O Grupo Guaritas (Eocambriano da Bacia do Camaquã, RS) é formado por rochas siliciclásticas, predominantemente arenosas e conglomeráticas, interpretadas como de origem aluvial e eólica. Esta unidade estratigráfica pode apresentar mais de 1500 m de espessura de sedimentos e abrange as formações Guarda Velha, Pedra das Torrinhas, Varzinha, Pedra Pintada e Serra do Apertado. O Grupo Guaritas relaciona-se a importantes eventos geológicos do sul do Brasil, pois registra o encerramento da sedimentação em bacia extensional do tipo rifte (Bacia do Camaquã) durante o Cambriano, a qual se desenvolveu em área que seria posteriormente recoberta por ampla bacia intracratônica (a Bacia do Paraná), a partir do Ordoviciano. Para contribuir com novas informações sobre a proveniência das unidades eopaleozóicas brasileiras, as rochas arenosas do Grupo Guaritas foram submetidas à análise de minerais pesados, petrografia de lâminas delgadas e luminescência opticamente estimulada (LOE). As análises de minerais pesados foram realizadas na fração areia muito fina de 44 amostras coletadas em afloramentos. Essas análises abrangeram a identificação e quantificação da assembléia de minerais pesados transparentes não-micáceos, além da determinação dos índices ZTR (zircão+turmalina+rutilo), ATi (apatita/(apatita+turmalina)), ZTi (zircão/(turmalina+zircão)) e ZRi (zircão/(rutilo+zircão). As seções delgadas foram utilizadas para descrever os componentes deposicionais e diagenéticos e para classificar os arenitos estudados. Quatro amostras selecionadas foram submetidas ainda à análise da sensibilidade LOE de grãos individuais de quartzo. A sensibilidade LOE foi calculada utilizando a integral da curva LOE assim como de seus componentes, chamados informalmente de rápido, médio e lento. A sensibilidade LOE foi usada para avaliação de grau de retrabalhamento sedimentar. As amostras estudadas foram classificadas como arcóseos, subarcóseos e sublitoarenitos. Os minerais pesados identificados e suas porcentagens médias foram: zircão (36%), turmalina (13%), rutilo (3%), apatita (23%), granada (16%), anatásio (7%), titanita (1%), sillimanita (1%), monazita (<1%), epidoto (<1%), hornblenda (<1%), estaurolita (<1%) e cianita (<1%). Esses minerais pesados foram descritos em todas as unidades estudadas do Grupo Guaritas. Os valores médios do índice ZTR variam de 20 (Fm. Serra do Apertado) a 40 (Fm. Pedra Pintada) enquanto que o índice ZTi apresenta valores médios entre 62 (Fm. Guarda Velha) e 73 (Fm. Pedra Pintada). Os valores médios dos índices ZRi e ATi variam de 81 (Fm. Guarda Velha) a 90 (Fm. Varzinha) e de 79 (Fm. Guarda Velha) a 83 (Fm. Serra do Apertado), respectivamente. As médias da sensibilidade LOE total do quartzo apresentaram valores médios maiores para as unidades inferiores (Fm. Guarda Velha = 3295 contagens e Fm. Varzinha = 3655 contagens) em relação às superiores (Fm. Pedra Pintada = 2271contagens e Fm. Serra do Apertado = 2457 contagens). As médias dos componentes LOE rápido (15-19%), médio (37-38%) e lento (43-46%) não apresentam diferenças marcantes entre as unidades. A assembléia de minerais pesados dominada por zircão, apatita e turmalina sugere que os sedimentos arenosos do Grupo Guaritas são derivados principalmente de rochas ígneas ácidas (granitos neoproterozóicos). A pequena variação do índice ZRi aponta manutenção da configuração litológica da área-fonte durante a deposição das unidades estudadas. A abundância de feldspatos, fragmentos líticos e, principalmente, de apatita indica deposição em ambiente árido e/ou soterramento rápido. Isto é coerente com a sensibilidade LOE do quartzo, que é relativamente reduzida, indicando baixo grau de retrabalhamento sedimentar para as areias do Grupo Guaritas. A sensibilidade LOE mais elevada das areias da Formação Guarda Velha representaria maior contribuição de sedimentos distais mais retrabalhados.A sensibilidade LOE do quartzo permite avaliar o grau de retrabalhamento de sedimentos antigos (Cambriano), já que até então este método tinha sido aplicado somente à sedimentos quaternários. / The