The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report ...The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report two atomically precise gold NCs,[Au_(9)(DPPF)_(4)]Cl_(3)(DPPF=bis(diphenylphosphino)ferrocene)(Au_(9))and[Au_(8)(DPPF)_(4)]Cl_(2)(Au_(8)),identified by single-crystal X-ray diffraction(SCXRD)and electrospray ionization mass spectrometry(ESI-MS).SCXRD analysis revealed that the two gold NCs contain a similar Au_(8)unit enclosed by a tetrahedral framework consisting of four DPPF ligands,and the only difference is the addition of a gold atom on the kernel surface of the Au_(9)NC,which can be resected to form the Au_(8)NC.This represents the achievement of precise atomic“tailoring”of the surface of a kernel of a gold NC without altering the other parts of the structure.Notably,the two NCs allow for the identification of free valence electrons(6e).A further investigation into their electronic structures and electrocatalytic CO_(2)reduction reaction activity was performed to explore the functionality of such minimal kernel tailoring at the atomic level.This study not only enriches the family of diphosphine-protected small-sized gold NCs but also realizes the atomic-level tailoring of specific sites on a nanoparticle.展开更多
基金supported by the National Natural Science Foundation of China(22371108,21971246,22209002)the Taishan Scholar Foundation of Shandong Province(tsqn202211242)the Natural Science Foundation of Shandong Province(ZR2024MB125,ZR2024MB007,ZR2024QB238,and ZR2020QB031).
文摘The atom-level manipulation of atomically precise metal nanoclusters(NCs)has attracted considerable attention due to its potential for facilitating the elucidation of structure-property relationships.Herein,we report two atomically precise gold NCs,[Au_(9)(DPPF)_(4)]Cl_(3)(DPPF=bis(diphenylphosphino)ferrocene)(Au_(9))and[Au_(8)(DPPF)_(4)]Cl_(2)(Au_(8)),identified by single-crystal X-ray diffraction(SCXRD)and electrospray ionization mass spectrometry(ESI-MS).SCXRD analysis revealed that the two gold NCs contain a similar Au_(8)unit enclosed by a tetrahedral framework consisting of four DPPF ligands,and the only difference is the addition of a gold atom on the kernel surface of the Au_(9)NC,which can be resected to form the Au_(8)NC.This represents the achievement of precise atomic“tailoring”of the surface of a kernel of a gold NC without altering the other parts of the structure.Notably,the two NCs allow for the identification of free valence electrons(6e).A further investigation into their electronic structures and electrocatalytic CO_(2)reduction reaction activity was performed to explore the functionality of such minimal kernel tailoring at the atomic level.This study not only enriches the family of diphosphine-protected small-sized gold NCs but also realizes the atomic-level tailoring of specific sites on a nanoparticle.
