, caracterizado por infravermelho, UV-Vis, 1H e 13C RMN, análise elementar, espectroscopia de massas por ESI(+)TOF, difração de raios X em monocristal. Os triazenos 1,1’-bis[1-fenil-3(H)triazeno]ferroceno (Composto 1) e 1,1’-bis(benzo-1,2,3-triazol-1-feniltriazeno)ferroceno (Composto 6) foram sintetizados por metalação via BuLi, seguida da substituição pela azida correspondente com rendimentos superiores a 70 %, com pontos de fusão de 151 e 160 °C, respectivamente, foram caracterizados por UV-Vis (Composto 1), 1H e 13C RMN, análise elementar, espectroscopia de massas por IE (Composto 1) ESI(+)TOF (Composto 6), difração de raios X em monocristal (Composto 1), difração de raio X de pó, microscopia eletrônica de varredura e análise termogravimétrica. A partir do Composto 1 foram sintetizados os complexos multinucleares: {[Fe(C5H4NNNH5C6)]2Ni2} (Composto 2), {[Fe(C5H4NNN(H)H5C6)]2Cl2Cu2} (Composto 3 com triazeno protonado), {[Fe(C5H4NNNH5C6)]2[Cu(PPh3)2]2} (Composto 4), {[Fe(C5H4NNN(H)H5C6)]2Cu4} (Composto 5). O Composto 6 e o Composto 7 não resultaram em cristais adequados para medida, com as análises por EM-ESI(+)TOF e 1H RMN pode-se fazer uma predição da estrutura baseada nas estruturas com o 1,1’-bis[1-fenil-3(H)triazeno]ferroceno. A síntese de novos triazenos pela metodologia estudada possui bom rendimento e é realizada em apenas duas etapas, a purificação dos triazenos é simples, envolvendo apenas a extração com solvente orgânico e a precipitação em água seguida de filtração possibilitando o desenvolvimento de novos triazenos com outros metalocenos e outras azidas.

Le cuivre est un micronutriment essentiel qui participe à de nombreux processus biologiques. Cependant, le cuivre libre est toxique pour l’organisme parce qu’il catalyse une réaction de type Fenton formant des espèces réactives de l’oxygène. Par conséquent la concentration en cuivre est finement régulée dans tous les organismes vivants. Les maladies de Menkes et de Wilson sont dues à des dérèglements de l’homéostasie du cuivre qui se manifestent respectivement par une déficience ou une accumulation de cuivre dans l’organisme. La maladie de Wilson est traitée avec des chélateurs du cuivre, qui provoquent des effets secondaires importants chez certains patients.Mon projet de doctorat consiste en l’élaboration de trois familles de peptides qui contiennent des acides aminés cystéines et en l’étude de leurs complexes de Cu(I) pour déterminer s’ils sont des candidats adaptés pour le traitement de la maladie de Wilson. L'interaction de certains peptides avec les ions Hg(II) ou Zn(II) a également été étudiée. En effet, le Hg(II) est un cation métallique possédant des propriétés similaires au Cu(I) et donc souvent utilisé pour modéliser le Cu(I) qui est sensible à l'oxygène et se dismute dans l’eau. Le Zn(II) est quant à lui omniprésent dans les cellules et un compétiteur intracellulaire potentiel du Cu().Les séquences des peptides ont été choisies selon trois stratégies différentes. Dans la première, des séquences inspirées de la boucle de liaison du cuivre de la protéine bactérienne CueR (copper efflux regulator), contenant deux cystéines, ont été étudiées afin de bénéficier de la sélectivité et de la sensibilité de ce régulateur. Dans une deuxième approche, des peptides contenant trois cystéines dans les motifs CxCxxC et CxCxC ont été étudiés pour combiner les avantage des peptides (bonne internalisation dans les cellules hépatiques quand ils sont judicieusement fonctionnalisés) et des tripodes (très forte affinité pour le Cu(I)) de l’équipe CIBEST. Finalement, la pré-organisation a été exploitée dans un tétrapeptide rigide où les deux cysteines sont liées dans un coude β préformé.Les trois peptides modèles du régulateur CueR miment la capacité de la protéine à accueillir exclusivement un ion Cu(I) dans des conditions d'excès de ligand et une forte affinité et sélectivité par rapport au Zn(II). Ces caractéristiques sont avantageuses dans la perspective du développement de nouveaux chélateurs du Cu(I).Les peptides contenant trois cystéines s’avèrent trop flexibles pour contrôler la spéciation des complexes du Cu(I). Par ailleur, ces peptides sont bien adaptés pour une coordination efficace du Hg(II) par trois groupes thiolates. Les différences structurales n’ont qu’une influence modeste sur les stabilités des complexes. La différence dans la coordination des peptides vis-à-vis des deux ions mous Hg(II) et Cu(I) démontre que l'utilisation du Hg(II) comme ion modèle pour la coordination du Cu(I) avec des peptides ou des protéines riches en soufre dans des conditions physiologiques n’est pas toujours appropriée.La pré-organisation de la structure peptidique est un élément clé du contrôle de la spéciation du complexe Cu(I) et de l’affinité des ligands pour le Cu(I). Le peptide CDPPC forme uniquement le cluster Cu4P3 avec une grande stabilité et une bonne sélectivité Cu(I)/Zn(II). Au contraire, les données expérimentales avec le tétrapeptide plus flexible CPGC montrent la formation d’un mélange de complexes polymétalliques de Cu(I). Il est intéressant de noter que le peptide simple CDPPC est capable d’imiter la formation des clusters Cu(I)-thiolates identifiés dans de nombreuses protéines impliquées dans l’homéostasie du cuivre, comme Cox17 ou Ctr1. CDPPC est intéressant pour mettre au point un chélateur intracellulaire du Cu(I), et sa fonctionnalisation afin de pouvoir cibler les cellules hépatiques pour le traitement de maladie Wilson sera donc pertinente dans le futur