Guaritas Group (Eocambrian of the Camaquã Basin, southern Brazil) is mainly composed of fine to coarse-gravelly sandstones, interpreted as a record of fluvial and aeolian depositional systems. This stratigraphic unity may present more than 1500m thick of sediments, comprising the Guarda Velha, Pedra das Torrinhas, Varzinha, Pedra Pintada and Serra do Apertado formations. The Guaritas Group relates to important geological events occurred in southern Brazil during the Eopaleozoic. Its deposition marks the final episode of sedimentary filling of an extensional rift basin (Camaquã Basin) during the Cambrian, in an area after covered by a huge intracratonic basin (Paraná Basin) during the Ordovician. To contribute with new information about the provenance of Eopalaezoic Brazilian sediments, the sandy rocks of the Guaritas Group were analyzed through heavy minerals, thin section petrography and luminescence methods. Heavy minerals analyses were carried out in the very fine sand fraction of 44 rock samples collected from outcrops. These analyses included the identification and quantification of the transparent non-micaceous heavy minerals as well as the determination of the ZTR (zircon+tourmaline+rutile), ATi (apatite/(apatite+tourmaline)), ZTi (zircon/(tourmaline+zircon)) and ZRi (zircon/(rutile+zircon) indices. Thin section petrography was used to describe depositional and diagenetic components and classify the studied sandstones. Further, four samples were selected for measurements of optically stimulated luminescence (OSL) sensitivity in quartz single-grains. The OSL sensitivity was calculated using the total OSL curve as well as specific components, informally named fast, medium and slow. The OSL sensitivity of quartz has been used as a proxy for sedimentary reworking. The studied sandstones were classified as arkoses, subarkoses and sublitharenites. The identified heavy minerals and their mean percentages were: zircon (36%), tourmaline (13%), rutile (3%), apatite (23%), garnet (16%), anatase (7%), titanite (1%), sillimanite (1%), monazite (<1%), epidote (<1%), hornblende (<1%), staurolite (<1%) and kyanite (<1%). These heavy minerals were described in all studied units of the Guaritas Group. The mean values of the ZTR indice varied from 20 (Serra do Apertado Fm.) to 40 (Pedra Pintada Fm.) while the ZTi indice presented mean values between 62 (Guarda Velha Fm.) and 73 (Pedra Pintada Fm.). The mean values of the ZRi and ATi indices ranged from 81 (Guarda Velha Fm.) to 90 (Varzinha Fm.) and from 79 (Guarda Velha Fm.) to 83 (Serra do Apertado Fm.), respectively. The total OSL sensitivity of quartz demonstrated higher mean values for the bottom units (Guarda Velha Fm. = 3295 counts; Varzinha Fm. = 3655 counts) than for the upper units (Pedra Pintada Fm. = 2271 counts, and Serra do Apertado Fm. = 2457 counts). The means of the fast OSL component (15-19%), medium (37-38%) and slow (43-46%) did not differ markedly among the units. The heavy minerals assemblage dominated by zircon, tourmaline and apatite suggests that the sandy sediments of the Guaritas Group are mainly derived from acid igneous rocks (neoproterozoic granites).The low range of variation of the ZRi indice points out the maintenance of similar primary source rocks during the deposition of the Guaritas sediments. The abundance of unstable grains such as feldspars, lithic fragments and apatite indicates deposition under arid climate and/or high rate of sediment accumulation. The OSL sensitivity of quartz grains is relatively low, suggesting sands with low degree of reworking. This is compatible with the high content of unstable sand grains (apatite, feldspar and lithic fragments) and elevated rate of sediment accumulation. The greater proportion of grains with higher OSL sensitivity in the Guarda Velha Formation represents an increased contribution of sediments from distal more reworked sources.The OSL sensitivity of quartz allows evaluate the degree of reworking of older sediments (Cambrian), since this method had been applied only to Quaternary sediments.

