Inorganic and Organometallic Chemistry
Awards:
Current Research Programs: The research carried out in our group focuses on the synthesis, structural characterisation and physical properties of high nuclearity, metal cluster particles. There are three primary reasons and objectives behind the development of this key area of chemical research: (i) the controlled synthesis of large metal or mixed main group-metal colloids and clusters may lead to a size regime wherein the electronic properties of these molecules no longer resemble those of smaller, discrete molecular units nor do they mimic those of the corresponding bulk materials. Such complexes hold great promise for use in microelectronic applications, such as in the development of quantum dots where only discrete, quantised energy levels (and thus the need for a strictly regular array of metal atoms) are available. (ii) The use of discrete 'premixed' binary or ternary phase clusters, with labile ancillary ligands has been shown to afford alternate, low temperature routes into corresponding (and possibly new) solid state materials. The use of preformed molecules in the preparation of solids allows for lower reaction temperatures and times for the formation of solids, thus implying kinetic versus thermodynamic control during sample preparation. (iii) The development of heterogeneous catalysts using supported large clusters or colloids of known structure, chemical composition and nuclearity is expected to lead to greater selectivity versus conventional systems where the size distribution of the dispersed metal particles can also lead to a distribution of the products obtained. Our efforts in these areas can be categorized in the following areas: i) ligand stabilised ternary phase nanocluster systems; ii) the use of (p) conjugated organic spacer molecules in order to link polymetallic sites in one, two and three dimensions whereby electronic communication between them is thus made possible and iii) the incorporation of nanoclusters into sized restricted, one directional nanosilicate materials. Students working on these projects learn the techniques of inert atmosphere synthesis and utilise a wide arsenal of characterisation techniques including X-ray crystallography (single crystal and powder), combination TGA-GC/MS, NMR (multinuclear, solution and solid state), UV-VIS and FT-IR spectroscopy and electrochemistry. Selected Publications: M. W. DeGroot, K. M. Atkins, A. Borecki, H. Rösner and John F. Corrigan, J. Mater. Chem., 2008, 18, 1123 - 1130. Molecular Precursor Approach for the Synthesis of Composition-Controlled ZnxCd1-xS and ZnxCd1-xSe Nanoparticles. E. A. Turner, H. Rösner, Y. Huang, J. F. Corrigan, J. Phys. Chem. C, 2007, 111; 7319-7329. Accessing Binary CdE [E = S, Se, Te] and Ternary CdxZn1-xE [E = S, Se] Materials in Mesoporous Architectures Using Silylated-Chalcogen Reagents. A. Borecki and J. F. Corrigan, Inorg. Chem., 2007, 46, 2478-2484. New Copper- and Silver-Trimethylsilylchalcogenolates. C. Nitschke, D. Fenske, J. F. Corrigan, Inorg. Chem., 2006, 45,9394-9401. Ferrocenyl Functionalized Copper-Selenium Clusters. M. W. DeGroot, H. Rösner, J. F. Corrigan,Chem. - A Eur. J., 2006, 12, 1547-1554. Control of Metal Ion Composition in the Synthesis of Ternary II-II'-VI Nanoparticles Using a Mixed-Metal Cluster Precursor Approach. |