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

Abstract

The intermolecular catalysis toward the oxidation of hydrocarbons has been studied with a series of nanoscale coordination cages [Cu I 4 L 4 ] 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.