High resolution dating of loess on the Chinese Loess Plateau (CLP) using Optically Stimulated Luminescence (OSL) has increased the understanding of past monsoon climate but also raised questions regarding dust mass accumulation rate (MAR), the presence of disturbances or gaps in the sediment record, a possible teleconnection between North Atlantic and East Asian monsoon climate, and whether these events are due to climate variability, local settings, or age model uncertainties. This study undertakes a detailed (&lt;20cm sampling resolution) -OSL investigation of the Lingtai section to create an independent age model using linear regression, to reconstruct monsoon climate changes using magnetic susceptibility(MS) and grain size (GS) proxies, as well as to calculate MAR for the site. The data shows that between 44-15 ka climate changes from a period of strong summer monsoon to a strong winter monsoon. GS data show variable trends attributed to changes in dust storm activity and local environmental conditions. MAR data does not correlate with grain size and is different from other loess records on the CLP. Such differences are either due to local variations or age model uncertainties. No clear correlation with Heinrich events or teleconnection with North Atlantic climate is visible in the records over the Last Glacial period, and hiatuses or gaps are not obviously present at this site. It is suggested that using linear regression for continuous age model construction from the luminescence ages comes with uncertainties due to subjective bias when fitting the lines and determining shifts in the data, especially during MAR calculations. Further studies are needed to ascertain optimal methods for creating age models, and to constrain the reasons behind the variability between different sites and loess records on the CLP. / Högupplöst OSL-datering av loessjordar från CLP har ökat förståelsen av dåtida monsunklimat, men har även lyft frågan gällande MAR, närvaron av avbrott eller småskaliga event i jordsektionerna, möjligheten av en relation mellan de Nordatlantiska och Ostasiatiska monsunklimaten, och om dessa förändringar sker till följd av faktisk klimatvariation, lokala förutsättningar, eller osäkerheter i åldersmodellen. Studien genomförde en detaljerad (&lt;20cm) OSL-undersökning av Lingtai-sektionen för att skapa en oberoende åldersmodell, återge monsunklimatförändringarna genom tillämpning av MS och GS proxies, samt beräkna MAR från platsen. Resultaten påvisar att mellan 44-15 ka förändrades klimatet från en period av stark sommar- till en stark vinter-monsun. Kornstorleks-resultaten påvisar stora variationer vilka kan kopplas till en förändring i sandstormsaktivitet samt de lokala förutsättningarna för deposition av sediment. MAR-resultaten överensstämmer inte med kornstorleksdatan och skiljer sig från den övriga empirin, detta kan bero på lokala variationer i regionen eller osäkerheter i åldermodellen. Det finns ingen klar korrelation mellan "Heinrich events" eller en "teleconnection" i sektionen, och avbrott samt störningar i sektionen är inte förekommande. Avsaknaden av korrelation antyder att användningen av regressionslinjer för att skapa kontinuerliga åldermodeller kommer innebära fortsatta osäkerheter i empirin, speciellt gällande beräking av MAR. Ytterligare studier krävs för att bestämma optimala metoder för att framställa åldersmodeller, samt att utröna orsaken till skillnaden mellan resultat från olika platser på plat

This work describes an investigation into the solution-phase binding of anionic guests by bimacrocyclic lanthanide complexes. It outlines the preparation of different classes of complexes bearing two metallic domains, and the effects of association on both the complex and the guest. Chapter one provides a cursory introduction to the fundamental properties of the lanthanides with a focus on luminescence. A brief literature review is given on the use of emissive lanthanide probes for the sensing of analytes. Chapter two concerns the preparation and properties of a series of binuclear complexes in which the two centres are linked with a short spacer group, with the aim of selectively sequestering small anions such as the halides in solution. The concept of luminescence titration will be introduced and then used to assess the binding parameters of a selection of guests. Chapter three describes a related class of ditopic lanthanide complexes in which the two metal centres are separated by a semi-rigid butyne linking group. Luminescence studies are again used to evaluate the binding constants of homologous series of dianions to ascertain how the size, geometry and functionalization of the anionic guest impacts on binding. Chapter four explores the coordination of phosphate species and assesses the ability to bind biologically significant phosphates of some of the complexes from Chapter 3. Chapter five details an investigation into the effects on guest-selectivity of further lengthening the linking unit which separates the two macrocyclic binding domains. Chapter six summarises the work done throughout the thesis and draws some overarching conclusions, as well as highlighting areas for further study. Chapter seven describes the experimental procedures.

