We report the synthesis and characterization of selenophenolate-capped 25-gold-atom nanoclusters via a ligand-exchange approach. In this method, phenylethanethiolate (PhCH2CH2S) capped Au25 nanoclusters are utilized as the starting material, which is subject to ligand-exchange with selenophenol (PhSeH). The as-obtained cluster product is confirmed to be selenophenolate-protected Au25 nanoclusters through characterization by electrospray ionization (ESI) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), thermogravimetric analysis (TGA), elemental analysis (EA), UV-Vis and 1H/13C NMR spectroscopies. The ligand-exchange synthesis of [Au25(SePh)18]−[(C8H17)4N]+ nanoclusters demonstrates that the core size of gold nanoclusters is retained in the thiolate-to-selenolate exchange process and that the 18 surface thiolate ligands can be completely exchanged by selenophenolate, rather than giving rise to a mixed ligand shell on the cluster. The two types of Au25L18 (L = thiolate or selenolate) nanoclusters also show some differences in stability and optical properties.
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