Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells

Juanzhu Yan; Sami Malola; Chengyi Hu; Jian Peng; Birger Dittrich; Boon K Teo; Hannu Häkkinen; Lansun Zheng; Nanfeng Zheng

doi:10.1038/s41467-018-05584-9

Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells

Nat Commun. 2018 Aug 22;9(1):3357. doi: 10.1038/s41467-018-05584-9.

Authors

Juanzhu Yan¹, Sami Malola², Chengyi Hu¹, Jian Peng¹, Birger Dittrich³, Boon K Teo¹, Hannu Häkkinen⁴, Lansun Zheng¹, Nanfeng Zheng⁵

Affiliations

¹ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China.
² Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014, Jyväskylä, Finland.
³ Heinrich-Heine Universität Düsseldorf, Anorganische Chemie und Strukturchemie, Universitätsstrasse 1, Gebäude 26.42.01.21, 40225, Düsseldorf, Germany.
⁴ Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014, Jyväskylä, Finland. [email protected].
⁵ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China. [email protected].

Abstract

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.

Publication types

Research Support, Non-U.S. Gov't