La cellule photovoltaïque à porteurs chauds est un dispositif de conversion de l’énergie solaire en énergie électrique dont les rendements théoriques approchent les 86%. Additionnellement à une cellule photovoltaïque standard, ce dispositif permet de convertir l’excédent d’énergie cinétique des porteurs photogénérés, en énergie électrique. Pour cela, le phénomène de thermalisation doit être réduit et des contacts électriques sélectifs en énergie ajoutés. Afin de déterminer les performances potentielles des absorbeurs, tout en surmontant le défi de fabrication des contacts électriques sélectifs, un montage et une méthode de cartographie d’intensité absolue de photoluminescence résolue spectralement ont été utilisés. Ceci a permis d’obtenir la température d’émission et la séparation des quasi-niveaux de Fermi, les deux grandeurs thermodynamiques caractéristiques de la performance des absorbeurs. Dans cette étude, des absorbeurs à base de puits quantiques d’InGaAsP sur substrat d’InP sont utilisés. Les grandeurs thermodynamiques sont estimées et la technique de caractérisation utilisée permet l’accès à des grandeurs tel que le facteur de thermalisation mais aussi un coefficient thermoélectrique, appelé photo-Seebeck. L’analyse quantitative de porteurs chauds dans des conditions pertinentes pour le photovoltaïque est une première ; le dispositif étudié permettrait de dépasser la limite de Schockley-Queisser. Enfin, le dispositif étant muni de contacts des caractérisations électriques sont faites et comparé aux mesures optiques. Afin de mieux comprendre l’évolution des grandeurs thermodynamiques étudiées, une première simulation est proposée. / The hot carrier solar cell is an energy conversion device where theoretical conversion efficiencies reach almost 86%. Additionally to a standard photovoltaic cell, the device allows the conversion of kinetic energy excess of photogenerated carriers into electrical energy. To achieve this, the thermalisation process must be limited and electrical energy selective contacts added. In order to determine potential absorber performances and overcome the fabrication challenge of energy selective contacts, a set-up and the related method of mapping absolute photoluminescence spectra were used. This technique allows getting quasi-Fermi levels splitting and temperature of emission, both thermodynamic quantities characteristic of the performance of the absorbers. In this study, absorbers based on InGaAsP multiquantum wells on InP substrate were used. The thermodynamic quantities are determined and allow to access at quantities such as thermalisation rate but also a thermoelectric coefficient, so-called Photo-Seebeck. The quantitative analysis of the hot carriers regime, in relevant conditions for photovoltaic is a first: the analysed device indicates a potential photovoltaic conversion over the Schockley-Queisser limit. At last, as the device is supplied with electrical contacts, electrical characterization are made and compared to optical measurements. A first simulation is proposed to better understand the thermodynamic quantities evolution as a function of the electrical bias.

Mon travail au sein de l'équipe Chimie du Solide et Matériaux (CSM) à l'Institut des Sciences Chimiques de Rennes a porté sur la synthèse et la caractérisation de nouveaux composés hybrides à clusters, en particulier des clustomésogènes. Depuis leur publication en 2010, les clustomésogènes représentent une nouvelle famille de cristaux liquides, combinant les propriétés physiques des clusters, en particulier la luminescence, avec les propriétés de mise en forme et d'organisation des cristaux liquides. La première partie de ce manuscrit est consacrée à la synthèse, aux études de luminescence, d'oxydo-réduction et aux calculs DFT d'un nouveau composé à clusters, K4[Re6Sei8(N3)a6]·4H2O, précurseur de briques moléculaires pour l'élaboration de nanomatériaux hybrides. La deuxième partie porte sur la synthèse et l'étude de trois clustomésogènes (CL3, CL6 et CL9) présentant différentes densités en unités mésogéniques grâce à la modulation d'un espaceur entre le coeur inorganique et l'unité mésogénique. LC3, LC6 et LC9 possèdent respectivement une chaine aliphatique de 3, 6 et 9 carbones entre le cluster et les unités mésogéniques de type cyanobiphényls. Finalement, une prospective de simulation par dynamique moléculaire a été menée dans le but de comprendre les interactions entre ces macromolécules cristal-liquides, les clustomésogènes, afin de comprendre et prévoir les processus d'auto-assemblage de ces composés hybrides. Ce travail est une première étape pour le développement futur de clustomésogènes de structures contrôlées pour des applications dans les domaines de l'affichage et de l'éclairage. / My work took place in the material and solid chemistry team (CSM) from the institute of chemical Sciences of Rennes. It dealt with the synthesis and characterisation of new hybrid compounds : the clustomesogens, which generate luminescent properties assigned to the cluster and self-organisation from liquid-crystal material. The first chapter describes the state of art of the cluster chemistry and the basic knowledge to understand liquid-crystal and in particular clustomesogen material. The second chapter describes the synthesis, characterisation, luminescence and redox analysis and finally DFT calculations of a new inorganic cluster compound K4[Re6Sei8(N3)a6]·4H2O, precursor of molecular building block for the development of hybrid materials. The third chapter deals with the synthesis and study of three specific clustomesogens. Differing by the density in mesogenic units around the cluster core, the compound LC3, LC6 and LC9 have respectively an aliphatic chain of 3, 6 and 9 carbons between the cluster and the mesogenic cyanobiphenyl units. The fourth chapter presents a prospective of molecular dynamic simulations in order to understand the interaction between the clustomesogen supermolecular systems and anticipate the selfarrangement processes. This work is a first step for the future development of new and specific building blocks based on clustomesogens for applications in the field of display or lighting.

