Valorização de resíduos industriais na formulação de produtos e pigmentos cerâmicos: processamento e desenvolvimento de cor

A valorização de diferentes resíduos industriais provenientes dosector de tratamento/revestimento de superfícies metálicas pode ser obtida utilizando-os como matérias-primas na formulação de pigmentos cerâmicos, sintetizados pelo método cerâmico convencional. Neste trabalho avaliou-se a viabilidade de incorporar lamas geradas pelos processos de (i) anodização, ricas em alumínio, (ii) de niquelagem e cromagem de torneiras, usadas como fonte de níquel e crómio, e (iii) da decapagem química de aços de uma trefilaria, ricas em ferro, utilizadas por si só, ou em conjunto com matérias-primas comerciais, para a obtenção depigmentos cerâmicos que coram, de forma estável, diversas matrizes cerâmicas e vítreas. Esta solução assegura ainda a inertização de potenciaisespécies perigosas presentes nos resíduos, resultando produtos inócuospara a saúde pública. Procedeu-se à caracterização de cada resíduo, em termos de composição química e mineralógica, comportamento térmico, grau de toxicidade, distribuição granulométrica, teor de humidade, etc. Verificou-se a constância das características das lamas, recorrendo à análise de lotes recolhidos em momentos distintos. Os resíduos são essencialmente constituídos por hidróxidos metálicos e foram utilizados após secagem e desagregação. No entanto, a lama de anodização de alumínio sofreu um tratamento térmico suplementar a 1400ºC. O método de síntese dos pigmentos englobou as seguintes etapas: (i) doseamento; (ii) homogeneização; (iii) calcinação; (iv) lavagem e moagem.Procedeu-se à caracterização dos pigmentos, avaliando a cor por espectroscopia de reflectância difusae pelo método CIELAB e determinando as características físico-químicas relevantes. Posteriormente, testou-se o seu desempenho em produtos cerâmicos distintos (corpos e vidrados), aferindo o desempenho cromático e a estabilidade. Numa primeira fase, desenvolveram-se e caracterizaram-se tipos distintos de pigmentos: (i) com base na estrutura do corundo (ii) verde Victória deuvarovite (iii) violeta de cassiterite com crómio (iv) pigmento carmim de malaiaíte; (v)pretos e castanhos com base na estrutura da espinela. Aprofundaram-se depois os estudos do pigmento carmim de malaiaítee do pigmento preto com base na estrutura da espinela. O pigmento carmim de malaiaíte, CaSnSiO5:Cr2O3, é formulado coma lama gerada no processo de niquelagem e cromagem. Avaliou-se a influência do teor de lama na temperatura de síntese e na qualidade cromática, em comparação com um pigmento formulado com reagentes puros. O pigmento preto com estrutura de espinela de níquel, crómio e ferro, foii formulado exclusivamente a partir das lamas geradas nos processos de cromagem/niquelagem e de decapagem química do aço. Avaliaram-se as características cromáticas e o grau de inertização dos elementos tóxicospresentes, em função da estequiometria e do tratamento térmico. Estudou-se ainda um novo sistema com base na estrutura da hibonite(CaAl12O19), que permite a obtenção de pigmentos azuis e que utiliza a lama de cromagem e niquelagem. As espécies cromóforas (Ni2+ ou Co2+) assumem coordenação tetraédrica quando substituem os iões Al3+ que ocupam as posições M5 da rede da hibonite. A formação simultânea de anortite permite reduzir a temperatura de síntese.Para além do carácter inovador deste pigmento de dissolução sólida, a qualidade cromática e a sua estabilidade são interessantes. Além disso, os teores de cobalto ou níquel são reduzidosrelativamente aos utilizados em formulações comerciais de pigmentos azuis, o que se traduz em importantes vantagens económicas e ambientais.