The essential micronutrient copper participates in several biological processes, like respiration, iron homeostasis, antioxidant defense or pigment formation. However, excess of copper can promote ROS formation and thus induce oxidative damages. Therefore, intracellular copper concentration is under strict control. Menkes and Wilson’s diseases are genetic disorders causing impairment in copper homeostasis leading to copper deficiency or overload, respectively. Wilson’s disease is treated by chelation therapy, but the presently used drugs have several adverse side effects.The aim of my Ph.D. work consisted of the design of three groups of cysteine containing peptides and the characterization of their Cu(I) complexes to determine whether they are appropriate candidates for the treatment of Wilson’s disease.The peptides were designed following three different approaches. In a first strategy, we attempted to take advantage of the outstanding selectivity and sensitivity of the bacterial copper efflux regulator protein CueR by studying oligopeptides based on the metal binding motif of CueR involving two cysteine residues. Second, three-cysteine containing linear and cyclic peptides were designed with the aim of merging the better internalization of peptides by hepatocytes and the high Cu(I) affinity of tripods previously studied in the Delangle’s lab. Finally, the advantages of a highly preorganized peptide structure were exploited in a short, rigid tetrapeptide where two cysteines were linked by a turn motif (CDPPC). For comparative purposes studies were also performed with another, less rigid tetrapeptide ligand containing the PG unit as a turn inducing motif.The three CueR model peptides resemble the ability of the protein to exclusively accommodate one metal ion under ligand excess conditions. This, combined with the large affinity and high selectivity vs. Zn(II), are the features that are advantageous in the view of the development of new Cu(I) chelators.The three-cysteine-containing peptides proved to be too flexible to control the speciation and hereby leading to the formation of several species. On the other hand, they are well adapted for an efficient trithiolate coordination of the thiophilic cation Hg(II). Structural differences in the three-cysteine containing peptides have minor effect on the affinity of the ligands towards Cu(I) and Hg(II) ions. The striking difference in the behavior of the peptides towards the two soft metal ions demonstrate that the use of Hg(II) as a probe for Cu(I) coordination with sulfur-rich peptides or proteins in physiological conditions may not always be fully appropriate.Preorganization of the peptide structure is a key element in the control of Cu(I) complex speciation and in the affinity of the ligands for Cu(I).CdPPC forms a single Cu4P3 cluster with high stability and displays large selectivity for Cu(I) with respect to the ubiquitous Zn(II). In contrast, The CPGC-Cu(I) system is characterized by a more complicated complex formation. It is worth to note, that the simple CdPPC peptide is able to mimic the Cu(I)-thiolate cluster formation that are typical in proteins like Ctr1 or Cox17. CDPPC is an interesting simple peptide candidate to be targeted to the liver cells for the localized treatment of Cu overload in Wilson’s disease

The solar industry is bigger than ever and continues to grow while competition between the solar cell manufacturers is increasing. This is something that has lowered the prices of solar cells and reduces the profitability for manufacturers. This thesis aims to lower the cost of production without losing efficiency by using copper wires as conductors in CIGS thin film solar cells. Silver paste is printed on the surface on the solar cell and represents 1/5 of the cell manufacturing costs. That is why this project focuses on how to lower the amount of silver in the solar cell without losing efficiency, this is a hands-on project. The work is done by improving the solar cell with implementation of own ideas and innovations. This is made by taking advantage of the benefits of copper wires and by changing the solar cell pattern. The results showed that one can reduce the amount of silver paste by up to 70% in each solar cell by producing a new silver print with much less silver. The silver-coated copper wires gave the highest results as conductors to lead out electricity from the surface because they can be made much thinner than today's solar cells conductors and obscure the surface less. This gave efficiencies of 10-11% which is in line with the production solar cells modules on Midsummer. The system has also been proved stable.
