Abstract
Developing new approaches to fulfill the enantioseparation of nanocluster racemates and construct cluster-based nanomaterials with optical activity remains highly desired in cluster science,because it is an essential prerequisite for fundamental research and extensive applications of these nanomaterials.We herein propose a strategy termed"active-site exposing and partly re-protecting"to trigger the symmetry breaking of highly symmetrical nan-oclusters and to render cluster crystals optically active.The vertex PPh3 of the symmetrical Ag29(SSR)12(PPh3)4(SSR=1,3-benzenedithiol)nanocluster was firstly dissociated in the presence of counterions with large steric hindrance,and then the exposed Ag active sites of the obtained Ag29(SSR)12 nanocluster were partly re-protected by Ag+,yielding an Ag29(SSR)12-Ag2 nanocluster with a symmetry-breaking construction.Ag29(SSR)12-Ag2 fol-lowed a chiral crystallization mode,and its crystal displayed strong optical activity,derived from CD and CPL characterizations.Overall,this work presents a new approach(i.e.,active-site exposing and partly re-protecting)for the symmetry breaking of highly symmetrical nanoclusters,the enantioseparation of nanocluster racemates,and the achievement of highly optical activity.
基金项目
国家自然科学基金(21631001)
国家自然科学基金(21871001)
国家自然科学基金(22101001)
Ministry of Education,and the University Synergy Innovation Program of Anhui Province(GXXT-2020-053)
NETL
NSTL
万方数据