Structural Isomerization in Cu(I)Clusters:Tracing the Cu Thermal Migration Paths and Unveiling the Structure-Dependent Photoluminescence  

作　　者：Xi Fan Furong Yuan Jiaqi Wang Zhibin Cheng Shengchang Xiang Huayan Yang Zhangjing Zhang 

机构地区：[1]Fujian Provincial Key Laboratory of Polymer Materials,College of Chemistry and Materials Science,Fujian Normal University,Fuzhou,Fujian 350007 [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,Fujian 350002 [3]Health Science Center School of Biomedical Engineering,Shenzhen University,Shenzhen 518000

出　　处：《CCS Chemistry》2023年第2期350-360,共11页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.22101048,22005054,and 21975044);the Natural Science Foundation of Fujian Province(grant no.2021J01150).

摘　　要：Revealing structural isomerization in metal clusters would bridge a huge structural gap between small molecular isomerization and solid–solid phase transformation.However,genuine structural isomerism in metal clusters is still rare.In this work,we report the first example of structural isomerismin Cu clusters.By utilizing the coordination flexibility of alkyne to enable the migration of partial Cu atoms in Cu metal cores,two Cu_(15)cluster complexes(Cu_(15)-a and Cu_(15)-c)possessing identical composition but different metal core structures have been successfully isolated.Interestingly,although the structure of Cu_(15)-a can be retained in CH_(2)C_(l2)solution below 27°C,it will gradually change to give an intermediate state,Cu_(15)-b,as the temperature rises(at about 31°C)before it eventually transforms into Cu_(15)-c(at 40∼65°C).Significantly,atomically precise Cu_(15)-b clearly provides footprints for tracing the thermal migration process of Cu atoms during the thermal transformation from Cu_(15)-a to Cu_(15)-c.In addition,Cu_(15)-a and Cu_(15)-c exhibit diverse crystallization-induced emission enhancement phenomena.Crystalline Cu_(15)-c displays redshifted photoluminescence(820 nm)compared with Cu_(15)-a(726 nm)due to the shorter mean Cu···Cu distance in Cu_(15)-c.Notwithstanding,crystalline Cu_(15)-a exhibits much more intense photoluminescence at room temperature than that in Cu_(15)-c,which might be attributed to the stronger intermolecular C–H⋯πinteractions in Cu_(15)-a.These results indicate that cluster isomerism provides valuable opportunities for insight into the structure–property relationships and understanding the complex evolution of phase transformation in nanometallic solids.

关 键 词：cluster compounds metal clusters structural isomerism isomeric transformation structure–property relationships 

分 类 号：O641.4[理学—物理化学]