Magnetic impurities in nanostructured materials

Os resultados apresentados aqui foram alcançados no âmbito do programa de doutoramento intitulado “Impurezas Magnéticas em Materiais Nanoestruturados”. O objectivo do estudo foi a síntese e caracterização de óxido contendo impurezas magnéticas. Durante este trabalho, sínteses de sol-gel não-aquoso têm sido desenvolvidos para a síntese de óxidos dopados com metais de transição (ZnO e ZrO2). A dopagem uniforme é particularmente importante no estudo de semicondutores magnéticos diluídos (DMSs) e o ponto principal deste estudo foi verificar o estado de oxidação e a estrutura local do dopante e para excluir a existência de uma fase secundária como a origem do ferromagnetismo. Para alargar o âmbito da investigação e explorar plenamente o conceito de "impurezas magnéticas em materiais nanoestruturados" estudamos as propriedades de nanopartículas magnéticas dispersas em uma matriz de óxido. As nanopartículas (ferrita de cobalto) foram depositadas como um filme e cobertas com um óxido metálico semicondutor ou dielétrico (ZnO, TiO2). Estes hetero-sistemas podem ser considerados como a dispersão de impurezas magnéticas em um óxido. As caracterizações exigidas por estes nanomateriais têm sido conduzidas na Universidade de Aveiro e Universidade de Montpellier, devido ao equipamento complementar.

Estudo da maquinabilidade das ligas Ti-6Al-4V e Co-28Cr-6Mo na fresagem de dispositivos biomédicos

Os estudos de maquinabilidade de biomateriais e outros materiais aplicados na área médica são extensos. Todavia, muitos destes estudos recorrem a modelos de geometria regular e operações elementares de maquinagem. Relativamente a estas, os estudos académicos atualmente disponíveis mostram que a tecnologia preferencial é o torneamento, opção que se fundamenta na simplicidade de análise (corte ortogonal). Saliente-se ainda que, neste contexto, a liga de titânio Ti-6Al-4V constitui o biomaterial mais utilizado. Numa perspetiva complementar, refira-se que as publicações científicas evidenciam que a informação disponível sobre a fresagem Ti-6Al-4V não é muito extensa e a do Co-28Cr-6Mo é quase inexistente. A presente dissertação enquadra-se neste domínio e representa mais uma contribuição para o estudo da maquinabilidade das ligas de Titânio e de crómio-cobalto. A aplicação de operações de maquinagem complexas, através do recurso a programas informáticos de fabrico assistido por computador (CAM), em geometrias complexas, como é o caso das próteses femorais anatómicas, e o estudo comparativo da maquinabilidade das ligas Co-28Cr-6Mo e Ti-6Al-4V, constituem os objetivos fundamentais deste trabalho de doutoramento. Neste trabalho aborda-se a problemática da maquinabilidade das ligas metálicas usadas nos implantes ortopédicos, nomeadamente as ligas de titânio, de crómiocobalto e os aços Inoxidáveis. Efetua-se ainda um estudo da maquinagem de uma prótese femoral com uma forma geométrica complexa, onde as operações de corte foram geradas recorrendo às tecnologias de fabrico assistido por computador (CAD/CAM). Posteriormente, procedeu-se ao estudo da maquinabilidade das duas ligas usadas neste trabalho, dando uma atenção particular à determinação das forças de corte para diferentes velocidades de corte. Para além da monitorização da evolução da força de corte, o desgaste das ferramentas, a dureza e a rugosidade foram avaliadas, em função da velocidade de corte imposta. Por fim, com base nas estratégias de maquinagem adotadas, analisa-se a maquinabilidade e selecionam-se os parâmetros de corte mais favoráveis para as ligas de Titânio e Crómio-cobalto. Os resultados obtidos mostram que a liga de crómio-cobalto induz maior valor de força de corte do que a liga de titânio. Observa-se um aumento progressivo das forças de corte quando a velocidade de corte aumenta, até atingir o valor máximo para a velocidade de corte de 80m/min, após a qual, a força de corte tende a diminuir. Apesar do fabricante das ferramentas recomendar a velocidade de corte de 50 m/min para ambos os materiais, conclui-se que a velocidade de corte de 65 m/min induz o mesmo desgaste na ferramenta de corte no caso da liga de titânio, e menor desgaste no caso da liga de crómio-cobalto.

