Phosphides with clusters structures

Table 4.16. Selected metal Phosphides with cluster structures...

The second example comes from solid-state chemistry, and the coimection with cluster chemistry is less obvious. Despite this, it is an excellent example of how E/M variation can lead to systematic variation in structure and, consequently, to properties. Although the example is taken from solid-state metal borides, the silicides see Silicon Inorganic Chemistry) and phosphides (see Phosphides Solid-state Chemistry) could have been used. 

Various compounds have been prepared by solvothermal reactions metals, metal oxides, chalcogenides, - ° nitrides, - -" phosphides, open-framework structures, - oxometalate clusters, - organic-inorganic hybrid materials, - - and even carbon nanotnbes. - Most of the solvothermal products are nano- or microparticles with well-defined morphologies. The distribution of the particle size of the prodnct is nsnally qnite narrow, and formation of monodispersed particles is freqnently reported. - When the solvent molecules or additives are preferentially adsorbed on (or have a specific interaction with) a certain surface of the products, growth of the surface is prohibited and therefore products with unique morphologies may be formed by the solvothermal reaction. - - Thus nanorods, wires, tnbes, and sheets of various types of products have been obtained solvothermally. 

Fhst, the number of valence functions (or frontier orbitals) and valence elechons (frontier orbital occupancy) determines the tendency toward cluster bonding. It is instructive to recall that the structural motif in elemental boron is the icosahedron with six-connected boron atoms see Borides Solid-state Chemistry), it is the tetrahedral carbon atom in the diamond form of elemental carbon with four-coimected carbon atoms and it is three-connected phosphorus atoms in the sheets of elemental black phosphorus (see Phosphides Solid-state Chemistry). Boron has more valence orbitals than valence elechons, naturally leading to orbitally rich cluster formation for example, BH has three orbitals and two elechons and forms... 

Careful analysis of both powder X-ray dilfraction and EXAFS spectroscopic data located the cadmium sulfide as (CdS)4 cubes occupying the space within sodalite cages, with the Cd ions coordinated to framework oxygen atoms (Fig. 6.10). Furthermore, the clusters were observed to order between adjacent sodalite cages, to give superclusters or a superlattice structure. In subsequent work, a variety of compounds and elements have been prepared as well-defined clusters within zeolite frameworks, including metal oxides, selenides and phosphides, and these have been studied mainly with the view of determining the effects of cluster size on optical and electronic properties. 

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