Synthesis of truly monodisperse (single size) nanoparticles and their structural characterization to atomic resolution are extremely important challenges in nanoscience. For many nanoscale materials important to next-generation electronic, magnetic, catalytic, and biomedical systems/devices, the ‘top-down’ approach is reaching its limits as the fabrication of monodisperse nanoparticles becomes more and more difficult with decreasing size. The bottom-up molecular approach to ultra-small (up to 3 nm or so) nanoparticles promises a powerful alternative route if high nuclearity clusters that have the same structure as the bulk material can be synthesized. Such ‘molecular nanoparticles’ (MNP’s) would bring the many powerful advantages of molecular chemistry to this area of nanoscience, particularly true monodispersity, solubility, and crystallinity, the latter allowing structural characterization to atomic resolution by single-crystal X-ray crystallography, including the monolayer shell of organic ligands that is extremely difficult to characterize for traditional nanoparticles. Nanoparticles of CeO2, various Fe oxides, Mn oxides, and others are widely used in many areas from industrial catalysis to medical applications. For CeO2, we have developed routes to a family of MNP’s with dimensions up to 2.4 nm using primarily carboxylate ligands, and since then breakthroughs have been achieved to MNPs of other important metal oxides. In addition, we have recently been targeting the use of MNP’s as supports for 3d and/or 4f heterometals on their surface to model magnetic units or catalysts supported on traditional nanoparticles or other surfaces. This presentation will describe a number of the above systems.

Molecular routes to ultra-small (1-3 nm) nanoparticles of important metal oxides

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