Orientador: Fernando Aparecido Sigoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T05:08:39Z (GMT). No. of bitstreams: 1 Bosshard_GabrielaZanotto_M.pdf: 4132378 bytes, checksum: abfa0f7115fb10b1aa31e7b1e9367ef8 (MD5) Previous issue date: 2012 / Resumo: O objetivo deste projeto foi investigar a síntese de óxido de zinco contendo enxofre obtido a partir de sulfeto de zinco nas fases wurtzita (hexagonal) e blenda de zinco (cúbica), assim como fazer a caracterização e estudar as alterações estruturais e ópticas dos materiais sintetizados e compará-las às propriedades do óxido de zinco sintetizado a partir de hidroxicarbonato de zinco. O método de síntese utilizado permite a obtenção de sulfeto de zinco hexagonal ou cúbico a baixa temperatura, permitindo um estudo comparativo da influência da estrutura cristalina do sulfeto de zinco na formação do óxido de zinco. Os estudos por difração de raios X mostram que há leve variação nos parâmetros de rede do material obtido, principalmente quando a síntese parte da fase hexagonal do ZnS. Somado a isso, a análise da luminescência dos materiais obtidos mostra emissão em torno de 520 nm, que pode ser atribuída a transição eletrônica entre defeitos de Frenkel (Zni e VZn") que foram formados a temperaturas inferiores à requerida para a formação deste tipo de defeito, indicando, portanto alterações na rede do óxido de zinco contendo enxofre. / Abstract: This project aimed to investigate the synthesis of sulfur-containing zinc oxide obtained from zinc sulfide in the wurtzite (hexagonal) or zinc blende (cubic) phases, in order to study possible changes in the structural and optical properties of the obtained, material which were compared to the properties of zinc oxide synthesized from zinc hydroxicarbonate. The used method of synthesis allowed obtaining zinc sulfide hexagonal or cubic at low temperature and therefore comparative studies of the influence of crystalline structure of zinc sulfide in the formation of zinc oxide was possible. X-ray diffraction data show that there is a slight variation in the lattice parameters of the obtained material, especially in the material synthesized from hexagonal ZnS. In addition to that, luminescence emission around 520 nm, assigned to the electronic transition among Frenkel defects (Zni and VZn"), indicate changes in the network of the sulfur-containing zinc oxide, since this type of defect is expected to be formed at temperatures above the ones used in the present work. / Mestrado / Quimica Inorganica / Mestra em Química

In this work samples of Barium Yttrium Fluoride (BaY2F8 -BaYF) doped with different concentrations of Tb3+, Er3+, Tm3+ e Nd3+ ions were characterized, aiming their application in radiation detection devices using their scintillating properties. Two types of samples were produced, polycrystalline samples, obtained via solid state reaction and single crystals, obtained via the floating zone melting method. The radioluminescence measurements (RL) revealed that the samples doped with 2.0 or 3.0 % Tb showed RL intensity at 545 nm two times higher than samples of CsI:Tl, although the total scintillation yield was smaller when compared to this commercial scintillator. Thermoluminescence (TL) results showed that all doped samples exhibited the same peak at 123 °C, which is characteristic of the matrix (BaY2F2). Comparison of the areas under the TL and RL curves for Tb3+ and Nd3+ doped BaYF revealed that the trapping centers are competing with the scintillation of the