Core-dependent properties of copper nanoclusters: valence-pure nanoclusters as NIR TADF emitters and mixed-valence ones as semiconductors
Publication in refereed journal


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)O-6]@Cu(i)(47) (C3) and {[Cu(ii)O-4]center dot[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.
著者Zhang LL, Zhou G, Zhou G, Lee H, Zhao N, Prezhdo OV, Mak TCW
期刊名稱Chemical Science
出版社Royal Society of Chemistry: Open Access / Royal Society of Chemistry
頁次10122 - 10128

上次更新時間 2020-22-11 於 23:11