Small Copper Nanoclusters Synthesized through Solid-State Reduction inside a Ring-Shaped Polyoxometalate Nanoreactor.

Cu nanoclusters exhibit distinctive physicochemical properties and hold significant potential for multifaceted applications. Although Cu nanoclusters are synthesized by reacting Cu ions and reducing agents by covering their surfaces using organic protecting ligands or supporting them inside porous materials, the synthesis of surface-exposed Cu nanoclusters with a controlled number of Cu atoms remains challenging. This study presents a solid-state reduction method for the synthesis of Cu nanoclusters employing a ring-shaped polyoxometalate (POM) as a structurally defined and rigid molecular nanoreactor. Through the reduction of Cu incorporated within the cavity of a ring-shaped POM using H at 140 °C, spectroscopic studies and single-crystal X-ray diffraction analysis revealed the formation of surface-exposed Cu nanoclusters with a defined number of Cu atoms within the cavities of POMs. Furthermore, the Cu nanoclusters underwent a reversible redox transformation within the cavity upon alternating the gas atmosphere (i.e., H or O). These Cu nanoclusters produced active hydrogen species that can efficiently hydrogenate various functional groups such as alkenes, alkynes, carbonyls, and nitro groups using H as a reductant. We expect that this synthesis approach will facilitate the development of a wide variety of metal nanoclusters with high reactivity and unexplored properties.