Assessment of the mineralogenic toxicity of aquatic pollutants

In ecotoxicology a major focus is in the aquatic environment, not only because it presents a great economic value to man but it is an ecosystem widely affected by the growing anthropogenic pollution. Most of the studies performed relate to adverse effects in development, reproductive or endocrine disruption but little is known about the possible effects in bone formation and skeletal development. In this study, we set out to evaluate the effects of 8 aquatic pollutants on the skeletal development using an in vivo system, the zebrafish larvae aged 20 days post-fertilization, through chronic exposure. Several endpoints were considered such as the cumulative mortality, total length, occurrence of skeletal deformities and marker gene expression. We were able to establish LD50 values for some pollutants, like 3-methylcholanthrene, lindane, diclofenac, cobalt and vanadate and found that the total length was not affected by any of the pollutants tested. Cobalt was the most harmful chemical to affect hatching time, severely affecting the ability of the zebrafish embryos to hatch and overall the number of deformities increased upon exposure to tested chemicals but no patterns of deformities were identified. We also propose that 3-methylcholanthrene has an osteogenic effect, affecting osteoblast and osteoclast function and that op levels can act as a mediator of 3-methylcholanthrene toxic stress to the osteoblast. In turn we found naphthalene to probably have a chondrogenic effect. Our results provided new insights into the potential osteotoxicity of environmental pollutants. Future studies should aim at confirming these preliminary data and at determining mechanisms of osteotoxicity.

Partial volume correction using bimodal contrast agents in PET-MRI

Tese de mestrado integrado em Engenharia Biomédica e Biofísica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2014

Carcinoembryonic antigen (CEA) in non digestive cancerous and normal tissues.

Carcinoembryonic antigen (CEA), immunologically identical to CEA derived from colonic carcinoma, was identified and purified from perchloric acid (PCA) extracts of bronchial and mammary carcinoma. CEA extracted from bronchial and mammary carcinoma was quantitated by single radial immunodiffusion and was found to be in average about 50-75 times less abundant in these tumors than in colonic carcinoma. CEA could also be detected in one normal breast in lactation and at lower concentrations in normal lung (1000-4000 times lower than in colonic carcinoma). The small amounts of CEA present in normal tissues are distinct from the glycoprotein of small mol. wt showing only partial identity with CEA, that we recently identified and extracted in much larger quantities from normal lung and spleen. The demonstration of the presence of CEA in non digestive carcinoma by classical gel precipitation analysis suggests that the CEA detected in the plasma of such patients by radioimmunoassay is also identical to colonic carcinoma CEA. Our comparative study of plasma CEA from bronchial and colonic carcinoma, showing that CEA from both types of patient has the same elution pattern on Sephadex G-200 and gives parallel inhibition curves in the radioimmunoassay, is in favor of this hypothesis. However, it should not be concluded that all positive CEA radioimmunoassay indicate the presence of an antigen identical to colonic carcinoma CEA. A word of warning concerning the interpretation of radioimmunoassay is required by the observation that the addition of mg amounts of PCA extract of normal plasma, cleared of CEA by Sephadex filtration, could interfere in the test and mimic the presence of CEA.

Predicting hematologic toxicity in patients undergoing radioimmunotherapy with 90Y-ibritumomab tiuxetan or 131I-tositumomab.

This study aimed at identifying clinical factors for predicting hematologic toxicity after radioimmunotherapy with (90)Y-ibritumomab tiuxetan or (131)I-tositumomab in clinical practice. Hematologic data were available from 14 non-Hodgkin lymphoma patients treated with (90)Y-ibritumomab tiuxetan and 18 who received (131)I-tositumomab. The percentage baseline at nadir and 4 wk post nadir and the time to nadir were selected as the toxicity indicators for both platelets and neutrophils. Multiple linear regression analysis was performed to identify significant predictors (P < 0.05) of each indicator. For both platelets and neutrophils, pooled and separate analyses of (90)Y-ibritumomab tiuxetan and (131)I-tositumomab data yielded the time elapsed since the last chemotherapy as the only significant predictor of the percentage baseline at nadir. The extent of bone marrow involvement was not a significant factor in this study, possibly because of the short time elapsed since the last chemotherapy of the 7 patients with bone marrow involvement. Because both treatments were designed to deliver a comparable bone marrow dose, this factor also was not significant. None of the 14 factors considered was predictive of the time to nadir. The R(2) value for the model predicting percentage baseline at nadir was 0.60 for platelets and 0.40 for neutrophils. This model predicted the platelet and neutrophil toxicity grade to within ±1 for 28 and 30 of the 32 patients, respectively. For the 7 patients predicted with grade I thrombocytopenia, 6 of whom had actual grade I-II, dosing might be increased to improve treatment efficacy. The elapsed time since the last chemotherapy can be used to predict hematologic toxicity and customize the current dosing method in radioimmunotherapy.

