Single-atom“surgery”on chiral all-dialkynyl-protected superatomic silver nanoclusters  

手性全双炔保护超原子银纳米团簇的单原子“手术”

作　　者：Chengkai Zhang Wei-Dan Si Wei-Dong Tian Wan-Jun Xiao Zhi-Yong Gao Zhi Wang Chen-Ho Tung Di Sun 张成凯;司为丹;田伟东;肖婉君;高志永;王芝;佟振合;孙頔

机构地区：[1]School of Chemistry and Chemical Engineering,State Key Laboratory of Crystal Materials,Shandong University,Jinan 250100,China [2]School of Chemistry and Chemical Engineering,Henan Normal University,Xinxiang 453007,China

出　　处：《Science Bulletin》2025年第3期365-372,共8页科学通报(英文版)

基　　金：supported by the National Natural Science Foundation of China(92361301,22325105,22201159,22171164,and 52261135637);the Instrument Improvement Funds of Shandong University Public Technology Platform(ts20220102).

摘　　要：The manipulation of single atom within the metallic kernel of nanoclusters has attracted considerable attention due to its potentials to elucidate kernel-based structure-property relationships at the single-atom level.Herein,new-designed chiral bialkynyl ligands,have been chosen as protective agents to isolate two pairs of 8-electron superatomic silver nanoclusters,R/S-Ag39 and R/S-Ag40.X-ray diffraction analysis reveals that Ag39 and Ag40 with the same number of chiral ligands,possess a closely analogous silver skeleton but a single-atomic difference.The incorporation of an extra Ag40th atom into Ag40 evokes two significant changes of structure and property compared to Ag39:(i)a reduction in the symmetry of the entire nanocluster,resulting in an enhancement of kernel-related asymmetry g-factor;(ii)a regulation of the transitions(1P→1D and Ligand(π)→1D)of excited state,leading to a second near-infrared(NIR-II,1000-1700 nm)phosphorescent emission red-shift from 1088 to 1150 nm.This work not only provides vital insights into the relationship between structures and ground/excited states chiroptical activities at the single-atom level,but also presents bialkynyl as a promising stabilizing agent for building superatomic metal nanoclusters.

关 键 词：Single atom manipulation Chiral bialkynyl ligands Superatomic silver nanoclusters NIR-Il phosphorescence 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O614.122[理学—无机化学]