Yes / Developing new methods to control the size and shape of the helical structures adopted by foldamers is highly important as the secondary structure displayed by these supramolecular scaffolds often dictates their activity and function. Herein, we report on a systematic study demonstrating that the helical pitch of ortho‐azobenzene/2,6‐pyridyldicarboxamide foldamers can be readily controlled through the nature of the terminal functionality. Remarkably, simply through varying the end group of the foldamer, and without modifying any other structural features of the scaffold, the helical pitch can be over doubled in magnitude (from 3.4 Å–7.3 Å). Additionally, crystallographic analysis of a library ten foldamers has identified general trends in the influence of a range of terminal functionalities, including carboxylbenzyl (Cbz), diphenylcarbamyl (N(Ph)2), ferrocene (Fc) and tert‐butyloxycarbonyl (Boc), in controlling the folding behaviour of these supramolecular scaffolds. These studies could prove useful in the future development of functional foldamers which adopt specific sizes and shapes. A crystallographic study into the influence of varying the terminal functionality on the helical pitch of a series of foldamers is reported. Herein, we show that through systematic modification of the terminal functionality in the foldamer, from carboxylbenzyl (Cbz), diphenylamide (N(Ph)2), ferrocene to tert‐butyloxycarbonyl (Boc) helical pitches between 3.4–7.3 Å can be readily accessed in these supramolecular scaffolds. / Royal Society of Chemistry. Grant Number: RF19-4013. Leverhulme Trust. Grant Number: RPG-2022-118. Royal Society. Grant Number: RGS/R1/231242. Engineering and Physical Sciences Research Council. Grant Number: MR/S035486/2

Das Ziel dieser Arbeit war die Synthese neuer heterocyclischer Hydroxyl-funktionalisierter Tekton-Moleküle, die über ein sperriges Grundgerüst verfügen und zur Bildung von porösen organischen Netzwerken sowie Koordinationspolymeren befähigt sind. Um die Sperrigkeit der Zielverbindungen und die Koordinationsfähigkeit bezüglich Metallionen zu gewährleisten, wurden durch Anknüpfung der Heterocyclen Pyridin, Thiophen und Benzo[b]thiophen an Spacer-Elemente, bestehend aus Benzen- und Alkin-Einheiten, entsprechende Derivate hergestellt und umfassend charakterisiert. Die synthetisierten Moleküle liefern eine Vielzahl von Einschlussverbindungen mit Neutralmolekülen, die hinsichtlich ihrer Zusammensetzung, Stabilität sowie Struktur untersucht wurden. Weiterhin konnte das Potenzial der Zielverbindungen als Sensormaterial gegenüber Neutralmolekülen in der Gasphase und unter Ausnutzung der Fluoreszenzeigenschaften gegenüber Metallionen in Lösung betrachtet sowie die Eignung als Linker-Moleküle zum Aufbau von Koordinationspolymeren überprüft werden.

