Utilization of a Mixed-Ligand Strategy to Tune the Properties of Cuboctahedral Porous Coordination Cages.

ABSTRACT

Ligand functionalization has been thoroughly leveraged to alter the properties of paddlewheel-based coordination cages where, in the case of ligand-terminated cages, functional groups are positioned on the periphery of synthesized cages. While these groups can be used to optimize solubility, porosity, crystal packing, thermal stability toward desolvation, reactivity, or optical activity, optimization of multiple properties can be challenging given their interconnected nature. For example, installation of functional groups to increase the solubility of porous cages typically has the effect of decreasing their porosity and stability toward thermal activation. Here we show that mixed-ligand cages can potentially address these issues as the benefits of various functional groups can be combined into one mixed-ligand cage. We further show that although ligand exchange reactions can be employed to obtain mixed ligand copper(II)-based cages, direct synthesis of mixed-ligand products is necessary for molybdenum(II) paddlewheel-based cages as these substitutionally inert clusters are resistant to ligand exchange. We ultimately show that highly soluble, highly porous, and thermally stable cuboctahedral cages are isolable by this strategy.