Metal-Metal Bonded Halides and their Derivatives

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Synthetic explorations for new and novel materials among the metal-rich halides of the early transition metals and their physical characterization will be pursued. The studies will feature the unique group of compounds in which metal cluster and condensed cluster phases are stabilized by strongly bound, interstitial elements, but new examples of other structures, properties and bonding will also be sought. The cluster host metals will include Sc, Y, the lanthanides, Ti, Hf and Nb, the halides will be chloride, bromide and iodide, and the interstitials studied will be both main group and transition (3d, 4d, 5d) elements. In addition to complete structural characterization, physical properties of new and interesting phases will be defined by conductivity, magnetic susceptibility, solid state NMR, and photoelectron spectroscopic measurements, and these will be coupled with extended-Huckel (band) calculations. Particular emphasis will be given to both the range of interstitials possible and the nature of the bonding in clusters centered by heavy transition elements, to the creation and properties of infinite chain and sheet structures in which these compounds provide heterometal arrays, to the relationship of these compounds to intermetallic phases, and to the solution chemistries of centered clusters as these provide both understanding of their stabilities and possible routes to new solid materials.