Synthesis and Properties of a Series of 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

The work described in this thesis revolves around the 1,1,n,ntetramethyl[n](2,11)teropyrenophanes, which are a series of [n]cyclophanes with a severely bent, board-shaped polynuclear aromatic hydrocarbons (PAH). The thesis is divided into seven Chapters. The first Chapter conatins an overview of the seminal work on [n]cyclophanes of the first two members of the “capped rylene” series of PAHs: benzene and pyrene. Three different general strategies for the synthesis of [n]cyclophanes are discussed and this leads in to a discussion of some slected syntheses of [n]paracyclopahnes and [n](2,7)pyrenophanes. The chemical, structural, spectroscopic and photophysical properties of these benzene and pyrene-derived cyclophanes are discussed with emphasis on the changes that occur with changes in the structure of the aromatic system. Chapter 1 concludes with a brief introduction to [n]cyclophanes of the fourth member of the capped rylene series of PAHs: teropyrene. The focus of the work described in Chapter 2 is the synthesis of of 1,1,n,ntetramethyl[n](2,11)teropyrenophane (n = 6 and 7) using a double-McMurry strategy. While the synthesis 1,1,7,7-tetramethyl[7](2,11)teropyrenophane was successful, the synthesis of the lower homologue 1,1,6,6-tetramethyl[6](2,11)teropyrenophane was not. The conformational behaviour of [n.2]pyrenophanes was also studied by 1H NMR spectroscopy and this provided a conformation-based rationale for the failure of the synthesis of 1,1,6,6-tetramethyl[6](2,11)teropyrenophane. Chapter 3 contains details of the synthesis of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7-9) using a Wurtz / McMurry strategy, which proved to be more general than the double McMurry strategy. The three teropyrenophanes were obtained in ca. 10 milligram quantities. Trends in the spectroscopic properties that accompany changes in the structure of the teropyrene system are discussed. A violation of Kasha’s rule was observed when the teropyrenophanes were irradiated at 260 nm. The work described in the fourth Chapter concentrates on the development of gram-scale syntheses of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) using the Wurtz / McMurry strategy. Several major modifications to the orginal synthetic pathway had to be made to enable the first several steps to be performed comfortably on tens of grams of material. Solubility problems severely limited the amount of material that could be produced at a late stage of the synthetic pathways leading to the evennumbered members of the series (n = 8, 10). Ultimately, only 1,1,9,9- tetramethyl[9](2,11)teropyrenophane was synthesized on a multi-gram scale. In the final step in the synthesis, a valence isomerization / dehydrogenation (VID) reaction, the teropyrenophane was observed to become unstable under the conditions of its formation at n = 8. The synthesis of 1,1,10,10-tetramethyl[10](2,11)teropyrenophane was achieved for the first time, but only on a few hundred milligram scale. In Chapter 5, the results of an investigation of the electrophilic aromatic bromination of the 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) are presented. Being the most abundant cyclophane, most of the work was performed on 1,1,9,9-tetramethyl[9](2,11)teropyrenophane. Reaction of this compound with varying amounts of of bromine revealed that bromination occurs most rapidly at the symmetryrelated 4, 9, 13 and 18 positions (teropyrene numbering) and that the 4,9,13,18- tetrabromide could be formed exclusively. Subsequent bromination occurs selectively on the symmetry-related 6, 7, 15 and 16 positions (teropyrene numbering), but considerably more slowly. Only mixtures of penta-, hexa-, hepta and octabromides could be formed. Bromination reactions of the higher and lower homologues (n = 7, 8 and 10) revealed that the reactivity of the teropyrene system increased with the degree of bend. Crystal structures of some tetra-, hexa-, hepta- and octa-brominated products were obtained. The goal of the work described in Chapter 6 is to use 1,1,9,9- tetramethyl[9](2,11)teropyrenophane as a starting material for the synthesis of warped nanographenophanes. A bromination, Suzuki-Miyaura, cyclodehydrogenation sequence was unsuccessful, as was a C–H arylation / cyclodehydrogenation approach. Itami’s recently-developed K-region-selective annulative -extension (APEX) reaction proved to be successful, affording a giant [n]cyclophane with a C84 PAH. Attempted bay-region Diels-Alder reactions and some cursory host-guest chemistry of teropyrenophanes are also discussed. In Chapter 7 a synthetic approach toward a planar model compound, 2,11-di-tbutylteropyrene, is described. The synthesis could not be completed owing to solubility problems at the end of the synthetic pathway.