Postglacial paleoecology and effects of European settlement on the environment of Lake Hunger and Lake Lisgar, Southwestern Ontario /

This investigation has three purposes I to make a comparative chemical study on sediment cores collected for Lake Lisgar (man-made lake in an urban center) and Lake Hunger (natural basin in a rural community) encompassing the time since European settlement I to determine the postglacial chemical history of Lake Hunger, and to determine the vegetational history of the Lake Hunger area from postglacial time to the present. The minus 80 mesh fraction of 108 soil samples and 18 stream sediment samples collected in the vicinity of Lakes' Lisgar and Hunger were analyzed for cold hydrochloric acid soluble lead, zinc, nickel, cobalt, copper, aluminum, sodium, potassium, calcium, magnesium, iron and manganese. Lacustrine sediments from 5 boreholes in the Lake Lisgar basin were collected. Boreholes 1, 2, 3, and 4 were analyzed for palynological and chemical information and Borehole 5 was subjected to pollen and ostracode analysis. Lacustrine sediments from 6 boreholes in the Lake Hunger basin were collected. Palyno- -logical and chemical analysis were performed on Boreholes 1, 2, 3, 4, and 6 and Borehole 5 was analyzed for pollen. In addition, radiocarbon dates were obtained on sediment samples from Boreholes 4 and 5. A total of 8 surface samples were collected from the margins of the Lake Hunger basin and these were chemically analyzed in the laboratory. All of the lacustrine sediments were ashed and analyzed for cold hydrochloric acid soluble lead, zinc, nickel, cobalt, copper, aluminum, sodium, potassium, calcium, magnesium, iron and manganese using a Perkin Elmer 40) Atomic Absorption spectrophotometer. The results . obtained for the 12 elements were expressed as parts per million in dry sediments. It was found that man's influence on the element distribution patterns in the sediments of Lake Lisgar appeared to be related to his urbanizing developments within the lake vicinity, whereas, the rural developments in the vicinity of lake Hunger appeared to have had little effect on the element distribution patterns in the lake sediments. The distribution patterns of lead, zinc, nickel, cobalt, aluminum, magnesium, sodium and potassium are similar to the % ash curve throughout postglacial time indicating that the rate of erosion in the drainage basin is the main factor which controls the concentration of these elements in the sediments of Lake Hunger. The vegetational history, from palynological analysis, of Lake Hunger from postglacial time to the present includes the following stages: tundra, open spruce forest, closed boreal forest, deciduous forest and the trend towards the re-establishment of pine following the clearing of land and the subsequent settlement of the Lake Hunger area by European settlers. The concentrations of some elements (cobalt, nickel, iron, manganese, calcium, magnesium, sodium and potassium) in the sediments of Lake Hunger appears to be higher during pre-cultural compared to post-cultural times. At least one complete postglacial record of the chemical history within a lake basin is necessary in order to accurately assess man's effects on his environment.

