Thesis--Wisconsin. / Vita. Includes bibliographical references.

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A series of selectively fluorinated tolans of the general formulae C(_6)F(_5)-C=C-C(_6)H(_4)X and C(_6)H(_5)-C=C-C(_6)F(_4)X (where X = I, Br, CI) have been synthesized via homogeneous palladium-catalysed Sonogashira cross-coupling and organolithium chemistry. Several of their crystal structures have been solved from X-ray diffraction data, and their molecular packing is described in terms of arene-perfluoroarene and halogen-halogen interactions. Diffraction-quality crystals of a number of binary arene-perfluoroarene complexes of hexafluorobenzene and octafluoronaphthalene with several mismatched polyaromatic hydrocarbons have been obtained and their crystal structures solved from X-ray diffraction data. All of the structures have been shown to consist of infinite stacks of alternating components. The individual structures are compared and contrasted in detail, and those of the HFB complexes are found to closely resemble those predicted from ab initio DFT calculations, which implies that the interactions are over 90 % electrostatic in nature, in contrast with previous calculations on related complexes. A number of selectively fluorinated 4,4'-bis(phenylethynyl)tolan (BPET) derivatives containing fluorinated and non-fluorinated phenyl rings, have been synthesized from palladium-catalysed Sonogashira cross-coupling of various tolan-based precursors. They are observed to strongly absorb in the UV range 336 - 342nm, which are directly comparable to the absorptions for similarly fluorinated 1,4-bis(phenylethynyl)benzene derivatives which suggests that an effective conjugation length (ECL) of 3-4 repeat units is applicable for these phenylene ethynylene systems. They are observed to fluoresce very strongly in the range 372-410 nm. The diethynylbenzene derivatives 1,4-diethynyltetrafluorobenzene and 1,4- diethynyl-2,5-difluorobenzene have been synthesized from the hydrodesilation of their trimethylsilylated precursors. Their crystal structures have been solved from X-ray diffraction data, and are described in terms of C=C-H F and C=C-H π(C=C) interactions.

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Le premier néolithique de la Méditerranée occidentale est représenté par un ensemble d'expressions culturelles polymorphes qui se sont développées au cours du VIème millénaire AEC et qui sont définies traditionnellement par la présence de céramiques imprimées. En traçant la variabilité morphologique et décorative des productions céramiques, on peut suivre les dynamiques de diffusion du Néolithique selon un modèle de progression arythmique, d’est en ouest, caractérisée par un renouvellement continu des composantes technoculturelles.Dans ce cadre, à partir du début du VIème millénaire AEC, la Ligurie se révèle comme un espace particulièrement représentatif des transformations sociales et culturelles en jeu et constitue donc un domaine privilégié pour la compréhension des mécanismes de diffusion néolithique en Méditerranée nord-occidentale. Cette recherche s’est focalisée sur l'analyse technologique de la production céramique pour décoder les systèmes techno-économiques des groupes néolithiques, à travers une étude structurée sur deux niveaux progressifs et complémentaires, du site à l'échelle régionale.Les récentes fouilles effectuées aux Arene Candide (1997-2012) ont documenté en détail une séquence stratigraphique relative aux premières phases du Néolithique et ont fourni de nouvelles et cohérentes données contextuelles. La lecture technologique de l’assemblage céramique issu de ces recherches a permis de reconstruire le système de production céramique en relation avec l’articulation stratigraphique et chronologique, en mettant en évidence une évolution des comportements techniques et stylistiques au cours du VIème millénaire AEC. On a pu ainsi élaborer un modèle de périodisation, fondé sur des marqueurs techno-stylistiques spécifiques des différents horizons chrono-culturels. Ce modèle a été ensuite appliqué dans le cadre d’une révision systématique des céramiques provenant des sites contemporains, répartis entre la région de Finale et le Val Pennavaira, souvent très peu considérées parce que provenant généralement de contextes jugés peu fiables. Cette approche a permis de clarifier l'attribution chronologique et culturelle de ces séries céramiques, en fournissant des éléments pour une reconstruction diachronique des dynamiques de peuplement, et pour l'organisation et la gestion du territoire au cours du VIème millénaire AEC. Ces résultats ont alimenté le débat sur les interactions culturelles dans le bassin occidental de la Méditerranée. / The early Neolithic of the western Mediterranean is represented by a polymorphic set of cultural expressions, traditionally defined by the presence of impressed wares, that developed during the sixth millennium BCE. By tracing the morphological and decorative variability of these ceramic productions, it was possible to outline a model of arrhythmic progression of the Neolithic package diffusion, from east to west, characterized by a continuous renewal of its techno-cultural components. Within this context, from the beginning of the sixth millennium BCE, Liguria is a particularly representative space of the social and cultural transformations that took place in the western Mediterranean and represents a privileged area for the untangling of the mechanisms of Neolithic diffusion in this area. This research focused on the technological analysis of ceramic production in order to decode the techno-economic systems of the Neolithic groups, through an integrated study, which was structured in two progressive and complementary levels, from infra-site to a regional scale.Recent excavations at the Arene Candide cave (1997-2012) documented in detail a clear stratigraphic sequence related to the early Neolithic phases, providing new and consistent proxy data. The technological analysis of the ceramic assemblage resulting from these researches allowed for the reconstruction of the pottery production system in relation to the stratigraphic and chronological articulation, highlighting an evolution of technical and stylistic behaviours during the sixth millennium BCE. This led to the elaboration of a diachronic model, articulated in different chrono-cultural horizons, each characterized by specific techno-stylistic markers. The systematic revision of the pottery from the contemporary sites of the region, mainly distributed between the Finalese region and Val Pennavaira, and often neglected due to their absent or unreliable contextual documentation, was also implemented. This revision allowed for the clarification of the chronological and cultural attribution of these ceramic sets, providing new elements for a diachronic reconstruction of settlement dynamics, as well as of the organization and management of the territory during the sixth millennium BCE, and finally revealed cultural interactions with the western Mediterranean basin.In general, the results obtained by this study increase, both quantitatively and qualitatively, the data relating to the early Neolithic stages of the region, unlocking the informative potential of a holistic approach to the analysis of the ceramic document, even when applied to remarkably fragmentary materials. These new results contribute to the ongoing debate on the complex phenomenon of the neolithization of the western Mediterranean.

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Thesis advisor: Shih-Yuan Liu / Described herein are two distinct research projects focused on the development of metal-catalyzed late-stage functionalization strategies for 1,2-dihydro-1,2-azaborines separated into three chapters. The first chapter discusses the development, synthesis, and recent contributions to the field of azaborine chemistry. The second chapter details the development of rhodium catalyzed B-H bond activation for the synthesis of a new class of BN-stilbenes as well as the discovery of a novel B-H to B-Cl transformation that is successful both with B-H azaborines as well as other B-H containing compounds. The third chapter pertains to the development of a B-H and B-Cl tolerant C(3) functionalization strategy through the use of Negishi cross-coupling. Using this methodology, previously unreported isomers of BN-naphthalene and BN-indenyl have been synthesized and characterized. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.