Thesis (Ph. D.)--Rutgers University, 2007. / "Graduate Program in Chemistry and Chemical Biology." Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references (leaves [165]-173).

Orientador: Pascoal Jose Giglio Pagliuso / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-10T19:13:39Z (GMT). No. of bitstreams: 1 Bufaical_LeandroFelixdeSousa_M.pdf: 1501359 bytes, checksum: 7c304c6377511ffd74495c952b919ec0 (MD5) Previous issue date: 2006 / Resumo: Um grande número de óxidos de metais de transição se forma em estrutura perovskita simples ou em uma de suas variantes, e muitos deles apresentam propriedades físicas interessantes, como supercondutividade, magneto-resistência colossal e ferroeletricidade. Uma das variantes da estrutura perovskita simples, a perovskita dupla ordenada (PDO), pode se cristalizar em simetria cúbica ou em variantes distorcidas, e possui fórmula geral A2B¿B" O6, em que o íon A ocupa os vértices do cubo enquanto os cátions B¿ e B¿¿ se alternam nos centros dos octaedros de oxigênio. Dentre os compostos com estrutura perovskita dupla já reportados na literatura, Sr2FeRe O6e Sr2FeMoO6são particularmente interessantes devido à suas interessantes propriedades físicas e à sua potencialidade como dispositivos magneto-eletrônicos. As propriedades estruturais, de transporte e magnéticas desses materiais estão altamente conectadas, e acredita-se que essas propriedades das PDO sejam fortemente dependentes do grau de hibridização dos orbitais d dos cátions B" (ex.: Re e Mo). Portanto, para se comprovar a potencialidade dos compostos PDO como dispositivos magnetoeletrônicos, além entender os mecanismos microscópicos responsáveis por suas propriedades magnéticas e eletrônicas, é essencial que se investigue em detalhes outros exemplos de PDOs que possam confirmar as idéias correntes propostas na literatura. Nesse trabalho descrevemos o processo de síntese e as propriedades físicas da série inédita Ca2-xL axFeIrO6, onde o Ir, assim como o Re e o Mo, é metal de transição, no caso com caráter 5d, e pode possuir diferentes estados de valência. Espectros de difração de raios-x e Refinamento Rietveld mostraram que os compostos da série se cristalizam em uma estrutura monoclínica, com grupo espacial P21/n, com uma grande presença de desordem catiônica nos sítios Fe/Ir. Medidas de magnetização indicaram que, aparentemente, os compostos tendem a evoluir de antiferromagnéticos nas extremidades da série, x = 0 e x = 2, para ferromagnéticos em regiões intermediárias da série. Medidas de espectroscopia Mössbauer mostraram que a valência do ferro é +3 ao longo da toda série, de modo que, possivelmente, a mudança na natureza das interações magnéticas estaria sendo causada pela alteração da valência do Ir devido a dopagem com La. Medidas de calor específico revelaram uma anomalia característica de uma transição magnética somente para a mostra de x = 0. Foram feitas medidas de resistividade em função da temperatura, em que se observou que os materiais apresentam comportamento isolante e praticamente nenhum efeito magneto-resistivo. Para as amostras no centro da série (em torno de x = 1,0) a presença de loops de histerese nas curvas MxH e um comportamento irreversível nas curvas de MxT sugerem uma competição entre fases ferrimagnéticas e antiferromagnética para esta região de concentração. Qualitativamente, nossos resultados podem ser interpretados considerando-se a mudança de valência do Ir, as regras de Goodenough-Kanamori-Anderson e a presença de desordem catiônica / Abstract: Perovskite structure and its variants host a great number of transition metals oxides that present a variety of interesting physical properties such as superconductivity, ferroelectricity and colossal magneto-resistance. A variant of the simple perovskite structure, the ordered double perovskite (ODP), also can grow in cubic (or lower) symmetry, with a general formula A2B¿B" O6, where the cation A occupies the vertices of the cube while B¿ and B" sits alternately at the center of the oxygen-octahedron. Among the compounds with ordered double-perovskite structure, Sr2FeReO6 and Sr2FeMoO6 are particularly interesting due to their interesting physical properties and their potentiality as magneto-electronic devices, having highly connected structural, transport and magnetic properties. It has been proposed that the magnetic and conducting ground states of ODP systems are