Three classes of bifunctional compounds related to frustrated Lewis pair chemistry were studied. The first class, alkynyl-linked phosphonium borates, was strategically synthesized and the corresponding neutral alkynyl-linked phosphine boranes generated in solution. They were reacted with THF, alkenes and alkynes to undergo either ring-opening or multiple bond addition reactions, giving rise to zwitterionic macrocycles. In two select alkynyl-linked phosphonium borates, thermolysis resulted in unique rearrangements transforming the phosphino- and boryl-substituted alkynyl moieties into C4 chains. The alkynyl-linked phosphine boranes were further demonstrated to coordinate as η3-BCC ligands in Ni(0) complexes. The rigid nature of the coordination was confirmed by dimerization without cleavage of the Ni–B interaction upon the addition of acetonitrile or carbon monoxide. Moreover, reactions with Al-, Zn- and B-based Lewis acids prompted hydride transfer within the alkynyl-linked phosphonium borate and interesting functional group transfer reactions. The second class of the bifunctional systems, a series of gem-substituted bis-boranes, was subjected to reactions with tBu3P and CO2. The O-linked bis-borane was shown to coordinate the phosphino-carboxylate moiety with one B, while the methylene-linked bis-boranes were demonstrated to chelate the carboxyl group. The third bifunctional system class, vinyl-group tethered boranes, was examined to elucidate the mechanism of the frustrated Lewis pair addition reaction to olefins. Using a bis(pentafluorophenyl)alkylborane, the close proximity of the olefinic protons and the ortho-fluorine nuclei were evident by both NOE measurements and DFT calculations. Moreover, its reactions with phosphine bases suggested that an initial interaction between the highly electrophilic borane and the olefinic fragment precedes such frustrated Lewis pair addition reaction. Furthermore, a bis(pentafluorophenyl)alkoxyborane was synthesized and reacted with P-, N-, C- and H-based nucleophiles, demonstrating the wide range of Lewis bases that can be applied in olefin addition reactions with complementary regioselectivity.

The synthesis of monodentate biphenyl-amido proligands is reported as well as a series of complexes of lithium with these ligand systems. The solid-state molecular structure of these lithium amides are described as well as their use as synthons in the preparation of amido-arene aluminum complexes. Structural and spectroscopic data suggest that these species exhibit weak arene to metal donation. Attempts to generate aluminum cations from these species are detailed. A new synthetic route to titanium “constrained geometry” precatalysts was utilized to prepare a series of titanium complexes with similar pendant arene groups. The homopolymerization activity of these catalyst systems with ethylene and styrene is detailed. Combination of a sterically encumbered phosphine and large, electrophilic borane was used to effect heterolytic cleavage of disulfides to afford novel thiophosphoniumthioborate salts. A series of exchange reactions demonstrated the facile reversal of this reaction. Similar phosphine-borane systems are found to exhibit divergent reactivity with terminal alkynes, affording either phosphonium-alkynylborate salts from deprotonation or phosphonium-vinyl-borate zwitterions from addition. The scope of Lewis acid, Lewis base and alkyne combinations used to effect similar reactivity is detailed. It was found that the reaction of pyrroles, boranes, and alkynes formed similar addition products that were found to undergo further reactivity to afford C-vinyl pyrroles and nitrogen-boron bicyclic compounds. The synthesis of N-alkyl-bis(pentafluorophenyl)boryl amidinates is presented. The reactivity of these compounds with a variety of small molecules is reported. Reaction with CO2, CO, di-iso-propylcarbodiimide, tert-butyl isocyanide, and benzaldehyde as well as thermally-induced intramolecular rearrangement of these compounds affords a variety of novel nitrogen-boron heterocycles.