Properties of NaxCoO2 /

Polycrysttdline samples of NaiCoOa were prepared using the "Rapid heat-up" method. One set of samples was annealed in flowing O2, while the other set in flowing Argon. X-Ray diffraction measurements indicated a stable phase of Nao.7Co02 mixed with C03O4 for all the samples even though they differed in concentration of Na. Argon annealed samples were insulators, whereas the ones annealed in O2 were metallic. Most of the measurements were performed on the sample Nao.7Co02, because it is the host compound for the superconductor sample Nao.35Co02-H20. Magnetization measurement showed that the magnetic moment decreased with increasing sodium concentration. This is due to the existence of C03O4 in samples with Na^ 0.7. As sodium concentration decreases, the magnetic moment increases due to the increasing concentration of C03O4 and its large magnetic moment. Magnetization measurements showed that the magnetic moment of Nao.7Co02 is field-dependent in low fields eind field-independent in fields higher than 100 G. Resistivity changes with temperature (dp/dT) increased with increasing Na concentration. Also resistivity measurements were performed under different hydrostatic pressures on Nao.7Co02. Two transitions were observed; one at a temperature Ti ~20 K and the other at T2 ^280 K, the transition at Ti has a magnetic origin and the one at T2 is a structiural transition. It was noticed that pressure aJfects resistivity of the sample. At higher pressures resistivity changes faster with temperature. Magnetoresistance measurement showed a small change in the resistivity, especially at lower temperatures. A novel layered superconductor Nao.35Co02H20 was prepared using de-intercalation of Na from the host compound Nao.7Co02. FVom the temperature dependence of the magnetization, the superconducting transition temperature and lower critictil field have been estimated as Tc=4.12 K and Hci=66 G, respectively.

Sample preparation and heavy metal determination by atomic spectrometry /

Microwave digestions of mercury in Standards Reference Material (SRM) coal samples with nitric acid and hydrogen peroxide in quartz vessels were compared with Teflon® vessel digestion by using flow injection cold vapor atomic absorption spectrometry. Teflon® vessels gave poor reproducibiUty and tended to deliver high values, while the digestion results from quartz vessel show good agreement with certificate values and better standard deviations. Trace level elements (Ag, Ba, Cd, Cr, Co, Cu, Fe, Mg, Mn, Mo, Pb, Sn, Ti, V and Zn) in used oil and residual oil samples were determined by inductively coupled plasma-optical emission spectrometry. Different microwave digestion programs were developed for each sample and most of the results are in good agreement with certified values. The disagreement with values for Ag was due to the precipitation of Ag in sample; while Sn, V and Zn values had good recoveries from the spike test, which suggests that these certified values might need to be reconsidered. Gold, silver, copper, cadmium, cobalt, nickel and zinc were determined by continuous hydride generation inductively coupled plasma-optical emission spectrometry. The performance of two sample introduction systems: MSIS™ and gas-liquid separator were compared. Under the respective optimum conditions, MSIS^"^ showed better sensitivity and lower detection limits for Ag, Cd, Cu, Co and similar values for Au, Ni and Zn to those for the gas-liquid separator.

Arsenic and germanium determination by hydride generation in the D.C. plasma optical emission spectrometer

Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).

Investigation into the determination of arsenic by direct current plasma atomic emission spectrometer

Improvements have been made on the currently available hydride generator system manufactured by SpectraMetrics Incorporated, because the system was found to be unsatisfactory with respect to the following: 1. the drying agent, anhydrous calcium chloride, 2. the special sample tube, 3. the direction of argon flow through the Buchner funnel when it came to dealing with real sample, that is, with reference only to aqueous extracts of soil samples. Changes that were made on the system included the replacement of anhydrous calcium chloride with anhydrous calcium sulphate and the replacement of the special sample tube with a modified one made from silica. Re-directing the flow of argon through the top of the Buchner funnel appeared to make the system compatible with aqueous extracts of soil samples. The interferences from 1000 ~g/mL of nickel(II) , cobalt(II), iron(III), copper(II) have been eliminated with the aid of 1.4 M hydrochloric acid and 1% (weight/volume) L-cystine. Greater than 90% recovery of 0.3 ~g/mL arsenic signal was achieved in each case. Furthermore, 103% of arsenic signal was accomplished in the presence of 1000 ~g/mL cadmium with 5 M Hel. tVhen each of the interferents was present in solution at 1000 ppm, a recovery of 85% was achieved by using 5 M hydrochloric acid and 3% (weight/volume) L-cystine. Without L-cystine and when 1.4 M hydrochloric acid was used, the recoveries were 0% (Ni), 0% (Co), 88% (Fe), 15% (Cu), 18% (Cd). Similarly, a solution containing 1000 ppm of each interferent gave a zero percent recovery of arsenic. The reduction of trivalent and pentavalent arsenic at a pH less than one has also been investigated and shown to be quantitative if peak areas are measured. The reproducibility determination of a 0.3 Vg/mL standard arsenic solution by hydride generation shows a relative standard deviation of 3.4%. The detection limits with and without Porapak Q have been found to be 0.6 ng/mL and 1.0 ng/mL, respectively.