strongly dependent on the delocalization level of the cation B" 5d electrons (ex: Re, Mo). However in order to prove the potentiality of composites ODP as magnetoeletronics devices, and to understand the microscopical mechanisms responsible for its magnetic and electronic properties, it is necessary to further investigate other examples of ODP that can confirm the current ideas proposed in literature. In this work we have synthesized and studied the Ca2-xLaxFeIrO6 series, where Ir, as well as Re and Mo, is transition metal with a 5d character which can possess different valence states. X-rays diffraction spectra and Rietveld Refinement analyses have shown that the Ca2-xLaxFeIrO6 compounds series crystallized in a monoclinic structure, space group P21/n, with an unavoidable cationic Fe/Ir site disorder. Measurements of temperature/field dependent magnetization have indicated that the magnetic interactions in these compounds evolves from antiferromagnetic in the extremities of the series, x = 0 and x = 2, for ferromagnetics in intermediate regions of the series. Mössbauer spectroscopy measurements revealed that the valence of the Fe is +3 in the whole series, in a way that the change in the nature of the magnetic interactions can be possibly caused by the variation of Ir valence due the La doping. Specific heat measurements have revealed an anomaly associated to a magnetic phase transition only for the x = 0 compound while measurements of electrical resistivity as a function of the temperature have shown insulating behavior and absence of magneto resistance for all studied samples. For the samples with x ~ 1.0, the presence of ferromagnetic loops and ZFC and FC hysteresys in the MxT curves indicates the competition between ferrimagnetic and antiferromagnetic phases in a disordered system. Qualitatively, all our results can be understood in terms of a valence changes in the Ir ions, the Goodenough-Kanamori-Anderson rules and the role of cationic disorder / Mestrado / Física da Matéria Condensada / Mestre em Física

Luminescent transition metal complexes have arisen as viable alternatives to organic dyes for sensory applications due to their notable advantages. This thesis aimed to synthesize different kinds of iridium(III) complexes as chemosensors and G-quadruplex probes for the detection of metal ions, small molecules, proteins and DNA to demonstrate the versatility of iridium(III) complex in luminescence sensing. Iridium(III) complex chemosensors were synthesized and developed for the detection of Cu2+ and cysteine. The iridium(III) complex plays the role of the "signaling unit", which transduces the analyte binding event into an optical (luminescent) signal and the "receptor unit" attached to the metal complex selectively binds the analyte of interest. Meanwhile, a series of iridium(III) complexes incorporating a variety of C^N and N^N donor ligands were synthesized and were shown to exhibit G-quadruplex-selective binding properties via emission titration, fluorescence resonance energy transfer melting and G-quadruplex fluorescent intercalator displacement experiments. These G-quadruplex-selective Ir(III) complexes were utilized as signal transducers to monitor the conformational changes of oligonucleotides in label-free oligonucleotide-based luminescent detection platforms for metal ion (Ag+), small molecules (cocaine), protein (insulin and AGR2) and gene deletion.

The iridium(III) methyl diarylphosphide complexes, Ir(CH₃PR₂-[N(SiMe₂CH₂PPh₂)₂] (2a: R = phenyl, 2b: R = meta-tolyl) had been prepared previous to this work. The iridium(III) dimethylphosphide complex, Ir(CH₃)PMe₂-[N(SiMe₂CH₂PPh₂)₂], 2c, is readily prepared in situ by transmetallation of the Ir(CH₃)I[N(SiMe₂CH₂PPh₂)₂] with KPMe₂ at -30°C. The synthesis of the phenylphosphide complex Ir(CH₃)PHPh[N(SiMe₂CH₂PPh₂)₂], 2d, involves deprotonation of the six-coordinate iridium(III) phenylphosphine complex, Ir(CH₃)I-(PH₂Ph)[N(SiMe₂CH₂PPh₂)₂], with KO¹Bu. Thermolysis of 2a and 2b yields the six-coordinate iridium(III) cyclometallated hydride complexes fac-Ir(ɳ²-CH₂PR₂)H[N(SiMe₂CH₂PPh₂)₂], 3a and 3b. The dimethylphosphide complex 2c undergoes the same rearrangement to afford 3c but more rapidly. Thermolysis of 3a-3c yields the square planar iridium(I) phosphine complexes of the formula, Ir(PCH₃R₂)[N(SiMe₂CH₂PPh₂)₂], 4a-4c. Some of the intermediates proposed in the thermolysis of 2a are synthesised independently by the reaction of iridium methylidene complex, Ir=CH₂[N(SiMe₂CH₂PPh₂)₂]. 