Solcellsbranschen är större än någonsin tidigare och fortsätter växa samtidigt som konkurrensen mellan solcellstillverkare ökar, detta är något som pressar ner priserna på solceller och minskar lönsamheten för tillverkarna. Därför fokuserar detta projekt på hur man kan sänka mängden silver i solcellen utan att förlora verkningsgrad. Detta genomförs genom att arbeta som en problemlösare ihop med egna idéer. Genom att dra nytta av fördelarna med koppartrådar och skapa ett nytt solcellsmönster är detta möjligt då silver utgör 1/5 av tillverkningskostnaden. Projektet domineras av praktiskt arbete med fokus på innovation av standardsolcellen. Resultatet visade att man kan sänka silverpasta mängden med upp till 70 % i varje solcell genom att ta fram ett nytt silvertryck med mycket mindre silver ihop med koppartrådar. Det användes silver-belagda koppartrådar som ledare för att leda ut ström från ytan med fördelarna att det är tunna och blockerar därför solljuset mindre. Resultaten gav en verkningsgrad på 10-11% vilket är i nivå med produktionssolcellsmodulerna på Midsummer. Systemet bevisades även stabilt.

La présente thèse décrit la synthèse de briques de base de fullerènes pour la préparation de dispositifs moléculaires photoactifs combinant C60 et porphyrines. La cycloaddition alcyne-azoture catalysée au cuivre (I) a été utilisée comme outil de synthèse pour la préparation des dérivés C60 complexes.L’utilité synthétique de synthons C60 a été montrée avec la préparation d’édifices moléculaires complexes présentant des propriétés spécifiques pour diverses applications. Ainsi, un système photoactif flexible combinant C60 et porphyrine a été synthétisé. Cependant la flexibilité de l’espaceur liant les sous-unités de ce composé conduit à des variations de structurales importantes et complique ainsi l’analyse des études photophysiques.Dans ce contexte, nous nous sommes proposé dans une première partie de la présente thèse de parfaitement contrôler l’orientation et la distance des différentes sous-unités au sein de systèmes C60-donneurs. Afin de répondre à ce besoin, nous avons construit une brique de base de C60 rigide ayant un groupe azoture aromatique. Ainsi, la réaction « click » avec un phénylacétylène conjugué au groupement donneur conduit à un espaceur rigide entre les deux sous-unités.La deuxième partie de ce travail a été consacrée à la synthèse d’hexa-adduits du C60 portant différents groupements fonctionnels. Une méthode de synthèse permettant de préparer des hexa-adduits du C60 fonctionnalisés a été mise au point au laboratoire.Cette stratégie a été modifiée et des composés de C60 comportant dix fonctions azotures et une fonction alcyne protégée ont été synthétisés; dans ce cas il est possible d’introduire dans un premier temps par une réaction click dix groupes fonctionnels. Et dans un second temps; après déprotection de la fonction alcyne, une seconde réaction de click permet alors de greffer un fonctionnel différent
The present PhD thesis manuscript is focused on the use of fullerene building blocks for the preparation of photoactive molecular devices combining C60 and porphyrins. Cu(I) Catalyzed alkyne-azide cycloaddition was used as a synthetic tool for the preparation of complex C60 derivatives. Specifically, in the first part (Chapter II-B), a flexible fullerene-porphyrin triad has been developed and the photophysical studies were performed. The flexible linker between the fullerene core and the azide groups prevented any conformational control on the relative orientation and distance between the two photoactive subunits connected together. This prompted the development of an analogous building block in which the azide unit is directly connected to the bridging phenyl ring (Chapter II-C). In this way, the click reaction with porphyrin-alkyne derivatives give access to hybrid systems with a controlled relative orientation of the two moieties. This is of fundamental importance for a better understanding of the structural parameters affecting the electron and/or energy transfer kinetic in such dyads.In the second part (Chapter III), a fullerene hexaadduct scaffold is used to build up sophisticated multiporphyrin systems for various applications. The preparation of these multi-chromophoric ensembles relies on the click-click approach developed in our group

