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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

          While valence-pure copper alkynyl nanoclusters show near-infrared TADF, the mixed-valence ones exhibit semiconductivity.

          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)O 6]@Cu( i) 47 ( C3) and {[Cu( ii)O 4]·[VO 4] 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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          Author and article information

          Journal
          Chem Sci
          Chem Sci
          Chemical Science
          Royal Society of Chemistry
          2041-6520
          2041-6539
          7 September 2019
          21 November 2019
          7 September 2019
          : 10
          : 43
          : 10122-10128
          Affiliations
          [a ] Department of Chemistry and Center of Novel Functional Molecules , The Chinese University of Hong Kong , Hong Kong SAR , People's Republic of China . Email: tcwmak@ 123456cuhk.edu.hk
          [b ] Department of Electronic Engineering , The Chinese University of Hong Kong , Hong Kong SAR , People's Republic of China
          [c ] Department of Chemistry , University of Southern California , Los Angeles , California 90089-1062 , USA
          Author notes

          ‡These authors contributed equally to this work.

          Article
          c9sc03455b
          10.1039/c9sc03455b
          7003970
          This journal is © The Royal Society of Chemistry 2019

          This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)

          Categories
          Chemistry

          Notes

          †Electronic supplementary information (ESI) available. CCDC 1907665–1907669 and 1907707. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc03455b

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