纳米团簇
光致发光
价(化学)
铜
金属
材料科学
荧光
结晶学
半导体
光化学
化学
化学物理
纳米技术
光电子学
有机化学
量子力学
物理
冶金
作者
Leon Li-Min Zhang,Guodong Zhou,Guoqing Zhou,Hung Kay Lee,Ni Zhao,Oleg V. Prezhdo,Thomas C. W. Mak
出处
期刊:Chemical Science
[The Royal Society of Chemistry]
日期:2019-01-01
卷期号:10 (43): 10122-10128
被引量:41
摘要
We report herein that copper alkynyl nanoclusters show metal-core dependent properties via a charge-transfer mechanism, which enables new understanding of their structure-property relationship. Initially, nanoclusters 1 and 2 bearing respective Cu(i)15 (C1) and Cu(i)28 (C2) cores were prepared and revealed to display near-infrared (NIR) photoluminescence mainly from the mixed alkynyl → Cu(i) ligand-to-metal charge transfer (LMCT) and cluster-centered transition, and they further exhibit thermally activated delayed fluorescence (TADF). Subsequently, a vanadate-induced oxidative approach to in situ generate a nucleating Cu(ii) cation led to assembly of 3 and 4 featuring respective [Cu(ii)O6]@Cu(i)47 (C3) and {[Cu(ii)O4]·[VO4]2}@Cu(i)46 (C4) cores. While interstitial occupancy of Cu(ii) triggers inter-valence charge-transfer (IVCT) from Cu(i) to Cu(ii) to quench the photoluminescence of 3 and 4, such a process facilitates charge mobility to render them semiconductive. Overall, metal-core modification results in an interplay between charge-transfer processes to switch TADF to semiconductivity, which underpins an unusual structure-property correlation for designed synthesis of metal nanoclusters with unique properties and functions.
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