Landscape geochemical investigations in the vicinity of a lead deposit near Snertingdal, southern Norway

Landscape geochemical investigations were conducted upon portions of a natural uniform landscape in southern Norway. This consisted of sampling both soil profile samples and spruce tree twigs for the analysis of twelve chemical elements. These elements were cobalt, copper, nickel, lead, zinc, manganese, magnesium, iron, calcium, sodium, potassium and aluminum which were determined by atomic absorption analysis on standardized extraction techniques for both organic and inorganic materials. Two "landscape traverses" were chosen for a comparative study of the effects of varying landscape parameters upon the trace element distribution patterns throughout the landscape traverses. The object of this study was to test this method of investigation and the concept of an ideal uniform landscape under Norwegian conditions. A "control traverse" was established to represent uniform landscape conditions typical of the study area and was used to determine "normal" or average trace element distribution patterns. A "signal traverse" was selected nearby over an area of lead mineralization where the depth to bedrock is very small. The signal traverse provided an area of similar landscape conditions to those of the control traverse with significant differences in the bedrock configuration and composition. This study was also to determine the effect of the bedrock mineralization upon the distribution patterns of the twelve chemical elements within the major components of the two landscape traverses (i.e. soil profiles and tree branches). The lead distribution within the soils of the signal traverse showed localized accumulations of lead within the overburden with maximum values occurring within the organic A horizon of soil profile #10. Above average concentrations of lead were common within the signal traverse, however, the other elements studied were not significantly different from those averages determined throughout the soils of the control traverse. The spruce twig samples did not have corresponding accumulations of lead near the soil lead anomaly. This is attributable to the very localized nature of the lead dispersion pattern within the soils. This approach to the study of the geochemistry of a natural landscape was effective in establishing: a) average or "normal" trace element distribution patterns b) local variations in the landscape morphology and c) the effect of unusually high lead concentrations upon the geochemistry of the landscape (i.e. within the soil profiles and tree branches). This type of study provides the basis for further more intensive studies and serves only as a first approximation of the behaviour of elements within a natural landscape.

Spin labile conducting metallopolymers : a new architecture for hybrid multifunctional materials

The synthesis of 3-ethynylthienyl- (2.07), 3-ethynylterthienyl- (2.19) substituted qsal [qsalH = N-(8-quinolyl)salicylaldimine] and 3,3' -diethynyl-2,2' -bithienyl bridging bisqsal (5.06) ligands are described along with the preparation and characterization of eight cationic iron(III) complexes containing these ligands with a selection of counteranions [(2.07) with: SCN- (2.08), PF6- (2.09), and CI04- (2.10); (2.19) with PF6 - (2.20); (5.06) with: cr (5.07), SeN- (5.08), PF6- (5.09), and CI04- (5.10)]. Spin-crossover is observed in the solid state for (2.08) - (2.10) and (5.07) - (5.10), including a ve ry rare S = 5/2 to 3/2 spin-crossover in complex (2.09). The unusal reduction of complex (2.10) produces a high-spin iron(I1) complex (2.12). Six iron(II) complexes that are derived from thienyl analogues of bispicen [bispicen = bis(2-pyridylmethyl)-diamine] [2,5-thienyl substituents = H- (3.11), Phenyl- (3.12), 2- thienyl (3.13) or N-phenyl-2-pyridinalimine ligands [2,5-phenyl substituents = diphenyl (3.23), di(2-thienyl) (3.24), 4-phenyl substituent = 3-thienyl (3.25)] are reported Complexes (3.11), (3.23) and (3.25) display thermal spin-crossover in the solid state and (3.12) remains high-spin at all temperatures. Complex (3.13) rearranges to form an iron(II) complex (3.14) with temperature dependent magnetic properties be s t described as a one-dimensional ferromagnetic chain, with interchain antiferromagnetic interactions and/or ZFS dominant at low temperatures. Magnetic succeptibility and Mossbauer data for complex (3.24) display a temperature dependent mixture of spin isomers. The preparation and characterization of two cobalt(II) complexes containing 3- ethynylthienyl- (4.04) and 3-ethynylterhienyl- (4.06) substituted bipyridine ligands [(4.05): [Co(dbsqh(4.04)]; (4.07): [Co(dbsq)2(4.06)]] [dbsq = 3,5-dbsq=3,5-di-tert-butylI ,2-semiquinonate] are reported. Complexes (4.05) and (4.07) exhibit thermal valence tautomerism in the solid state and in solution. Self assembly of complex (2.10) into polymeric spheres (6.11) afforded the first spincrossover, polydisperse, micro- to nanoscale material of its kind. . Complexes (2.20), (3.24) and (4.07) also form polymers through electrochemical synthesis to produce hybrid metaUopolymer films (6.12), (6.15) and (6.16), respectively. The films have been characterized by EDX, FT-IR and UV-Vis spectroscopy. Variable-temperature magnetic susceptibility measurements demonstrate that spin lability is operative in the polymers and conductivity measurements confirm the electron transport properties. Polymer (6.15) has a persistent oxidized state that shows a significant decrease in electrical resistance.

