Tuning the Magic Size of Atomically Precise Gold Nanoclusters via Isomeric Methylbenzenethiols.

Toward controlling the magic sizes of atomically precise gold nanoclusters, herein we have devised a new strategy by exploring the para-, meta-, ortho-methylbenzenethiol (MBT) for successful preparation of pure Au130(p-MBT)50, Au104(m-MBT)41 and Au40(o-MBT)24 nanoclusters. The decreasing size sequence is in line with the increasing hindrance of the methyl group to the interfacial Au-S bond. That the subtle change of ligand structure can result in drastically different magic sizes under otherwise similar reaction conditions is indeed for the first time observed in the synthesis of thiolate-protected gold nanoclusters. These nanoclusters are highly stable as they are synthesized under harsh size-focusing conditions at 80-90 °C in the presence of excess thiol and air (i.e., without exclusion of oxygen).