Grant: Discovery Grants Program - Individual

REDOX-GENERATED FREE RADICALS: BASIC SCIENCE TO NANOMATERIALS My research program in the field of synthetic and structural chemistry deals with fundamental studies of the formation and investigation of compounds of non-metal elements with odd numbers of electrons. My group studies the design, preparation and stability of such ""free radicals"" of both fundamental and practical interest with a special focus on the interconversion, stability and potential decay of such species as a result of electron transfer processes, what chemist call ""redox"" events (for oxidation-reduction). Analytical electrochemistry is a key tool in understanding and then controlling these processes. However, the application of electrochemistry to modern non-aqueous chemistry of the non-metallic elements is a severely neglected area of study (as opposed to their classical aqueous electrochemistry as found in most text books). This means that fundamental data and key investigative methods, which are relatively well developed for transition and lanthanide metal compounds, are non-existent for studies of the non-metals and the so-called ""main group"" metals. Hence ongoing method development and survey studies remain important as foundations for our group's research programme. From this starting point we have developed two highly-novel applications of non-metal element free-radicals to the emerging world of nanotechnology. Nanomaterials are composed of discrete entities with diameters below one micrometer and we will focus on entities with diameters ranging from 20-100 nanometers. In one project we propose to link stable redox-switchable phosphine/phosphoniumyl radicals to nanoscale dendrimeric molecules for the specific purpose of monitoring the flexibility and rotational dynamics of this novel class of mono-disperse, discrete starburst polymers when dissolved in suitable solvents. In the second project, we propose to incorporate stable heterocyclic radicals into the backbones of metal frameworks, metal-rings and metal-cage species. These will form paramagnetic guests that are expected to provide specific interactions with high spin host molecules leading to novel soft magnetic materials.