samples. However, this was not true for the Er3+ and Tm3+ doped samples and it was found that the scintillation yield is independent of the trap concentration up to a certain concentration limit. From this point on, the scintillation yields started increasing as the trap concentration increased. The radiation damage defects in BaYF:Tb3+ were studied via optical absorption (OA) and correlated with TL, showing that trapping centers are connected to the color centers. All samples exhibited different luminescence decay processes with time constants ranging from microseconds, for the fast processes, milliseconds, for the intermediate ones, and phosphorescent processes with decay time on the order of seconds. For the Nd3+ doped samples, very fast decay process was also found with time constants of about 60ns and that is an indication that this material can be used in fast detection systems, although its scintillation efficiency was weak. The combined results obtained with these techniques together with an analysis of X ray absorption spectroscopy (XAS) and X-rays Excited Optical Luminescence (XEOL) allowed the development of a model for the scintillation mechanism for the rare earth doped BaYF systems. / Neste trabalho as principais propriedades ópticas do Fluoreto de Bário e Ítrio (BaY2F8 - BaYF) dopado com diferentes concentrações dos íons Tb3+, Er3+, Tm3+ e Nd3+ foram estudadas visando a compreensão do mecanismo de cintilação e a aplicação em dispositivos que utilizam o princípio da cintilação para detecção de radiação. As amostras foram produzidas no Centro de Lasers e Aplicações no IPEN-SP. Dois tipos de amostras foram estudadas: amostras policristalinas, obtidas via síntese de estado sólido e amostras monocristalinas, obtidas pelo método de Fusão Zonal. Medidas de Radioluminescência (RL) revelaram que as intensidades de RL do BaYF dopado com 2,0 e 3,0 % de Tb3+ tanto para o monocristal quanto para o policristal são cerca de duas vezes maiores em 545 nm do que a do cintilador comercial CsI:Tl, apesar da eficiência de cintilação em todo o espectro visível ser menor do que a deste último. Utilizando a técnica de Termoluminescência (TL) observamos que todas as amostras dopadas apresentaram o mesmo pico em 123 °C característico da matriz (BaY2F2). Comparação entre as áreas sob a curva de RL e TL, para o BaYF dopado com Tb3+ e Nd3+, revelou que os centros de armadilhamento estão competindo com a cintilação da amostra, todavia este efeito não acontece para as amostras dopadas com Er3+ e Tm3+. Os defeitos gerados pelo dano de radiação para o BaYF:Tb3+ foram estudados através da Absorção Óptica (AO) e correlacionados com a TL, revelando que os centros de armadilhamento estão relacionados com centros de cor. Todas as amostras apresentaram diferentes processos de decaimento da luminescência com tempos característicos na ordem de microssegundos, para os mais rápidos, na ordem de milissegundos para os processos intermediários e, fosforescência de longa duração com tempos da ordem de segundos. A amostra dopada com Nd, apesar de possuir cintilação pouco intensa apresentou ainda um processo com tempo de vida muito curto, na ordem de nanosegundos, o que permite indicar a utilização deste material como detector rápido. Os resultados obtidos com estas técnicas, juntamente com análises de espectroscopia de absorção de raio X (XAS) e da emissão luminescente das amostras excitadas com raios X (XEOL), possibilitaram a elaboração de um modelo para o mecanismo de cintilação do BaY2F8 dopado.

