Abstract
Porous nanostructures and materials based on metal-mediated self-assembly have developed into a vibrantly studied subdiscipline of supramolecular chemistry during the past decades. In principle, two branches of such coordination compounds can be distinguished: Metal-organic frameworks (MOFs) on the one side represent infinite porous networks of metals or metal clusters that are connected via organic ligands to give solid-state materials. On the other hand, metal-organic cages (MOCs) are discrete and soluble systems with only a limited number of pores. Formation of a particular structure type is achieved by carefully balancing the donor site angles within the ligands as well as the nature and coordination geometry of the metal component. Years of research on MOFs and MOCs has yielded numerous types of well-defined porous crystals and complex supramolecular architectures. Since various synthetic routes and postsynthetic modification methods have been established, the focus of recent developments has moved toward the preparation of multifunctional systems that are able to mimic the structural and functional complexity of natural enzymes. This Account compares different strategies to prepare multifunctional MOFs and heteroleptic MOCs and gives a perspective on where to move forward. While the preparative toolbox for multifunctional MOFs is already quite mature, pore accessibility and substrate diffusion within the crystal have been identified as major challenges yet to be overcome. Only recently have a set of different strategies for the assembly of heteroleptic MOCs been developed. Such multifunctional cages can be formed from either partially protected or "naked" metal cations. Controlled assembly, producing single products rather than statistical mixtures, leans on assembly-dependent approaches making use of either steric effects or shape complementarity between the ligands. Further strategies include coordination-site engineering and hierarchical assembly of preformed components. The main challenge with heteroleptic, functional MOCs is to find a balance between the required dynamic assembly fidelity and the stability of the resulting system under operating conditions. If these limitations can be overcome in the future, chemists will be able to design multifunctional systems of similar activity and complexity as nature's enzymes from simple and easily accessible synthetic building blocks. Major impacts on chemical sensing, small-molecule recognition and sequestration, drug delivery, and catalysis will be achieved by these materials.