ABSTRACT
To use atomically precise metal nanoclusters (NCs) in various application fields, it is essential to establish size-selective synthesis methods for the metal NCs. Studies on thiolate (SR)-protected gold NCs (Au n (SR) m NCs) revealed that the atomically precise Au n (SR) m NC, which has a different chemical composition from the precursor, can be synthesized size-selectively by inducing transformation in the framework structure of the metal NCs by a ligand-exchange reaction. In this study, we selected the reaction of [Au25(SC2H4Ph)18]- (SC2H4Ph = 2-phenylethanethiolate) with 4-tert-butylbenzenethiol ( t BuPhSH) as a model ligand-exchange reaction and attempted to obtain new metal NCs by changing the amount of thiol, the central atom of the precursor NCs, or the reaction time from previous studies. The results demonstrated that [Au23(SPh t Bu)17]0, [Au26Pd(SPh t Bu)20]0 (Pd = palladium) and [Au24Pt(SC2H4Ph)7(SPh t Bu)11]0 (Pt = platinum) were successfully synthesized in a high proportion. To best of our knowledge, no report exists on the selective synthesis of these three metal NCs. The results of this study show that a larger variety of metal NCs could be synthesized size-selectively than at present if the ligand-exchange reaction is conducted while changing the reaction conditions and/or the central atoms of the precursor metal NCs from previous studies.
ABSTRACT
Metal nanoclusters (NCs), which consist of several, to about one hundred, metal atoms, have attracted much attention as functional nanomaterials for use in nanotechnology. Because of their fine particle size, metal NCs exhibit physical/chemical properties and functions different from those of the corresponding bulk metal. In recent years, many techniques to precisely synthesize metal NCs have been developed. However, to apply these metal NCs in devices and as next-generation materials, it is necessary to assemble metal NCs to a size that is easy to handle. Recently, multiple techniques have been developed to form one-, two-, and three-dimensional connected structures (CSs) of metal NCs through self-assembly. Further progress of these techniques will promote the development of nanomaterials that take advantage of the characteristics of metal NCs. This review summarizes previous research on the CSs of metal NCs. We hope that this review will allow readers to obtain a general understanding of the formation and functions of CSs and that the obtained knowledge will help to establish clear design guidelines for fabricating new CSs with desired functions in the future.
