Ordered Arrays of Metals with Polynitrile or Cyanide Ligands

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This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides support for research on synthesis of organonitrile-bridged transition metal compounds by Dr. Kim R. Dunbar of the Chemistry Department, Michigan State University. Chain, layered and three-dimensional assemblies will be constructed and crystallized, and their magnetic and conducting properties determined. Acetonitrile compounds undergo facile substitution reactions so that a variety of ligands can be added to moderate properties. Solubility for extended arrays will be enhanced by varying charge on metal precursors, varying substituents on organic groups, and varying outer sphere ions present in extended networks. Compounds will be of two main types. One type of compound will contain transition metals sigma-bonded to the nitrogen atom lone pairs of polynitrile acceptors. Species such as tetracyanoethylene (TCNE) will be used. In these systems, paramagnetic metal centers are assembled into the organic radical network. The second type of compound consists of transition metal cyanide complexes reacted to form extended arrays of ferro- or ferrimangnetically coupled chains or two-dimensional networks. In this research, synthesis of transition metal nitrile compounds will be controlled so that pure crystals of one-, two-, or three-dimensional arrays will be formed. The arrays are expected to exhibit unusual magnetic properties which will be able to be correlated with structural arrangement. By manipulating the organic groups attached to the metals, the solubility of the compounds will be controlled in order to build specific types of molecular arrangements and crystal growth.