Compression-Driven Internanocluster Reaction for Synthesis of Unconventional Gold Nanoclusters

Can the active kernels in ultrasmall metal nanoparticles (nanoclusters, NCs) react with one another, or can the internanocluster reaction occur when they are in close enough proximity? To resolve this fundamental issue, we investigated the solid-state internanocluster reaction of the most studied gold NC Au-25(SR)(18) (SR: thiolate). A novel NC was produced by increasing the pressure to 5 GPa, whose composition was determined to be Au-32(SC2H4Ph)(24) by mass spectrometry and thermogravimetric analysis. As revealed by single-crystal X-ray crystallography, the structure, a bicuboid Au-14 kernel and three pairs of interlocked trimetric staples, has not been reported and endows the NC with obvious photoluminescence. DFT calculations indicate that the staples contribute substantially to the absorption properties. Further experiments reveal the pressure (internanocluster distance) can tune the internanocluster reaction, and the resulting product is not necessarily the thermodynamic product.