Coastal geomorphology, processes and erosion at the tourist destination of Ferryland, Newfoundland and Labrador

The community of Ferryland is located on the southeastern coast of the Avalon Peninsula. The town traditionally relied on a fishing-based economy until the collapse of the fishery in the early 1990s. The present economy emphasizes sustainable development in the tourism sector with focus on archaeology, geotourism and other recreational uses. This paper discusses coastal erosion and impacts on sites and infrastructure using methods including: local knowledge, Real Time Kinematic (RTK) surveying and other survey techniques, seawater level measurement, meteorological data from a locally-installed station, custom-made drifter tube buoys, photography, HD video, and investigation using various modes of transport including inflatable boat. The major findings of the study include that the residents and stakeholders are genuinely interested in and knowledgeable of coastal erosion. The causes of coastal erosion include: large waves, surge, longshore currents, harbour oscillations, mass wasting, and location of infrastructure causing alterations of these processes. Freeze-thaw Cycles (FTC), rainfall, and gravity loosen and transport rock, till, and fill materials downslope. Large waves and currents transport the materials alongshore or into the nearshore. Harbour oscillations causing high velocity currents (> 2 m/s) are responsible for shoreline erosion and damage to property in The Pool. Historical resources such as gun batteries and ordnance pieces which date to the 1700s are being lost or threatened through coastal erosion of till and rock cliffs. Improper drainage and maintenance is responsible for erosion of roads and supporting shoulders, necessitating mitigation measures. Sediment transport and deposition during and after large wave and surge events lead to undercutting of infrastructure and increased risk of washover of existing infrastructure. Erosion is ongoing at Bois Island and Ferryland Head Isthmus through slope processes and undercutting; The Pool and the lower Colony of Avalon site through harbour oscillations and related undermining; the tombolo and the main breakwater through wave attack; and Meade’s Cove including the East Coast Trail through wave attack and undercutting. The floor of the latrine in the lower Colony of Avalon site indicates that sea level was approximately 1.25m below present in the 1620s, a relative sea level rise rate of 3.2 mm/y. The recommendations include suggested mitigation to reduce impacts specific to each site.

Experimental investigation of water, snow and granular ice effects on ice failure processes and impact loads

A large series of laboratory ice crushing experiments was performed to investigate the effects of external boundary condition and indenter contact geometry on ice load magnitude under crushing conditions. Four boundary conditions were considered: dry cases, submerged cases, and cases with the presence of snow and granular ice material on the indenter surface. Indenter geometries were a flat plate, wedge shaped indenter, (reverse) conical indenter, and spherical indenter. These were impacted with artificially produced ice specimens of conical shape with 20° and 30° cone angles. All indenter – ice combinations were tested in dry and submerged environments at 1 mm/s and 100 mm/s indentation rates. Additional tests with the flat indentation plate were conducted at 10 mm/s impact velocity and a subset of scenarios with snow and granular ice material was evaluated. The tests were performed using a material testing system (MTS) machine located inside a cold room at an ambient temperature of - 7°C. Data acquisition comprised time, vertical force, and displacement. In several tests with the flat plate and wedge shaped indenter, supplementary information on local pressure patterns and contact area were obtained using tactile pressure sensors. All tests were recorded with a high speed video camera and still photos were taken before and after each test. Thin sections were taken of some specimens as well. Ice loads were found to strongly depend on contact condition, interrelated with pre-existing confinement and indentation rate. Submergence yielded higher forces, especially at the high indentation rate. This was very evident for the flat indentation plate and spherical indenter, and with restrictions for the wedge shaped indenter. No indication was found for the conical indenter. For the conical indenter it was concluded that the structural restriction due to the indenter geometry was dominating. The working surface for the water to act was not sufficient to influence the failure processes and associated ice loads. The presence of snow and granular ice significantly increased the forces at the low indentation rate (with the flat indentation plate) that were higher compared to submerged cases and far above the dry contact condition. Contact area measurements revealed a correlation of higher forces with a concurrent increase in actual contact area that depended on the respective boundary condition. In submergence, ice debris constitution was changed; ice extrusion, as well as crack development and propagation were impeded. Snow and granular ice seemed to provide additional material sources for establishing larger contact areas. The dry contact condition generally had the smallest real contact area, as well as the lowest forces. The comparison of nominal and measured contact areas revealed distinct deviations. The incorporation of those differences in contact process pressures-area relationships indicated that the overall process pressure was not substantially affected by the increased loads.