The synthesis of monodentate biphenyl-amido proligands is reported as well as a series of complexes of lithium with these ligand systems. The solid-state molecular structure of these lithium amides are described as well as their use as synthons in the preparation of amido-arene aluminum complexes. Structural and spectroscopic data suggest that these species exhibit weak arene to metal donation. Attempts to generate aluminum cations from these species are detailed. A new synthetic route to titanium “constrained geometry” precatalysts was utilized to prepare a series of titanium complexes with similar pendant arene groups. The homopolymerization activity of these catalyst systems with ethylene and styrene is detailed. Combination of a sterically encumbered phosphine and large, electrophilic borane was used to effect heterolytic cleavage of disulfides to afford novel thiophosphoniumthioborate salts. A series of exchange reactions demonstrated the facile reversal of this reaction. Similar phosphine-borane systems are found to exhibit divergent reactivity with terminal alkynes, affording either phosphonium-alkynylborate salts from deprotonation or phosphonium-vinyl-borate zwitterions from addition. The scope of Lewis acid, Lewis base and alkyne combinations used to effect similar reactivity is detailed. It was found that the reaction of pyrroles, boranes, and alkynes formed similar addition products that were found to undergo further reactivity to afford C-vinyl pyrroles and nitrogen-boron bicyclic compounds. The synthesis of N-alkyl-bis(pentafluorophenyl)boryl amidinates is presented. The reactivity of these compounds with a variety of small molecules is reported. Reaction with CO2, CO, di-iso-propylcarbodiimide, tert-butyl isocyanide, and benzaldehyde as well as thermally-induced intramolecular rearrangement of these compounds affords a variety of novel nitrogen-boron heterocycles.

The goal of this thesis is to investigate and propose housing that increases density while offering a better quality of life for citizens inhabiting Toronto’s Avenues. This thesis compares three different building prototypes, all of varying scales and typological characteristics. The viability of each prototype is discussed with regards to the current economic and regulatory conditions within the city, as well as the varying quality of life that each prototype creates.

Soft materials have attracted much scientific and technical interest in recent years. In this thesis, attention has been placed on the underpinning relations between molecular structure and properties of one type of soft matter - main chain liquid crystalline elastomers (MCLCEs), which may have application as shape memory or as auxetic materials. In this work, a number of siloxane-based MCLCEs and their linear polymer analogues (MCLCPs) with chemical variations were synthesized and examined. Among these chemical variations, rigid p-phenylene transverse rod and flat-shaped anthraquinone (AQ) mesogenic monomers were specifically incorporated. Thermal and X-ray analysis found a smectic C phase in most of our MCLCEs, which was induced by the strong self-segregation of siloxane spacers, hydrocarbon spacers and mesogenic rods. The smectic C mesophase of the parent LCE was not grossly affected by terphenyl transverse rods. Mechanical studies of MCLCEs indicated the typical three-region stress-strain curve and a polydomain-to-monodomain transition. Strain recovery experiments of MCLCEs showed a significant dependence of strain retentions on the initial strains but not on the chemical variations, such as the crosslinker content and the lateral substituents on mesogenic rods. The MCLCE with p-phenylene transverse rod showed a highly ordered smectic A mesophase at room temperature with high stiffness. Mechanical properties of MCLCEs with AQ monomers exhibit a strong dependence on the specific combination of hydrocarbon spacer and siloxane spacer, which also strongly affect the formation of ð-ð stacking between AQ units. Poisson s ratio measurement over a wide strain range found distinct trends of Poisson s ratio as a function of the crosslinker content as well as terphenyl transverse rod loadings in its parent MCLCEs.

The purpose of this study is to find the motivation to use of Facebook, the social presence of Facebook and the popular network media now, and verifying how the major motivations on Facebook and social presence on Facebook and the other popular network media affect to the frequency of use on these platforms. It tested hypotheses through questionnaire. By the random sampling method, 202 returned online questionnaires in total were regarded as valid (64.74% response rate). The findings have been summarized as the following: 1. The male to female ratio of Facebook users are close, the students are majority job, and many users are also workers. 2. If Facebook and internet community media characteristics are different, it will affect the user's social presence. 3. If there are Facebook users have different motivations to use, it won¡¦t influence the frequency of use of the Internet community media. 4. The higher level of social presence when the more biased nature of personal communication medium of the Internet community. 5. The differences in social presence will influence the frequency of use of the communication media. 6. Relax and browse information on the motivation are major motivations for the user of Facebook.

