New high-spin clusters featuring transition metals

Three possible routes to polynuclear transition metal complexes are discussed. The first route, oligomerization induced by desolvation of small cages, is exemplified by synthesis of a dodecanuclear cobalt cage, and by reactions which give octa- and dodecanuclear chromium cages. The second route involves linking cages through organic spacers, and is illustrated by use of phthalate to link together cobalt and nickel cages. For the nickel case a complex consisting of four cubanes and a sodium octahedron is found. The third route involves the use of water to introduce hydroxide bridges into cages. One method of introducing water is to use hydrated metal salts; the transformation of a Cu6Na cage into a Cu12La8 illustrates this approach. Alternatively, adventitious water within solvents can be used as a source, and this approach has led to a Co-24 cage. The structures and magnetic properties of these various cages are discussed.