10, with PHPh₂. The complex fac-Ir(ɳ²-CHPhPMe₂)H[N(SiMe₂CH₂PPh₂)₂] is generated from the reaction of Ir(CH₂Ph)Br[N(SiMe₂CH₂PPh₂)₂] with KPMe₂ without intermediacy of the corresponding phosphide complex. The photolysis of 2a-2c also yields species 4a-4c; however, no intermediacy of the cyclometallated hydride complexes 3a-3c is observed during this transformation. Upon thermolysis of the phenylphosphide complex 2d, only the corresponding iridium(I) phosphine complex, Ir(PHCH3Ph)[N(SiMe2CH2PPh2)2], 4d, is obtained, which is also the photolysis product of 2d. Ir(CH₃)PPh₂[N(SiMe₂CH₂PPh₂)₂], 2a, reacts at -78°C with dimethyl-acetylenedicarboxylate to yield an octahedral iridium(III) complex in which the alkyne has bridged between the phosphide ligand and the phosphine group of the chelating ligand. In addition, one of the phenyl groups from the chelating phosphine has migrated to the metal. On the other hand, Ir(CH₃)PMe₂[N(SiMe₂CH₂PPh₂)₂], 2c, reacts with the same alkyne to yield a product in which the alkyne has bridged between the phosphide group and the iridium centre. The reaction of 2a with diphenylacetylene affords Ir(PhC≡CPh)[N(SiMe₂CH₂PPh₂)₂] and free methyl-diphenylphosphine. Complex 2a reacts with terminal alkynes (RC≡CH; R = H, Ph, ¹Bu) to yield acetylide complexes of formula Ir(CH₃)PHPh₂(C≡CR)[N(SiMe₂CH₂PPh₂)₂]- The methylidene complex, lr=CH₂[N(SiMe₂CH₂PPh₂)₂], 10, prepared by the reaction of Ir(CH₃)I[N(SiMe₂CH₂PPh₂)₂] with KO¹Bu, reacts with phosphines PHR₂ (R = Ph, ¹Bu) to afford the cyclometallated hydride complexes, fac-Ir(ɳ²-CH₂PR₂)H[N(SiMe₂CH₂PPh₂)₂], via a five-coordinate methylidene phosphine intermediate. The reaction of 10 with PH₂Ph yields similar cyclometallated hydride product, but in this case the five-coordinate intermediate is not observed. The methylidene complex 10 reacts with the electrophiles MeI and AlMe₃ to yield Ir(ɳ²-C₂H₄)H(I)[N(SiMe₂CH₂PPh₂)₂] and Ir((µ-AlMe₂)H[N(SiMe₂CH₂PPh₂)₂], respectively. Reaction of 10 with HC≡CH affords an ɳ³˗allyl acetylide complex Ir(ɳ³-C₃H₅)(C≡CH)[N(SiMe₂CH₂PPh₂)₂]. A trimethylenemethane complex, fac-Ir{ɳ⁴-C(CH⁴₂)₃}[N(SiMe₂CH₂PPh₂)₂], is obtained readily upon exposing 10 to 1,2-propadiene. The reaction of 10 with 1,3-butadiene affords a pentenyl product, Ir(σ-ɳ³-C₅H₈)[N(SiMe₂CH₂PPh₂)₂]. In previous studies, the iridium(I) ɳ²-cyclooctene species, Ir(ɳ²-C₈H₁₄)-[N(SiMe₂CH₂PPh₂)₂], 25, has served as a useful starting material in the preparation of a number of iridium(I) and iridium(III) amide complexes. This complex is thermally stable, but upon photolysis, it yields Ir(H)₂[N(SiMe₂CH₂PPh₂)₂] and a mixture (2:1) of free 1,3-and 1,5-cyclooctadiene. This dehydrogenation process proceeds through ɳ³-allyl hydride intermediate, Ir(ɳ³-C₈H₁₃)H[N(SiMe₂CH₂PPh₂)₂]- The cyclo-octene ligand in 25 can be replaced by 1,3-butadiene and. 1,2-propadiene. The products obtained from these reactions are Ir(ɳ⁴-C₄H₆)[N(SiMe₂CH₂PPh₂)₂] and Ir(ɳ²-C₃H₄)[N(SiMe₂CH₂PPh₂)₂]. respectively. The reaction of 25 with AlMe₃ affords Ir(µ-AlMe₂)Me[N(SiMe₂CH₂PPh₂)₂]. / Science, Faculty of / Chemistry, Department of / Graduate

Orientador: Abner de Siervo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-24T13:12:45Z (GMT). No. of bitstreams: 1 Silva_CaioCesar_M.pdf: 10782612 bytes, checksum: 2408c43fe374c29c1bb91a7fecdf39c0 (MD5) Previous issue date: 2014 / Resumo: O material bidimensional grafeno possui um conjunto fascinante de propriedades que não são vistas juntas em qualquer outro material. Grafeno pode substituir outros materiais em diversas aplicações existentes, além de abrir uma janela para uma série de novas aplicações. As propriedades do grafeno foram mostradas em amostras sintetizadas através do método de esfoliação, no entanto, este método requer vários passos de litografia durante a preparação da amostra. Por outro lado, grafeno tem sido sintetizado pelo método de CVD (Chemical Vapor Deposition) por grandes áreas e com grande qualidade. O processo de CVD envolve um substrato metálico que interage com o grafeno, assim, um sistema alternativo que permite o estudo das propriedades do grafeno é o chamado grafeno quasi-free-standing, ou seja, grafeno que preserva suas propriedades mesmo quando _e suportado por um substrato. Estudos recentes demonstram que Ir(111) permite a preparação de grafeno com alta qualidade