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[Cu23(PhSe)16(Ph3P)8(H)6]·BF4: Atomic-Level Insights into Cuboidal Polyhydrido Copper Nanoclusters and Their Quasi-simple Cubic Self-Assembly

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    [Cu23(PhSe)16(Ph3P)8(H)6]·BF4: Atomic-Level Insights into Cuboidal Polyhydrido Copper Nanoclusters and Their Quasi-simple Cubic Self-Assembly
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    • Ren-Wu Huang
      Ren-Wu Huang
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Ren-Wu Huang
    • Jun Yin
      Jun Yin
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Jun Yin
      Orcidhttp://orcid.org/0000-0002-1749-1120
    • Chunwei Dong
      Chunwei Dong
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Chunwei Dong
    • Partha Maity
      Partha Maity
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Partha Maity
      Orcidhttp://orcid.org/0000-0002-0293-7118
    • Mohamed Nejib Hedhili
      Mohamed Nejib Hedhili
      Core Labs, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Mohamed Nejib Hedhili
    • Saidkhodzha Nematulloev
      Saidkhodzha Nematulloev
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Saidkhodzha Nematulloev
    • Badriah Alamer
      Badriah Alamer
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      Department of Chemistry, College of Sciences, Taif University, Taif 11099, Saudi Arabia
      More by Badriah Alamer
    • Atanu Ghosh
      Atanu Ghosh
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Atanu Ghosh
      Orcidhttp://orcid.org/0000-0002-4938-8793
    • Omar F. Mohammed
      Omar F. Mohammed
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      More by Omar F. Mohammed
      Orcidhttp://orcid.org/0000-0001-8500-1130
    • Osman M. Bakr*
      Osman M. Bakr
      Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      KAUST Catalysis Center (KCC), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
      *E-mail: [email protected]
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      Orcidhttp://orcid.org/0000-0002-3428-1002
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    ACS Materials Letters

    Cite this: ACS Materials Lett. 2021, 3, 1, 90–99
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    https://doi.org/10.1021/acsmaterialslett.0c00513
    Published December 17, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Polyhydrido copper nanoclusters are an emerging class of nanomaterials. Unfortunately, insights into the structural evolution and structure–property relationship of such copper nanoclusters are scant, because of the difficulty of synthesizing and crystallizing nanoclusters with high nuclearity and new morphologies. Here, we report an anisotropic cuboidal polyhydrido copper nanocluster, [Cu23(PhSe)16(Ph3P)8(H)6]·BF4, with a distorted cuboctahedral Cu13 core stabilized by two square protecting motifs and six hydrides. The cuboidal nanoclusters self-assemble into a quasi-simple cubic packing pattern with perfect face-to-face contact of neighboring nanoclusters and interdigitation of intercluster surface ligands. Atomic-level observations reveal the crucial role that subtle synergies between nanocluster geometry and intercluster noncovalent interactions play in guiding nanocluster self-assembly. In addition, a comparison with previously reported analogous metal nanoclusters points to bulky monodentate phosphine ligands as a potent inducing agent for the formation of rectangular hexahedral nanoclusters. These findings have significant implications for the controllable synthesis of polyhedral nanomaterials and their superstructures.

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    The Supporting Information is available free of charge on the ACS Publications website. (PDF) (CIF) The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmaterialslett.0c00513.

    • Details regarding instrumentation and characterization, including UV–vis, ESI-MS, NMR, X-ray crystallography, XPS, fs-TA analysis, and DFT calculations; supporting Figures S1–S27 and Tables S1–S3;CheckCIF/PLATON report of [Cu23(PhSe)16(Ph3P)8(H)6]·BF4 (PDF)

    • Crystallographic structure of the [Cu23(PhSe)16(Ph3P)8(H)6]·BF4 (CIF)

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    Cited By

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    This article is cited by 52 publications.

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    ACS Materials Letters

    Cite this: ACS Materials Lett. 2021, 3, 1, 90–99
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmaterialslett.0c00513
    Published December 17, 2020
    Copyright © 2020 American Chemical Society
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