ABSTRACT
We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to â¼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(â¼226)(SC12)(â¼76), Au(â¼253)(SC12)(â¼90), Au(â¼356)(SC12)(â¼112), and Au(â¼520)(SC12)(â¼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.