estrutural e com estrutura de banda praticamente idêntica à do grafeno puro. Determinar a topografia da superfície em nível atômico é fundamental para compreender a relação entre a estrutura eletrônica e a estrutura geométrica. O objetivo deste trabalho é determinar a estrutura do grafeno sobre Ir(111) através da técnica experimental de difração de fotoelétrons (XPD). A determinação da estrutura da superfície, com base em uma abordagem de cálculos de espalhamentos múltiplos, será apresentada e os resultados serão comparados ás previsões teóricas e a outros resultados experimentais / Abstract: The two-dimensional material graphene has a whole set of fascinating properties which are not seen together anywhere else. Graphene can replace many materials in a great number of existing applications and opens a window to several new applications. The properties of graphene were shown in samples synthesized through exfoliation method, however, this method requires several lithography steps during the graphene production. On the other hand, graphene has been synthesized by chemical vapor deposition method (CVD) through large areas with high quality. The CVD process involves a metallic substrate which interacts with graphene, thus, an alternative system that allows the study of the properties of graphene is quasi-free-standing graphene, i.e. graphene that preserves its properties even when it is supported by a substrate. Recent studies could demonstrate that Ir(111) does indeed allow for the preparation of extended graphene with high structural quality, and the band structure of graphene on Ir(111) is almost identical to the one of pristine graphene. Determination of the surface topography down to the atomic level is crucial in understanding the correlation between the electronic and geometric structure. The aim of this work is determine the structure of graphene on Ir(111) using the experimental technique of X-ray photoelectron diffraction (XPD). The surface structure determination based in a comprehensive multiple scattering calculation approach will be presented and the results will be compared with theoretical previsions and other experimental results / Mestrado / Física / Mestre em Física

Orientador: Abner de Siervo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-31T16:48:10Z (GMT). No. of bitstreams: 1 Ferreira_RodrigoCezardeCampos_M.pdf: 12900994 bytes, checksum: 7f4ff602b7e6aae7e2d8890e9f8d0a2b (MD5) Previous issue date: 2016 / Resumo: O grafeno é um alótropo bidimensional do carbono com hibridização do tipo sp2. Suas notáveis propriedades eletrônicas e estruturais provocaram um enorme interesse científico e tecnológico para o material na última década. Grafeno pode ser crescido em certos metais de transição através da técnica bem conhecida Chemical Vapor Deposition (CVD). A estabilidade do grafeno nesses substratos é garantida, porém as interações químicas entre eles modificam suas exóticas propriedades eletrônicas e estruturais. É possível sintetizar grafeno sobre Ir(111) sem defeitos estruturais substanciais e em um único domínio, quando realizado sob condições específicas de temperatura do substrato e da pressão do gás precursor (propileno). Na tentativa de isolar o grafeno do substrato, seja fisicamente ou eletricamente, existe a possibilidade da intercalação de diversas espécies, tais como gases, metais ou nanopartículas. Realizando tal procedimento, além da suspensão do material, é possível também dopar a banda eletrônica ou induzir abertura de gap. Neste contexto, o objetivo deste trabalho é estudar a dinâmica de crescimento e intercalação do ferro em Gr/Ir(111), seguindo os parâmetros termodinâmicos envolvidos e observando principalmente os deslocamentos químicos usando espectroscopia de fotoelétrons de raio-x (XPS) de alta resolução com síncrotron. Em paralelo, também usamos o microscópio de varredura por tunelamento (STM) para acompanhar a formação e intercalação das estruturas na superfície durante os ciclos de evaporação do ferro. Os resultados mostraram que, com o substrato à temperatura ambiente, o Fe interage fortemente com o grafeno e ocorre intercalação parcial. No caso de evaporação à temperaturas moderadas, houve intercalação total do Fe que permaneceu protegido pela folha de grafeno, indicando ser possível crescer um filme fino intercalado na superfície / Abstract: Graphene is a 2D carbon allotrope having sp2 hybridized