JBGIM · Functional Nanoscale Coordination Polymers: Controlled Growth by Metal-Containing Block Copolymer Templated Self-Assembly

Functional nanoscale coordination polymers: controlled growth by metal-containing block copolymer templated self-assembly

Work carried out and results: (a) The milestones / work plan for year 1 were as follows: (1) synthesis of metal-containing diblock copolymer polyelectrolytes, ligands, and model complexes as 'synthetic building blocks'; (2) self-assembly of coordination polymers by various methods as outlined in this proposal; (3) nanoscience applications of nanoscale coordination polymers. The research progressed on schedule: (1) Block copolymer polyelectrolytes containing Fe and Co were realised after a number of preliminary studies were conducted to find appropriate metal-containing monomers for subsequent polymerisation. Furthermore, the effects of counter ions on the solubility of the block copolymer polyelectrolytes, which is of great importance for self-assembly studies, have been explored. (2) Studies of the self-assembly behaviour of the heterobimetallic block copolymer polyelectrolytes realised have led to the realisation of block copolymer micelles with unprecedented structure. It was found that the presence of the polyelectrolyte block effected the crystallisation-driven self-assembly allowing for competitive growth in three dimensions from crystalline block copolymer micelle seeds. The self-assembly of homopolymers at the ends of block copolymer micelle seeds was also explored, resulting in remarkable controlled network formation. (3) Block copolymer micelles have been utilised as liquid crystalline materials. The micelles have been shown to align with an electric field, and the resulting aligned liquid crystals have been studied by wide and small angle X-ray scattering (WAXS and SAXS) studies at the Diamond Light Source Synchrotron facility (Didcot, United Kingdom). The studies resulted in the determination of the crystal structure of block copolymer micelle cores, a groundbreaking result in the field of functional block copolymer self-assembly. (b) The milestones / work plan for year 2 were as follows: (1) self-assembly of coordination polymers by various methods as outlined in this proposal; (2) nanoscience applications of nanoscale coordination polymers; (3) reporting of results in various international scientific journals and at international conferences. The research progressed on schedule: (1) Efforts towards the synthesis and self-assembly of metal-containing block copolymer polyelectrolytes were continued, yielding a wide range of building blocks for incorporation into functional nanoscale conducting polymers, including those obtained in year one. As part of our investigations, a mechanism for the thermal ring-opening polymerisation of (2)metallocenophanes was established, and a new reactivity pathway resulting in formation of a M-M bond between strained dicarba(2)metallocenophanes uncovered. Furthermore, conducting block copolymers were synthesised and their self-assembly behaviour evaluated for potential integration into functional nanoscale coordination polymers. (2) In year 2, we continued to investigate the liquid crystalline properties of block copolymer micelles with a crystalline core, and we will conduct neutron scattering experiments (ILL, Grenoble, France) in early July 2012 to gain further insight into the size and shape of the micelle core and surrounding corona. We have also established a protocol for the creation of conducting block copolymer micelles, and aim to evaluate their materials-based properties in the near future. (3) The project undertaken as part of this fellowship has been very productive, and has resulted in 5 publications in top scientific journals. In addition, there is one publication in press and another manuscript has been submitted for publication. The results have also been presented at 3 different international conferences, encompassing 4 different presentations. Please see section 2 for details of dissemination activities. The transfer of knowledge objectives of this proposal has also progressed on schedule, and I have continued to learn from and to train researchers (through collaboration) in the Manners group, the School of Chemistry, and the Department of Physics at the University of Bristol. Conclusions The work conducted during the fellowship period has resulted in significant contributions to the functional polymeric nanomaterials field, and has opened up new areas of research that will be explored by Dr Gilroy and others for many years to come. The impact of the work has been illustrated through publication in top scientific journals (J. Am. Chem. Soc., Angew. Chem. Int. Ed., etc.) and has been well received at international conferences. Several additional publications in similar journals are envisioned in the coming months, and the impact of Dr Gilroy's research will continue to develop through continuation of the projects undertaken during his fellowship. The fellowship has also provided Dr Gilroy a tremendous boost with respect to career development. As a result, Dr Gilroy has obtained an academic position (assistant professor) at Western University, one of Canada's most highly regarded institutes. The training and experience he gained while working with one of the world leaders in polymer chemistry and nanoscience (prof. Ian Manners) has provided him with the necessary foundation required to start his own research group. On his return to Canada, long-term collaborative projects between Dr Gilroy and prof. Manners and other researchers at the University of Bristol are envisioned. These collaborations will continue to strengthen the relationship between the Canadian and European scientific communities, and will have a prolonged socio-economic impact on the European Union (EU) and Canada alike based on the employment and commercialisation opportunities that will arise.

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