Submitted by Maria Dulce (mdulce@ndc.uff.br) on 2014-01-27T19:31:47Z No. of bitstreams: 1 Carvalho, Joao-Tese-2013.pdf: 1807693 bytes, checksum: 4d03f3ed4930a476f7b2035610bd270c (MD5) / Made available in DSpace on 2014-01-27T19:31:47Z (GMT). No. of bitstreams: 1 Carvalho, Joao-Tese-2013.pdf: 1807693 bytes, checksum: 4d03f3ed4930a476f7b2035610bd270c (MD5) Previous issue date: 2013 / O objetivo central da tese parte de uma leitura crítica das intepretações historiográficas mais tradicionais sobre a Baixa Idade Média portuguesa, em especial àquelas inscritas no período compreendido entre a regência do Infante D. Pedro até o fim do reinado de D. Afonso V (1438-1481), ao qual muitas vezes se atribui o adjetivo de neosenhorial, pivô de retrocessos na geração histórica do Portugal Moderno. Dessa forma, formulam-se análises que veem a estruturação estatal baixo-medieval lusitana como difusora e reprodutora de mecanismos de dominação nobiliárquica e de exploração feudal, por meio da teorização e prática de um projeto político ligado à ascensão da dinastia de Avis, apelidado projeto avisino. Longe de uma centralização despótica por parte da Coroa, proponho uma interpretação na qual a instituição monárquica ocupava papel central, sem com isso significar uma subversão do sistema social enraizado no senhorialismo perpetuado em toda Cristandade Ocidental. Buscando o afastamento de perspectivas estadualistas, anacrônicas em sua execução, opto pela identificação e pela compreensão das condições materiais de produção e de reprodução do poder e dos instrumentos de exploração. Levando, assim, em consideração a realidade social na qual tais relações se estabeleceram e ordenaram, assim como as condições conjunturais às quais precisaram se adaptar e agir no Portugal avisino do século XV. / This thesis main goal comes from a critical reading the most traditional historiographical interpretations on the Portuguese Late Middle Ages, especially the ones enrolled in the time period between the Infante D. Pedro’s regency and D. Afonso V’s reign (1438-1481), upon which is often given the adjective neoseigniorial, the setback pivot on the historical generation of the Modern Portugal. Thereby, analyzes in which the late medieval Portuguese state structure is seem as the diffuser and reproducer of nobiliary domination mechanisms and feudal exploration are formulated, through the theorization and practice of a political project bonded to the Avis dynasty ascension, surnamed projeto avisino. Far from a despotic centralization by the Crown, I propose an interpretation, in wich the monarchical institution occupied a central role, but didn’t subverted that social system, rooted on seigniorial practices spread all over the western Christendom. Searching deviation from estadualistas outlooks, anachronistic in its execution, I choose identifying and comprehending the material conditions by which the power and the exploration tools were produced and reproduced. Therefore considering the social reality in which such relations were established and arranged as well as the contextual conditions to which they needed to adapt and act through in the Fifteenth century Portugal.

Das Ziel dieser Arbeit war die Synthese neuer heterocyclischer Hydroxyl-funktionalisierter Tekton-Moleküle, die über ein sperriges Grundgerüst verfügen und zur Bildung von porösen organischen Netzwerken sowie Koordinationspolymeren befähigt sind. Um die Sperrigkeit der Zielverbindungen und die Koordinationsfähigkeit bezüglich Metallionen zu gewährleisten, wurden durch Anknüpfung der Heterocyclen Pyridin, Thiophen und Benzo[b]thiophen an Spacer-Elemente, bestehend aus Benzen- und Alkin-Einheiten, entsprechende Derivate hergestellt und umfassend charakterisiert. Die synthetisierten Moleküle liefern eine Vielzahl von Einschlussverbindungen mit Neutralmolekülen, die hinsichtlich ihrer Zusammensetzung, Stabilität sowie Struktur untersucht wurden. Weiterhin konnte das Potenzial der Zielverbindungen als Sensormaterial gegenüber Neutralmolekülen in der Gasphase und unter Ausnutzung der Fluoreszenzeigenschaften gegenüber Metallionen in Lösung betrachtet sowie die Eignung als Linker-Moleküle zum Aufbau von Koordinationspolymeren überprüft werden.

The thesis offers new paradigms for advancing socio-economic rights in Africa. Many States Parties to human rights instruments have failed to promote the common welfare of their citizens partly because of the justiciability debate, which continues to complicate intellectual and practical efforts at advancing socio-economic rights. The debate also prevents the normative development of these rights through adjudication. Furthermore, traditional human rights theory and practice have been state-centric, with non-state actors largely ignored in the identification, formulation, and implementation of human rights norms. Yet, the involvement of non-state entities in international arena has limited states' autonomies considerably, with serious implications for human rights. Transnational Corporations (TNCs) have capacities to foster economic well-being, development, tenchnological improvement, and wealth, but they also often cause deleterious human rights impacts through thei employment practices, environmental policies, relationships with suppliers and consumers, interactions with governments, and other activities. The thesis argues that socio-economic rights are normative and justiciable. It argues that traditional approaches are no longer sufficient to secure human rights and calls for a dismantatling of some structures erected by doctrinal systems; for realignment of relationships among social institutions; and for integrated bundles of fundamental interests that harness benefits of human rights norms and widen the landscape to commit both formal and informal regimes. Fashioning out a new paradigm for advancement of socio-economic rights requires addressing state capacity. It requires an integrative and global interpretive framework. It requires, finally, a new paradigm to commit non-state actors in Africa. The illustrative chapter uses the rights to work and to social security as templates for some prescriptions towards reaslising socio-economic rights in Africa. / Jurisprudence / LL.D.

