Final Activity Report Summary - NANOMANN (Nanoscience with Metal-Based Polymers) This project had as a major feature the use inorganic elements to make polymer chains with the vision that new processable materials will be created with a range of properties that approaches that possible with inorganic solid state materials. In line with this philosophy, the research focused on an exciting new fundamental research direction - nanoscience with metal-containing polymers. The project was divided into three sub-areas : 1. Nanoscience with phase-separated metal-containing block copolymers in the solid state We successfully initiated a research program that focuses on the generation of nanostructured films from the self-assembly of metal-containing block copolymers. New block copolymers are accessible via by either traditional anionic polymerization techniques or a remarkable new photopolymerisation procedure that requires subambient temperatures to work optimally. Studies of their self-assembly in thin films and in bulk have been performed. We have accessed metal-containing block copolymers that contain the metalloblock as the majority volume fraction. This should allow access to nanotemplates that permit inverse patterns to be created compared to the patterns reported to date from materials with the metalloblock as the minor phase. Through collaborations such materials have been shown to be useful for the creation of nanostructured metallic surfaces for surface-enhanced Raman spectroscopy, nanostructured magnetic surfaces with potential applications in data storage, and as carbon nanotube growth catalysts. 2. Metallopolymer and magnetic ceramic colloidal crystals for photonic applications The project and its collaborators have explored the preparation of metallopolymer colloidal crystals. Photonic crystals were prepared by using SiO2 colloidal microspheres. Magnetic materials have been prepared by etching and subsequent pyrolysis of the microporous solid product. We have found that in the materials used so far there is a loss of structural perfection during the pyrolysis process. This may be a consequence of inhomogeneous cross-linking and network formation. We will continue this work by designing new cross-linkable monomers with better-defined reactivity that will lead to magnetic photonic crystal replicas in which the structural integrity is better retained. New photonic crystal materials have been created by confining phase-separated metalloblock copolymers in the interstices of colloidal crystal arrays. Inverse structures were also created. 3. Swellable metallopolymer gels as inverted colloidal crystals We and our collaborators have explored the synthesis and development of a series of metallopolymer gels that potentially change shape reversibly with redox state. Composites have been prepared where first component is an inactive structural scaffold made of, for example, an ordered array of silica microspheres, and the second comprises a crosslinked network of an iron-based metallopolymer. This latter component actively mediates the lattice spacing of the silica spheres through a redox-driven swelling and shrinking process. Potential applications in sensors and displays are envisaged where Bragg diffraction effects lead to controlled colour changes.
