首页|Structural Isomerization in Cu(Ⅰ)Clusters:Tracing the Cu Thermal Migration Paths and Unveiling the Structure-Dependent Photoluminescence
Structural Isomerization in Cu(Ⅰ)Clusters:Tracing the Cu Thermal Migration Paths and Unveiling the Structure-Dependent Photoluminescence
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Revealing structural isomerization in metal clusters would bridge a huge structural gap between small molecular isomerization and solid-solid phase trans-formation.However,genuine structural isomerism in metal clusters is still rare.In this work,we report the first example of structural isomerism in Cu clusters.By utilizing the coordination flexibility of alkyne to en-able the migration of partial Cu atoms in Cu metal cores,two Cu15 cluster complexes(Cu15-a and Cu15-c)possessing identical composition but different metal core structures have been successfully isolated.Inter-estingly,although the structure of Cu15-a can be retained in CH2Cl2 solution below 27 ℃,it will gradu-ally change to give an intermediate state,Cu15-b,as the temperature rises(at about 31 ℃)before it even-tually transforms into Cu15-c(at 40～65 ℃).Signifi-cantly,atomically precise Cu15-b clearly provides footprints for tracing the thermal migration process of Cu atoms during the thermal transformation from Cu15-a to Cu15-c.In addition,Cu15-a and Cu15-c ex-hibit diverse crystallization-induced emission en-hancement phenomena.Crystalline Cu15-c displays redshifted photoluminescence(820 nm)compared with Cu15-a(726 nm)due to the shorter mean Cu…Cu distance in Cu15-c.Notwithstanding,crystalline Cu15-a exhibits much more intense photoluminescence at room temperature than that in Cu15-c,which might be attributed to the stronger intermolecular C-H…π inter-actions in Cu15-a.These results indicate that cluster isomerism provides valuable opportunities for insight into the structure-property relationships and under-standing the complex evolution of phase transforma-tion in nanometallic solids.
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