Nanosized Coordination Cages Incorporating Multiple Cu(I) Reactive Sites: Host–Guest Modulated Catalytic Activity

The intermolecular catalysis toward the oxidation of
hydrocarbons
has been studied with a series of nanoscale coordination cages [CuI4L4]4+, which are characteristic
of the inherent catalytic activity by installing multiple Cu+ redox active ions on the cage vertices. The catalytic reactions
take place out-cage on the surface active Cu+ sites, while
the catalytic activity can be modulated in-cage by the guest anions,
establishing an unprecedented host–guest regulable catalysis
structural model for coordination cages in the sense of supramolecular
catalysis. The catalytic behavior and mechanism, reactivity-structure
relationship, and recyclable use of the cage catalysts have been thoroughly
explored, in an effort to find the way to achieving robust catalysis
through careful tuning of the solution stability and redox activity
of cage structures by changing size and shape of guest anions.