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Chemical and architectural intricacy from nanoscale tetrahedra and their analogues

  • Nanoparticle Assemblies of Modern Complexity
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Abstract

The tetrahedron, as the simplest platonic shape, is a profound building block with the potential to create intricate superstructures. Noteworthy designs utilizing tetrahedral building blocks include the Sierpiński tetrahedron (the most fundamental three-dimensional fractal), a one-dimensional helical structure known as the tetrahelix, and various crystalline and quasicrystalline packings. Historically, the practicality of tetrahedral superstructures has been evident, providing stable, well-defined frameworks for various constructions, including truss bridges, tower cranes, and electricity transmission line pylons. In the field of self-assembled nanocrystal superlattices, tetrahedral nanocrystals, as building blocks, occupy a unique place among all the possible nanoscale particles. Mathematical models, simulation work, and experimental studies using nanocrystals in the laboratory have suggested that self-assembled structures derived from nanoscale tetrahedral building blocks are notably intricate, giving rise to new horizons of high-entropy nanocrystal superlattices. An important implication from previous works is that such tetrahedral nanocrystal superlattices form through highly delicate interparticle interactions, emphasizing the importance of the fine features of these nanocrystals. In this article, we summarize the advances in superlattices assembled from tetrahedral nanocrystals. We first define the tetrahedron and tetrahedron analogues based on Conway’s transformation and graph theory, underscoring their relevance to the crystallization process producing tetrahedral nanocrystals. Then, we showcase previous reports on the synthesis of tetrahedral nanocrystals and the resulting nanocrystal superstructures. Finally, we conclude by offering insights and perspective into the chemical and architectural intricacy that could emerge from tetrahedral nanocrystals.

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Adapted with permission from Reference 55. © 2006 AAAS. (b) Three-dimensional models demonstrating local packing of NCs within nanosheets from the side (left) and top (right). Adapted with permission from Reference 55. (c) Scanning electron microscopy (SEM) image of chiral twisted ribbons formed from bundles of tetrahelices. Three-dimensional model of twisted ribbon, with close-up to individual tetrahelix unit (inset). Adapted with permission from Reference 56. © 2020 American Chemical Society. (d) Circular dichroism (CD) spectrum for solutions of twisted ribbons, color-coded for solutions with L-, D-, and racemic-cysteine surface ligands. Adapted from Reference 56. (e) Three-dimensional model of twisted ribbon (left), with close-up views to individual tetrahelix units from side (center top) and top (center bottom) views, and atomic model of cysteine interactions between adjacent NCs (right). Adapted from Reference 56. (f) SEM images of left-handed (left) and right-handed (right) pinwheel superlattices (SLs), with 3D models (insets). Adapted with permission from Reference 59. © 2022 Springer Nature. (g) Formation mechanism of chiral pinwheel structures from achiral units. CW, clockwise; CCW, counterclockwise. Adapted with permission from Reference 59. (h) SEM images of pinwheel SLs, overlaid with a 3D model demonstrating NC size, displacement, and tilt angle. Adapted with permission from Reference 59. (i) SEM image of Au tetrahedral NCs within pinwheel SL. Adapted with permission from Reference 60. © 2022 Springer Nature. (j) Three-dimensional model displaying interparticle forces for bilayer assemblies of tetrahedral NCs. Adapted with permission from Reference 60. (k) SEM images of large-scale (left, top) and small-scale (left, bottom) pinwheel assemblies with identical chiral twist angles, with corresponding photon-induced near-field electron microscopy data (center) and finite-difference time-domain simulations (right). LD, large domain; SD, small domain. Adapted with permission from Reference 60. (l) Computer model of liquid cell TEM setup for in situ measurements. Adapted with permission from Reference 60. (m) Time-resolved snapshots of pinwheel self-assembly process, taken in situ using liquid cell TEM. Adapted with permission from Reference 60.

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Funding

O.C. acknowledges the support from the National Science Foundation through Award No. DMR-1943930. O.C. also acknowledges supports from the Camille & Henry Dreyfus Foundation through the Camille Dreyfus Teacher-Scholar Award program and the Alfred P. Sloan Foundation through the Sloan Research Fellowship Award program. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the US DOE’s National Nuclear Security Administration (Contract No. DE-NA-0003525). The views expressed in the article do not necessarily represent the views of the US DOE or the US government.

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  1. Department of Chemistry, Brown University, Providence, USA

    Jeremy Schneider, Yasutaka Nagaoka & Ou Chen

  2. Sandia National Laboratories, Albuquerque, USA

    Hongyou Fan

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J.S., Y.N., and O.C. wrote the manuscript. All authors commented on and edited the manuscript.

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Correspondence to Hongyou Fan or Ou Chen.

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Schneider, J., Nagaoka, Y., Fan, H. et al. Chemical and architectural intricacy from nanoscale tetrahedra and their analogues. MRS Bulletin 49, 319–329 (2024). https://doi.org/10.1557/s43577-024-00688-8

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