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

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Abstract

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.

Graphical abstract: Core-dependent properties of copper nanoclusters: valence-pure nanoclusters as NIR TADF emitters and mixed-valence ones as semiconductors

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Publication details

The article was received on 12 Jul 2019, accepted on 06 Sep 2019 and first published on 07 Sep 2019


Article type: Edge Article
DOI: 10.1039/C9SC03455B
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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

    L. L. Zhang, G. Zhou, G. Zhou, H. Lee, N. Zhao, O. V. Prezhdo and T. C. W. Mak, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03455B

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