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Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics

Abstract

The controllable packing of functional nanoparticles (NPs) into crystalline lattices is of interest in the development of NP-based materials. Here we demonstrate that the size, morphology and symmetry of such supercrystals can be tailored by adjusting the surface dynamics of their constituent NPs. In the presence of excess tetraethylammonium cations, atomically precise [Au25(SR)18] NPs (where SR is a thiolate ligand) can be crystallized into micrometre-sized hexagonal rod-like supercrystals, rather than as face-centred-cubic superlattices otherwise. Experimental characterization supported by theoretical modelling shows that the rod-like crystals consist of polymeric chains in which Au25 NPs are held together by a linear SR–[Au(I)–SR]4 interparticle linker. This linker is formed by conjugation of two dynamically detached SR–[Au(I)–SR]2 protecting motifs from adjacent Au25 particles, and is stabilized by a combination of CHπ and ion-pairing interactions between tetraethylammonium cations and SR ligands. The symmetry, morphology and size of the resulting supercrystals can be systematically tuned by changing the concentration and type of the tetraalkylammonium cations.

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Fig. 1: Crystallization of [Au25(p-MBA)18] NPs into hexagonal rod-like supercrystals.
Fig. 2: Packing structure determination of hexagonal rod-like supercrystals.
Fig. 3: Crystallization habit of [Au25(p-MBA)18] NPs in the presence of various ratios of tetraalkylammonium and lithium cations.
Fig. 4: Characterization of the supercrystals’ building blocks.
Fig. 5: Effects of tetraalkylammonium cations on the stability of [Au25(p-MBA)18] dimer.
Fig. 6: Shaping supercrystals into truncated rhomboid flakes.

Data availability

The datasets generated and analysed during the current study are available with the manuscript files and/or from the corresponding authors upon reasonable request. Source data are provided in the Source Data or Supplementary Data files. Extensive DFT and MD calculations have been performed to illustrate the structure of Au25 NP supercrystals, which generated hundreds of raw data files. The results have been summarized in the main and supplementary figures. Due to the large number of raw simulation files, these are not provided with the supporting material but are available from the authors on request. Source data are provided with this paper.

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Acknowledgements

We acknowledge the financial support of the Ministry of Education, Singapore (Academic Research Grant R-279-000-580-112 (J.X) and R-279-000-538-114 (J.X.)) and the National Natural Science Foundation of China (22071174 (J.X.)). The theoretical work at the University of Jyväskylä was supported by the Academy of Finland (grants 292352 (H.H.), 318905 (H.H.), 319208 (H.H.) and H.H.’s Academy Professorship). The computations were done at the CSC computing centre in Finland and in the FGCI–Finnish Grid and Cloud Infrastructure (persistent identifier, urn:nbn:fi:research-infras-2016072533). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

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Contributions

J.X. and Y.H. supervised the experimental work. J.X. and Q.Y. conceived the idea and designed the experiment. Q.Y., L.L., M.G. and H.X. carried out the experiments and characterizations. Z.W., T.C. and Y.C. contributed to data interpretation and theory development. H.H. supervised the theoretical and computational work. A.P. performed the image similarity analysis correlating Au25 NP models to the TEM data. S.M. performed DFT computations of the single NPs and linked NP models. M.F.M. performed the MD simulations of the linked NP models in aqueous solution. All authors contributed to manuscript writing.

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Correspondence to Yu Han, Hannu Häkkinen or Jianping Xie.

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Supplementary Information

Supplementary Methods, Figs. 1–99, Notes 1–9 and Table 1.

Supplementary Data 1

Source data for Supplementary Figs. 1, 2, 3, 5, 7, 8, 10, 14, 16, 18, 19, 21.

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Source data for Supplementary Figs. 73, 77, 78, 79, 80, 81, 82.

Supplementary Data 3

Source data for Supplementary Figs. 89, 90, 91, 92, 93, 94, 95, 97, 98.

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Source Data Fig. 1

Plottable source data for Fig. 1c,d,f,g.

Source Data Fig. 4

Plottable source data for Fig. 4.

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Yao, Q., Liu, L., Malola, S. et al. Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics. Nat. Chem. (2022). https://doi.org/10.1038/s41557-022-01079-9

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