Leitao, Erin M.Kumar, Vipin2021-08-302021-08-302021https://hdl.handle.net/2292/56300Today humanity is largely dependent on carbon-based products to meet the never-ending needs in our day-to-day lives, such as rubber, plastics etc. Even though carbon is not the most abundant element on the earth’s crust and is soon to become scarce, the rate at which humans are exploiting it is unsustainable. The time has come to diversify our elemental sources for materials from carbon to non-carbon elements. Silicon is a good enough substitute to carbon as it exhibits similar properties and it is the second most abundant element on the earth’s surface.1 The advancements in silicon chemistry have led to the development of long chain silicon polymers, polysilanes, which have exciting properties and have found applications ranging from energy materials to ceramics, presenting the potential of silicon to be used as a replacement for carbon in many molecules and materials. The properties and applications of polysilanes are discussed in detail in Chapter 1. One of the biggest drawbacks of these materials is their high sensitivity to external conditions such as UV light and heat owing to the weak Si-Si bonds. This feature readily leads to the cleavage of the bonds, therefore limiting the applications of polysilanes. In the Leitao lab we have begun to contribute to this field, our aim is to reinforce the Si-Si bonds by tethering the atoms together with a bridge. The goal is to produce polysilanes that are more robust where the Si-Si bond can reform in the case of homolytic cleavage. In this work, we explored various ways to synthesize bridged disilane monomers by manoeuvring around the challenges posed by silicon and silicon chemistry. Chapter 2 of this thesis describes an exploration to shortlist suitable bridging moieties and optimize synthetic routes to produce the bridged disilane monomers. Novel bridged disilanes were prepared and their photophysical properties were measured along with DFT calculations for comparison and deeper understanding. These results are discussed in Chapter 3. Silicon possesses the tendency to form hypervalent compounds. This property was explored in Chapter 4 where virtually bridged disilanes were prepared and studied using DFT calculations. With bridged disilane building blocks in hand, various attempts were made to produce the corresponding polymers using dehydrogenative coupling, as discussed in Chapter 5. Overall, this work has expanded our knowledge of silicon chemistry demonstrating some advancement towards robust polysilanes. A better understanding of the synthetic routes to access bridged disilanes as well as the feasibility of the bridging moieties has been gained. This work will act as a guide of the challenges associated with silicon chemistry to those interested in the field and consists of some ideas to attempt in order to expand this research in the future.Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated.Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated.https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htmhttps://creativecommons.org/licenses/by-nc-sa/3.0/nz/Thesis2021-07-05Copyright: The authorhttp://purl.org/eprint/accessRights/OpenAccessQ112955814