Otherwise Unstable Structures Self-Assemble in the Cavities of Cuboctahedral Coordination Cages

We present a method for the directed self-assembly of interlocked structures and coordination complexes in a set of metal–organic hosts. New homo- and heteroleptic metal complexesspecies that cannot be prepared outsideform within the cavities of cuboctahedral coordination cages. When linear bidentate guests and macrocycles are sequentially introduced to the host, a rotaxane is threaded internally; the resulting ternary host–guest complex is a new kind of molecular gyroscope. Tetradentate guests segregate the cavities of these cages into distinct spaces, promoting new stoichiometries and modes of ligand binding to metal ions. The behaviors of bound complexes were observed to alter markedly as a result of confinement: In situ oxidations and spin transitions, neither of which occur ex situ, were both observed to proceed. By providing a tailored space for new modes of coordination-driven self-assembly, the inner phases of cuboctahedral coordination cages provide a new medium for synthetic coordination chemistry.