Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics

Qiaofeng Yao; Lingmei Liu; Sami Malola; Meng Ge; Hongyi Xu; Zhennan Wu; Tiankai Chen; Yitao Cao; María Francisca Matus; Antti Pihlajamäki; Yu Han; Hannu Häkkinen; Jianping Xie

doi:10.1038/s41557-022-01079-9

Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics

Nat Chem. 2023 Feb;15(2):230-239. doi: 10.1038/s41557-022-01079-9. Epub 2022 Nov 10.

Authors

Qiaofeng Yao^#^{1

2}, Lingmei Liu^#³, Sami Malola^#⁴, Meng Ge⁵, Hongyi Xu⁵, Zhennan Wu¹, Tiankai Chen¹, Yitao Cao¹, María Francisca Matus⁴, Antti Pihlajamäki⁴, Yu Han⁶, Hannu Häkkinen^{7

8}, Jianping Xie^{9

10}

Affiliations

¹ Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore.
² Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, P. R. China.
³ Multi-scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, P. R. China.
⁴ Department of Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finland.
⁵ Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden.
⁶ Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia. yu.han@kaust.edu.sa.
⁷ Department of Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finland. hannu.j.hakkinen@jyu.fi.
⁸ Department of Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, Finland. hannu.j.hakkinen@jyu.fi.
⁹ Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore. chexiej@nus.edu.sg.
¹⁰ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, P. R. China. chexiej@nus.edu.sg.

^# Contributed equally.

PMID: 36357788
DOI: 10.1038/s41557-022-01079-9

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 CH⋯π 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.

Abstract

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