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.
|Original language||English (US)|
|State||Published - Nov 10 2022|
Bibliographical noteKAUST Repository Item: Exported on 2022-11-14
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.
ASJC Scopus subject areas
- Chemical Engineering(all)