L'etude du systeme cuo-bi#2o#3-sb#2o#5 a permis de mettre en evidence, outre quatre composes definis deja signales: bisbo#4, bi#3sbo#7, cusb#2o#6 et cubi#2o#4, un compose defini cu#4sb#2o#9 bixbyite et deux phases non-stchiometriques bi#1#-#xcu#xo#1#,#5#-#x#/#2 sillenite et cu#2#-#2#xbi#3#xsb#2#-#xo#7 pyrochlore. Les substitutions cationiques (la, y, gd-bi; nb-sb) realisees sur la phase prototype mb#1#,#5sb#1#,#5o#7 (m=cu, zn, cd) ont permis d'etudier l'influence des differents cations sur les proprietes cristallochimiques et les proprietes electriques qui en resultent

En los últimos años los ligando hemilábiles P,X (X= S,O), han sido de gran interés en el ámbito de la catálisis homogénea debido a que posee diversos heteroátomos en su estructura, con distinta capacidad coordinante. El objetivo de la presente tesis doctoral ha sido en el estudio de la reactividad de una serie de ligandos hemilábiles mono y difosfina con diferentes metales de transición y la evaluación de los correspondientes complejos en diversos procesos catalíticos. Se han obtenido diversos ligandos hemilábiles, siguiendo los procedimientos de síntesis desarrollados en nuestro grupo de investigación con anterioridad. Los ligandos obtenidos han sido el ligando bis-(2-difelnilfosfino)feniltioéter (DPTphos) y sus derivados monosulfurado P=S (DPTS) y disulfurado P=S,P=S (DPTS2),el compuesto bis(2-((difenilfosfino)metil)feniltioeter (DPTm) y la (2-fenilfosfino)-difeniltioéter (MPT). En el caso del ligando DPTm se han hecho ciertas mejoras en la síntesis ya descrita, y para la MPT se ha encontrado una ruta sintética alternativa, lo cual ha mejorado considerablemente los rendimientos de dichas reacciones. Se ha estudiado la reactividad de los ligandos DPTphos, DPTS1, DPTS2, DPTm y MPT con Ni(II) y los ligandos DPTm y MPT con Cu(I), Ag (I), obteniéndose diversos compuestos de coordinación. Dichos compuestos de coordinación han podido ser aíslados y caracterizados por las técnicas habituales de espectroscopía IR, RMN de 1H, 13C{1H} y 31P {1H}, microanálisis elemental, espectrometría de masas de alta resolución, y en los casos en que ha podido obtener cristales de cálidad adecuada, se ha hecho la resolución de la estructura cristalina mediante difracción de rayos X. Los compuestos de Cu(I) y Ni(II) obtenidos se han evaluado como agentes catalíticos para la formación de diariltioéteres por medio de reacciones de condensación de Ullmann. En el estudio de los blancos correspondientes a los ensayos anteriores, se ha podido observar la elevada efectividad catalítica de los sistemas consistentes en sales de Ni(II) y en ausencia de ligando, en el medio NaOH-DMF. En este caso, es posible obtener rendimientos de más del 99% en media hora de reacción. Estos estudios se han extendido a sales de Cu(I) con muy resultados. Se ha desarrollado nuevos métodos de obtención de diariltioéteres a partir de los correspondientes ariltiolatos y yodoarilos, utilizando NiCl2 como catalizador. La principal ventaja de estos procesos, es la ausencia de ligandos añadidos en el sistema catalítico. También podemos destacar, la obtención de altos rendimientos en cortos tiempos de reacción, a temperaturas no muy elevadas y con proporciones de catalizador inferiores a muchos de los procesos descritos en la bibliografía.