Orientador: Teresa Dib Zambon Atvars / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T20:25:11Z (GMT). No. of bitstreams: 1 Germino_JoseCarlos_M.pdf: 14479907 bytes, checksum: c9f86b7bc1995a755d797d3af0c41cfc (MD5) Previous issue date: 2014 / Resumo: Nesta dissertação foram estudadas as propriedades fotoluminescentes de alguns compostos de coordenação de Zn(II) com N,N'-bis(salicilidenos) em soluções de THF e DMSO e em estado sólido: N,N'-bis(salicilideno)-1,2-fenilenodiamino - salofeno (KG-15) e seu composto de coordenação de Zn(II) aquo[N,N'-bis(salicilideno)-1,2- fenilenodimino]zinco(II)([Zn(salofeno)(H2O)]; (KG-15/Zn)); N,N'-bis(salicilideno)-4,5- diaminopirimidina - sal-4,5-pym (KG-17) e seu composto de coordenação de Zn(II) aquo[N,N'-bis(salicilideno)-4,5-diaminopirimidina]zinco(II) ([Zn(sal-4,5-pym)(H2O)]; (KG- 17/Zn). Os N,N'-bis(salicilidenos) e seus compostos de coordenação de Zn(II) foram sintetizados, observando-se aumento de cerca de 30 % dos rendimentos reacionais sob irradiação ultrassônica. Foram caracterizados por FTIR, ressonância magnética nuclear 1D de hidrogênio (1H) e de carbono (13C), caracterização estrutural por CHN, no caso dos ligantes realizou-se a caracterização estrutural por difração de raios-X de monocristal, foram também determinados os potenciais de óxido-redução do [Zn(salofeno)(H2O)] por voltametria cíclica e os valores de energia das bandas foram comparados com dados de espectroscopia eletrônica de absorção. As espectroscopias de fluorescência estacionária e resolvida no tempo em solução diluída de THF e de DMSO (apenas KG-17) e no estado sólido mostraram evidências da ocorrência da transferência de prótons no estado eletrônico excitado nos ligantes livres e coordendados. O composto [Zn(salofeno)(H2O)] apresentou eletroluminescência muito fraca em um dispositivo formado por vidro/ITO/PEDOT:PSS/composto de coordenação/Ca/Al muito baixa. Um diodo montado por vidro/ITO/PEDOT:PSS/PVK:(PFOFPen:[Zn(salofeno)(H2O)])/Ca/Al apresentou luminescência do composto de coordenação de Zn(II) devido à processos de transferência de energia entre o PFOFPen (doador) e o [Zn(salofeno)(H2O)] (receptor), além da eletroluminescência do PFOFPen / Abstract: In this dissertation the photoluminescent properties of some coordination compounds of Zn(II) with N,N'-bis(salicylidenes) in THF and DMSO solutions and solid state were studied: N,N'-bis(salicylidene)-1,2-phenylenediamine - salophen (KG-15) and its Zn(II) coordination compounds aquo[N,N'-bis(salicylidene)-1,2- phenylenediaminate]zinc(II) - [Zn(salophen)(H2O)] (KG-15/Zn) , N,N'-bis(salicylidene)- 4,5-diaminepyrimidine - sal-4,5-pym (KG-17) and its Zn(II) coordination compounds aquo[N,N'-bis(salicylidene)-4,5-diaminate]zinc(II) - [Zn(sal-4,5-pym)(H2O)] (KG-17/Zn). The ligands N,N'-bis(salicylidenes) and their Zn(II) coordination compounds were synthesized, observing an increase of about 30 % of the reaction proceeds under ultrasonic irradiation. The ligands and Zn(II) coordination compounds were characterized by FTIR,1D nuclear magnetic resonance of hydrogen (1H) and carbon (13C), structural characterization by CHN elemental analysis, in the case of the ligands the structural characterization was performed by monocrystal X-ray diffraction. The oxyreduction potential of [Zn(salophen)(H2O)] were determined by cyclic voltammetry and the values of the electrochemical energy band gap were compared with optical data. The stationary and time resolved fluorescence spectroscopy of the compounds in dilute solutions of THF and of DMSO (only KG-17) and in solid state showed proton transfer in the electronic excited state locaded on the ligands. The [Zn(salophen)(H2O)] compound exhibit a very low electroluminescence in a device consisting by glass/ITO/PEDOT:PSS/PVK:[Zn(salophen)(H2O)]/Ca/Al. A diode assembled by glass/ITO/PEDOT:PSS/PVK:(PFOFPen:[Zn(salophen)(H2O)])/Ca/Al showed luminescence of Zn(II) coordination compound due to energy transfer processes between PFOFPen (donor) and [Zn(salophen)(H2O)] (acceptor), beyond the electroluminescence of the PFOFPen / Mestrado / Físico-Química / Mestre em Química