The thesis offers new paradigms for advancing socio-economic rights in Africa. Many States Parties to human rights instruments have failed to promote the common welfare of their citizens partly because of the justiciability debate, which continues to complicate intellectual and practical efforts at advancing socio-economic rights. The debate also prevents the normative development of these rights through adjudication. Furthermore, traditional human rights theory and practice have been state-centric, with non-state actors largely ignored in the identification, formulation, and implementation of human rights norms. Yet, the involvement of non-state entities in international arena has limited states' autonomies considerably, with serious implications for human rights. Transnational Corporations (TNCs) have capacities to foster economic well-being, development, tenchnological improvement, and wealth, but they also often cause deleterious human rights impacts through thei employment practices, environmental policies, relationships with suppliers and consumers, interactions with governments, and other activities. The thesis argues that socio-economic rights are normative and justiciable. It argues that traditional approaches are no longer sufficient to secure human rights and calls for a dismantatling of some structures erected by doctrinal systems; for realignment of relationships among social institutions; and for integrated bundles of fundamental interests that harness benefits of human rights norms and widen the landscape to commit both formal and informal regimes. Fashioning out a new paradigm for advancement of socio-economic rights requires addressing state capacity. It requires an integrative and global interpretive framework. It requires, finally, a new paradigm to commit non-state actors in Africa. The illustrative chapter uses the rights to work and to social security as templates for some prescriptions towards reaslising socio-economic rights in Africa. / Jurisprudence / LL.D.

Platinum(II) complexes [(NHC)Pt(L)] with various β-diketonate based auxiliary ligands (L: 3-meacac = 3-methylacetylacetonato, dpm = dipivaloylmethanato, dbm = dibenzoylmethanato, mesacac = dimesitoylmethanato, duratron = bis(2,3,5,6-tetramethylbenzoyl)methanato) and a C^C* cyclometalated N-heterocyclic carbene ligand (NHC: dpbic = 1,3-iphenylbenzo[d]imidazol-2-ylidene, dpnac = 1,3-diphenylnaphtho[2,3-d]imidazol-2-ylidene or bnbic = 1-phenyl-3-benzylbenzo[d]imidazol-2-ylidene) were found to show different aggregation and photophysical properties depending on the auxiliary ligand. Eight complexes were prepared from a silver(I)–NHC intermediate by transmetalation, cyclometalation and subsequent treatment with potassium-tert-butanolate and β-diketone. They were fully characterized by standard techniques including ¹⁹⁵Pt NMR. Five complexes were additionally characterized by 2D NMR spectroscopy (COSY, HSQC, HMBC and NOESY). Solid-state structures of five complexes could be obtained and show the tendency of the square-planar compounds to form pairs with different Pt–Pt distances depending on the bulkiness of the substituents at the auxiliary ligand. The result of the photophysical measurements in amorphous PMMA films reveals quantum yields of up to 85% with an emission maximum in the blue region and comparatively short decay lifetimes (3.6 µs). Density functional theory (DFT/TD-DFT) calculations were performed to elucidate the emission process and revealed a predominant ³ILCT/³MLCT character. Organic light-emitting devices (OLEDs) comprising one of the complexes achieved 12.6% EQE, 11.9 lm W⁻¹ luminous efficacy and 25.2 cd A⁻¹ current efficiency with a blue emission maximum at 300 cd m⁻². The influence of an additional hole-transporter in the emissive layer was investigated and found to improve the device lifetime by a factor of seven.