Considering revitalization as a way of improving three interrelated aspects of quality of life including physical quality, social and economic welfare, this study sets out an evaluation framework to measure the success of implementations aiming to revitalize historic commercial places. This framework emerges from the qualities of built environments which are defined with reference to the normative urban design theory developed by Kevin Lynch. Urban qualities are defined with a comprehensive approach which takes into account spatial, social, and economic aspects of creating urban places. The Main Street Program, subject of this study, is a historic commercial district revitalization program developed by the National Trust for Historic Preservation in the United States. This program introduces a preservation-based revitalization model. Based on a comprehensive approach, the program suggests working simultaneously on organization, design, economic restructuring, and promotion. This study analyzes the revitalization model of the Main Street Program by looking at its various aspects including organization models, funding tools, involvement of local communities, contributions of the federal and local governments, implementation, and self-evaluation. Besides, it introduces a citywide coordinating program, Boston Main Streets. Finally, it analyzes the revitalization of Washington Street in South End, Boston, one of the places where Main Street Program has been implemented. The street has been transformed from a vacant and deteriorated commercial street into a more vital, pedestrian oriented, mixed use place in a decade. This study aims to analyze the case from three different points. First, the success of the program is evaluated within the above framework. Second, the effectiveness of the program is examined through an outcome analysis. Finally, the organizational performance of the Main Street organization is analyzed.

The relationship between urban design and economic activity is seldom studied through empirical studies with a large number of cases due, in part, to the implicit and intangible nature of design. This study was intended to understand, analyze, and evaluate the complex relationship between the design and the economic revitalization of downtown districts with reference to the 78 active Texas Main Street Program districts. First, the design, promotion, organization, and economic restructuring components of the Main Street Program's comprehensive four-point approach were investigated. Next, the economic changes that occurred within those districts were analyzed from 1997-2001. Finally, employment, the number of jobs, the number of business establishments, the number of sales tax permits, the retail sales volume, and the commercial property values were compared for the same time period among three categories of cities: those active in the Main Street Program, those formerly active but now inactive, and those who have not participated. Findings revealed that several positive changes occurred in design, promotion, organization, and economic restructuring components of the four-point approach within the active Texas Main Street districts. It appears that these changes produced several positive outcomes for the physical, social, and economical environment of the active Main Street districts. Moreover, the findings suggests that these changes in the Main Street districts resulted in an increased economic activity, not only within the Main Street district by generating jobs, or producing private and/or public investment, but also across the Main Street city by creating community wide economic activity in most of the variables that were under investigation. The results indicate that the Texas Main Street Program, part of which is urban design oriented, is having a positive effect on economic activity within the active Main Street districts.

This study utilized historical population statistics data and related reports to investigate the population distribution and transition trend of Kaohsiung Main Urban Area. There were four purposes of this study; firstly to understand the current population distribution pattern of Kaohsiung Main Urban Area, secondly to investigate the change trend of Kaohsiung Main Urban Area in the past 36 years, thirdly using Kaohsiung Main Urban Area population data to verify the population density model and to examine the correspondence with the current society, and fourthly to explore the impact of the establishment of Kaohsiung Mass Rapid Transit System and Taiwan High Speed Rail to the transition and distribution of population in Kaohsiung Main Urban Area. This study employed the population statistical database from year 1972 to 2007, and divided the Kaohsiung metropolitan area into 32 sub-divisions. The population data was re-organized accordingly in order to perform the systematic analyses and exploration in making the understanding of the current population status and transition process. Furthermore, employing the population data of Kaohsiung metropolitan area, the validation of negative exponential model and quadratic exponential model, the population model proposed by Clark and Newling respectively 58 year ago, were performed to verify the applicability of the theories to modern society. In addition, this study also performed the exploration of population transition and distribution in Kaohsiung metropolitan area during the construction period of Kaohsiung Mass Rapid Transit System and Taiwan High Speed Rail and could be of reference to urban planning and development in the future. This study found that both Clark and Newling¡¦s population model still has high interpretation capability after 58 years later. The Kaohsiung metropolitan area population distribution model and trend forecast proposed by Ho in 1991 is still true. However, because of the slow down in overall development trend of Taiwan, the transition trend of Kaohsiung metropolitan also mitigated. Besides, due to the trend mitigation, the volcano peak phenomenon which was mentioned in the literature review will be postponed and expected to happen in year 2018.

Diss.--Philosophie--Berlin--Humboldt-Univ., 2001. / Bibliogr. p. 206-214.