Ligand Design for Dual Property Single Molecule Magnets

This thesis describes two different approaches for the preparation of polynuclear clusters with interesting structural, magnetic and optical properties. Firstly, exploiting p-tert-butylcalix[4]arene (TBC4) macrocycles together with selected Ln(III) ions for the assembly of emissive single molecule magnets, and secondly the preparation and coordination of a chiral mpmH ligand with selected 3d transition metal ions, working towards the discovery of chiral polynuclear clusters. In Project 1, the coordination chemistry of the TBC4 macrocycle together with Dy(III) and Tb(III) afforded two Ln6[TBC4]2 complexes that have been structurally, magnetically and optically characterized. X-ray diffraction studies reveal that both complexes contain an octahedral core of Ln6 ions capped by two fully deprotonated TBC4 macrocycles. Although the unit cells of the two complexes are very similar, the coordination geometries of their Ln(III) ions are subtly different. Variable temperature ac magnetic susceptibility studies reveal that both complexes display single molecule magnet (SMM) behaviour in zero dc field and the energy barriers and associated pre-exponential factors for each relaxation process have been determined. Low temperature solid state photoluminescence studies reveal that both complexes are emissive; however, the f-f transitions within the Dy6 complex were masked by broad emissions from the TBC4 ligand. In contrast, the Tb(III) complex displayed green emission with the spectrum comprising four sharp bands corresponding to 5D4 → 7FJ transitions (where J = 3, 4, 5 and 6), highlighting that energy transfer from the TBC4 macrocycle to the Tb(III) ion is more effective than to Dy. Examples of zero field Tb(III) SMMs are scarce in the chemical literature and the Tb6[TBC4]2 complex represents the first example of a Tb(III) dual property SMM assembled from a p-tert-butylcalix[4]arene macrocycle with two magnetically derived energy barriers, Ueff of 79 and 63 K. In Project 2, the coordination of both enantiomers of the chiral ligand, α-methyl-2-pyridinemethanol (mpmH) to Ni(II) and Co(II) afforded three polynuclear clusters that have been structurally and magnetically characterized. The first complex, a Ni4 cluster of stoichiometry [Ni4(O2CCMe3)4(mpm)4]·H2O crystallizes in a distorted cubane topology that is well known in Ni(II) cluster chemistry. The final two Co(II) complexes crystallize as a linear mixed valence trimer with stoichiometry [Co3(mpm)6]·(ClO4)2, and a Co4 mixed valence complex [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2], whose structural topology resembles that of a defective double cubane. All three complexes crystallize in chiral space groups and circular dichroism experiments further confirm that the chirality of the ligand has been transferred to the respective coordination complex. Magnetic susceptibility studies reveal that for all three complexes, there are competing ferro- and antiferromagnetic exchange interactions. The [Co(II)¬2Co(III)2(NO3)2(μ-mpm)4(ONO2)2] complex represents the first example of a chiral mixed valence Co4 cluster with a defective double cubane topology.