Incorporation of transition and Group I metal ions into the channels of materials composed of metal-assembled cages

Two new porous materials have been formed by allowing cobalt-assembled cages to self-assemble in the presence of potassium and cobalt ions. In both materials, the cages act as structural units that are linked by barium ions. During the assembly process, voids are created between the cages. In the case of the potassium material, K4Ba2Co412 (1=octaiminodiacetate resorcinarene), potassium ions either bind to the cages or are disordered in the channels of the material. For the cobalt material, Co2Ba2Co412, the cobalt counter cations are coordinated to water and carboxylate oxygens of 1 and reside within the voids. These materials have different structures than previously reported materials formed with cages and Group II cations. The channels in the K4Ba2Co412 material are 14×12 Å and run in two directions through the material. The channels in the Co2Ba2Co412 material are smaller (11×9 Å) and run in only one direction. In both materials the channels are surrounded by waters and methyl groups. These materials show how a single building unit, in this case a metal-assembled cage, can be used to construct various materials, even materials with transition and alkali metal ions in their channels.