atoms in a single-layer. Its remarkable electronic and structural properties attract an enormous scientific and technological interest to the material in the last decade. Graphene can be grown on certain transition metals by the well-known Chemical Vapor Deposition (CVD) technique. The stability of graphene in these substrates is guaranteed, but the chemical interactions between them modify its exotic electronic and structural properties. It is possible to grow graphene on the Ir(111) surface without substantial structural defects and withsingle domain, whenspecific conditions of substrate temperature and pressure of the precursor gas (propylene) are applied. While trying to retrieve the characteristic properties, the scientific community has been trying to isolate graphene from the metallic substrate, either physically or electrically, by intercalation of various species such as gases, metals or nanoparticles. By performing such procedures, it is possible, besides the desired suspension of the material, to induce changes such as gap opening and doping of the electronic band structures. In this context, the aim of this work is to study the dynamics of iron growth and intercalation in Gr/Ir(111), following the thermodynamic parameters involved and observing mainly the chemical shifts using high resolution x-ray photoelectron spectroscopy (XPS). In parallel, we also used the scanning tunneling microscope (STM) to follow the formation of Fe surface structures during the evaporation cycles and intercalation. The results show that at room temperature, Fe interacts strongly with graphene with partial intercalation. In the case of evaporation at moderate temperatures, there was full intercalation of Fe which remained protected by the graphene sheet / Mestrado / Física / Mestre em Física / 1423605/2014 / CAPES

No description available.

The characterization of work functions and field emission stability for molybdenum and iridium oxide coatings was examined. Single emission tips and flat samples of molybdenum and iridium oxide were prepared for characterization. The flat samples were characterized using X-ray Photoelectron Spectroscopy and X-ray diffraction to determine elemental composition, chemical shift, and crystal structure. Flat coatings of iridium oxide were also scanned by Atomic Force Microscopy to examine topography. Work functions were characterized by Ultraviolet Photoelectron Spectroscopy from the flat samples and by Field Emission Electron Distributions from the field emission tips. Field emission characterization was conducted in a custom build analytical chamber capable of measuring Field Emission Electron Distribution and Fowler-Nordheim I-V plots simultaneously to independently evaluate geometric and work function changes. Scanning Electron Microscope pictures were taken of the emission tips before and after field emission characterization to confirm geometric changes. Measurement of emission stability and work functions were the emphasis of this research. In addition, use of iridium oxide coatings to enhance emission stability was evaluated. Molybdenum and iridium oxide, IrO2, were characterized and found to have a work function of 4.6 eV and 4.2 eV by both characterization techniques, with the molybdenum value in agreement with previous research. The analytic chamber used in the field emission analysis demonstrated the ability to independently determine the value and changes in work function and emitter geometry by simultaneous measurement of the Field Emission Energy Distribution and Fowler-Nordheim I-V plots from single emitters. Iridium oxide coating was found to enhance the stability of molybdenum emission tips with a relatively low work function of 4.2 eV and inhibited the formation of high work function molybdenum oxides. However, the method of deposition of iridium and annealing in oxygen to form iridium oxide on molybdenum emitters left rather severe cracking in the protective oxide coating exposing the molybdenum substrate.

Classical methods of analyzing heat capacity data for the characteristic moments of the frequency distribution are applied to iridium and rhodium. Impurity moments are determined from high and low temperature f values. These moments are combined by modern theory to estimate the magnitude of the host-host to host-impurity force constant ratio. Ratios of the various host moments are also examined.