Ces travaux de recherche présentés ici traitent de la synthèse d’une nouvelle classe d’assemblages de coordination de platine luminescents. En raison du savoir-faire du groupe, deux stratégies ont été suivies: (i) La première approche consiste en l’auto-assemblage d’une nouvelle famille de métallocages de platine de formule [Pt2L4][OTf]4 contenant divers ligands bidentés rigides. Les structures moléculaires de plusieurs complexes ont été déterminées. Les propriétés d'absorption et d'émission de ces assemblages ont été étudiées. De plus, la cage Pt2L4 (L=5-methoxy-1,3-bis(pyridin-3-ylethynyl)benzène) a montré des propriétés intéressantes en tant que molécule hôte envers une série de complexes métalliques plan-carrés agissant comme invités. Remarquablement on a déterminé la structure moléculaire d’un rare exemple dans lequel l’anion complexe dithiobenzène or(III) [Au(bdt)2]-1 a été encapsulé. Le comportement en solution a également été déterminé. De plus (ii) dans une seconde approche, on a décrit la synthèse d’un unique type d’assemblages de platine luminescents contenant un nouvel organométalloligand comportant une fonction chirale. L’organométalloligand permet un contrôle précis de la chiralité de l’assemblage au niveau supramoléculaire aussi bien que la modulation des interactions intermoléculaires Pt···Pt et π-π. En effet, plusieurs structures moléculaires analysées par diffraction des rayons X, ont été obtenues et confirment ce comportement. Les propriétés de luminescence de ces composés ont été étudiées en solution et à l’état solide. Elles ont montré que ces composés agissent en tant qu’intenses émetteurs rouges avec de bons rendements quantiques. De plus les propriétés chiroptiques de ces complexes de platine énantiopurs ont été étudiées aussi bien que leurs propriétés de luminescence par lumière polarisée. / The PhD research work presented herein deals with the synthesis of novel class of luminescent coordination platinum assemblies. Owing to the now-how of the group two strategies were followed: (i) The first approach consists in the self-assembly of novel family the platinum metallacages of the formula [Pt2L4][OTf]4 containing various rigid bidentate ligands. The molecular structures of several complexes were determined. The absorption and emission properties of these metallacages were investigated. Moreover the Pt2L4 (L = 5-methoxy-1,3-bis(pyridin-3-ylethynyl)benzène) showed interesting properties as host molecule towards a series of square planar metal complexes acting as guests. Remarkably the molecular structure of a rare host-guest system in which the anion dithiobenzene gold(III) complex [Au(bdt)2]-1 was encapsulated is determined. The solution behavior was also investigated. Moreover (ii) in a second approach the synthesis of a unique type of luminescent platinum assemblies containing a novel organometalloligand bearing chiral function is described. The organometalloligand allows a fine control of the chirality of the assemblies at the supramolecular level as well as the modulation of the intermolecular Pt···Pt and π-π interactions. Indeed several X-ray molecular structures were determined and confirmed this behavior. The luminescent properties of these compounds were investigated in solution and in solid state and showed that these compounds act as deep red emitters with good quantum yields. Furthermore the chiroptical properties of the enantiopure platinum complexes were investigated as well as their circular polarized luminescence (CPL) properties.

Phosphorescent transition metal complexes make up an important group of compounds that continues to attract intense research owing to their intrinsic bioimaging applications that arise from bright emissions, relatively long excited state lifetimes, and large stokes shifts. Now for biomaging assay a model organism is required which must meet certain criteria for practical applications. The organism needs to be small, with a high turn-over of progeny (high fecundity), a short lifecycle, and low maintenance and assay costs. Our model organism C. elegans met all the criteria. The ideal phosphor has low toxicity in the model organism. In this work the strongly phosphorescent platinum (II) pyrophosphito-complex was tested for biological applications as a potential in vivo hypoxia sensor. The suitability of the phosphor was derived from its water solubility, bright phosphorescence at room temperature, and long excited state lifetime (~ 10 µs). The applications branched off to include testing of C. elegans survival when treated with the phosphor, which included lifespan and fecundity assays, toxicity assays including the determination of the LC50, and recovery after paraquat poisoning. Quenching experiments were performed using some well knows oxygen derivatives, and the quenching mechanisms were derived from Stern-Volmer plots. Reaction stoichiometries were derived from Job plots, while percent scavenging (or antioxidant) activities were determined graphically. The high photochemical reactivity of the complex was clearly manifested in these reactions.