New Functional Materials via Self-Assembly and Catalysis

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The proposal entitled "New Functional Materials via Self-Assembly and Catalysis" will cover two distinct areas of research in our group that have the potential to give rise to both impactful new fundamental science and also novel self-assembled and polymeric materials with useful properties and potential applications of societal relevance. 1) Self-Assembly A key current synthetic challenge involves the creation of uniform and functional polymer-based 1D fiber-like and 2D platelet particles that exist on a length-scale of nanometers to microns for various applications. In this proposal we outline a program to tackle this issue by exploiting, and addressing key challenges associated with, the living crystallization-driven self-assembly platform. Using this solution processing seeded-growth approach, amphiphilic block copolymers with crystallizable pi-conjugated blocks and related amphiphiles will be used to predictably construct 1D and 2D electroactive particles with controlled dimensions and spatially-defined chemistries. Our results published earlier this year for 1D conjugated polyfluorene-based particles created by living crystallization-driven self-assembly indicate that the hole-electron pairs or "excitons" formed by light-absorption are able to diffuse over the large distances needed (> 200 nm) to allow the creation of light-harvesting films of sufficient thickness to absorb virtually all of the incident light. This diffusion length is an order of magnitude larger than that normally found for conjugated polymers. The results indicate that particles created by living crystallization-driven self-assembly have potential applications in, for example, light-harvesting optoelectronic devices such as solar cells with improved efficiency and we aim to explore this exciting possibility. 2) Catalysis Over the past century the development of transition metal-catalyzed reactions has revolutionized the synthesis of organic molecules and polymers. In striking contrast, the synthetic methods used to create catenated structures based on main group elements are still limited. Our group has been at the forefront of the development of catalytic routes to bonds between p-block elements to facilitate the creation of improved routes to main group molecules and materials. In this proposal we target novel main group polymers based on phosphorus and other p-block elements with a range of potential applications which will become clear once their properties have been fully delineated. For example, with the phase-out of halogenated flame retardants, the development of new flame-retardant materials is pertinent and the new phosphorus-based p-block materials targeted may be particularly promising from this perspective. The proposed research aims to be at the leading edge of chemical and materials science internationally. The ultimate possibility of new commercially important products is realistic, and an excellent and broad training for young scientists is anticipated.