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    Dendrimer Ligand Directed Nanoplate Assembly
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    • Katherine C. Elbert
      Katherine C. Elbert
      Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
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      Orcidhttp://orcid.org/0000-0001-9019-1506
    • Thi Vo
      Thi Vo
      Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
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    • Nadia M. Krook
      Nadia M. Krook
      Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
      More by Nadia M. Krook
      Orcidhttp://orcid.org/0000-0003-3308-9040
    • William Zygmunt
      William Zygmunt
      Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
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    • Jungmi Park
      Jungmi Park
      Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
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    • Kevin G. Yager
      Kevin G. Yager
      Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States
      More by Kevin G. Yager
      Orcidhttp://orcid.org/0000-0001-7745-2513
    • Russell J. Composto
      Russell J. Composto
      Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
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      Orcidhttp://orcid.org/0000-0002-5906-2594
    • Sharon C. Glotzer*
      Sharon C. Glotzer
      Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
      Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
      Biointerfaces Institute, University of Michigan, Ann Arbor, Michigan 48109, United States
      *E-mail: [email protected]
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    • Christopher B. Murray*
      Christopher B. Murray
      Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
      Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States
      *E-mail: [email protected]
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    ACS Nano

    Cite this: ACS Nano 2019, 13, 12, 14241–14251
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    https://doi.org/10.1021/acsnano.9b07348
    Published November 22, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Many studies on nanocrystal (NC) self-assembly into ordered superlattices have focused mainly on attractive forces between the NCs, whereas the role of organic ligands on anisotropic NCs is only in its infancy. Herein, we report the use of a series of dendrimer ligands to direct the assembly of nanoplates into 2D and 3D geometries. It was found that the dendrimer-nanoplates consistently form a directionally offset architecture in 3D films. We present a theory to predict ligand surface distribution and Monte Carlo simulation results that characterize the ligand shell around the nanoplates. Bulky dendrimer ligands create a nontrivial corona around the plates that changes with ligand architecture. When this organic–inorganic effective shape is used in conjunction with thermodynamic perturbation theory to predict both lattice morphology and equilibrium relative orientations between NCs, a lock-and-key type of mechanism is found for the 3D assembly. We observe excellent agreement between our experimental results and theoretical model for 2D and 3D geometries, including the percent of offset between the layers of NCs. Such level of theoretical understanding and modeling will help guide future design frameworks to achieve targeted assemblies of NCs.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.9b07348.

    • Ligand synthesis procedures and characterization; additional microscopy; GISAXS data analysis; scaling theory for branching ligand architecture; mapping of scaling prediction to simulation (PDF)

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    Cited By

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    This article is cited by 26 publications.

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    ACS Nano

    Cite this: ACS Nano 2019, 13, 12, 14241–14251
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.9b07348
    Published November 22, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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