Ordered Arrays of Metals with Polynitrile or Cyanide Ligands

这一无机化学、生物无机化学和金属有机化学奖为密歇根州立大学化学系Kim R.Dunbar博士合成有机氰桥过渡金属化合物的研究提供了支持。链状、层状和三维组件将被构建和结晶，并确定其磁性和导电性能。乙腈化合物经过简单的取代反应，从而可以添加各种配体以获得中等的性质。通过改变金属前驱体上的电荷、有机基团上的不同取代基以及扩展网络中存在的不同的外球离子，可以提高扩展阵列的溶解度。化合物将有两种主要类型。一种类型的化合物将包含过渡金属西格玛键合到聚腈受体的氮原子孤对上。将使用四氰乙烯(TCNE)等物种。在这些体系中，顺磁性金属中心被组装成有机自由基网络。第二类化合物由过渡金属氰化物络合物反应而成，形成铁或铁磁偶联链或二维网络的扩展阵列。在这项研究中，将控制过渡金属腈化合物的合成，以便形成一维、二维或三维阵列的纯晶体。预计该阵列将表现出与结构排列相关的不寻常的磁性。通过操纵附着在金属上的有机基团，化合物的溶解度将被控制，以建立特定类型的分子排列和晶体生长。

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.