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

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

106 Citations (Scopus)

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. [Figure not available: see fulltext.].

Original language	English
Pages (from-to)	230-239
Number of pages	10
Journal	Nature Chemistry
Volume	15
Issue number	2
Early online date	10 Nov 2022
DOIs	https://doi.org/10.1038/s41557-022-01079-9
Publication status	Published - Feb 2023
Externally published	Yes

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title = "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 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. [Figure not available: see fulltext.].",

author = "Qiaofeng Yao and Lingmei Liu and Sami Malola and Meng Ge and Hongyi Xu and Zhennan Wu and Tiankai Chen and Yitao Cao and Matus, {Mar{\'i}a Francisca} and Antti Pihlajam{\"a}ki and Yu Han and Hannu H{\"a}kkinen and Jianping Xie",

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T1 - Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics

AU - Yao, Qiaofeng

AU - Liu, Lingmei

AU - Malola, Sami

AU - Ge, Meng

AU - Xu, Hongyi

AU - Wu, Zhennan

AU - Chen, Tiankai

AU - Cao, Yitao

AU - Matus, María Francisca

AU - Pihlajamäki, Antti

AU - Han, Yu

AU - Häkkinen, Hannu

AU - Xie, Jianping

PY - 2023/2

Y1 - 2023/2

N2 - 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. [Figure not available: see fulltext.].

AB - 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. [Figure not available: see fulltext.].

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Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics

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