A coordination cage hosting ultrafine and highly catalytically active gold nanoparticles.

Ultrafine metal nanoparticles (MNPs) with size <2 nm are of great interest due to their superior catalytic capabilities. Herein, we report the size-controlled synthesis of gold nanoparticles (Au NPs) by using a thiacalixarene-based coordination cage CIAC-108 as a confined host or stabilizer. The Au NPs encapsulated within the cavity of CIAC-108 (Au@CIAC-108) show smaller size (∼1.3 nm) than the ones (∼4.7 nm) anchored on the surface of CIAC-108 (Au/CIAC-108). The cage-embedded Au NPs can be used as a homogeneous catalyst in a mixture of methanol and dichloromethane while as a heterogeneous catalyst in methanol. The homogeneous catalyst Au@CIAC-108-homo exhibits significantly enhanced catalytic activities toward nitroarene reduction and organic dye decomposition, as compared with its larger counterpart Au/CIAC-108-homo and its heterogeneous counterpart Au@CIAC-108-hetero. More importantly, the as-prepared Au@CIAC-108-homo possesses remarkable stability and durability.