Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells
Yan, J., Malola, S., Hu, C., Peng, J., Dittrich, B., Teo, B. K., Häkkinen, H., Zheng, L., & Zheng, N. (2018). Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells. Nature Communications, 9, Article 3357. https://doi.org/10.1038/s41467-018-05584-9
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2018Copyright
© the Authors, 2018.
This paper reports co-crystallization of two atomically precise, different-size ligand-stabilized nanoclusters, a spherical (AuAg)267(SR)80 and a smaller trigonal-prismatic (AuAg)45(SR)27(PPh3)6 in 1:1 ratio, characterized fully by X-ray crystallographic analysis (SR = 2,4-SPhMe2). The larger cluster has a four concentric-shell icosahedral structure of Ag@M12@M42@M92@Ag120(SR)80 (M = Au or Ag) with the inner-core M147 icosahedron observed here for metal nanoparticles. The cluster has an open electron shell of 187 delocalized electrons, fully metallic, plasmonic behavior, and a zero HOMO-LUMO energy gap. The smaller cluster has an 18-electron shell closing, a notable HOMO-LUMO energy gap and a molecule-like optical spectrum. This is the first direct demonstration of the simultaneous presence of competing effects (closing of atom vs. electron shells) in nanocluster synthesis and growth, working together to form a co-crystal of different-sized clusters. This observation suggests a strategy that may be helpful in the design of other nanocluster systems via co-crystallization.
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https://converis.jyu.fi/converis/portal/detail/Publication/28231488
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Research Council of FinlandFunding program(s)
Academy Project, AoF; Research costs of Academy Professor, AoFAdditional information about funding
We thank the National Key R&D Program of China (2017YFA0207302) and National Natural Science Foundation of China (21731005, 21420102001, 21333008, and 21721001) for financial support. The financial support (to B.K.T.) from iChEM, Xiamen University is gratefully acknowledged. H.H. acknowledges the support from China’s National Innovation and Intelligence Introduction Base visitor program. The work in University of Jyvaskylä was supported by the Academy of Finland (grants 266492, 294217, and H.H. Academy Professorship). The computations were done at the CSC −the Finnish IT Center for Science in Espoo (Finland) and in Barcelona (Spain) supercomputing center under PRACE project “Nanometals”. ...License
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