Citation: HIGAKI Tatsuya, JIN Rongchao. Structural Evolution Patterns of FCC-Type Gold Nanoclusters[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 755-761. doi: 10.3866/PKU.WHXB201801191 shu

Structural Evolution Patterns of FCC-Type Gold Nanoclusters

HIGAKI Tatsuya ,
JIN Rongchao ^,

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States

Author Bio:
Rongchao Jin is currently a Professor of Chemistry at Carnegie Mellon University. He received his Ph.D. from Northwestern University in 2003. After three years of postdoctoral research at the University of Chicago, he joined the chemistry faculty of Carnegie Mellon University in 2006 and was promoted to Associate Professor in 2012 and Full Professor in 2015. His current research interests are atomically precise nanoparticles, nano-optics, and catalysis
Corresponding author: JIN Rongchao, rongchao@andrew.cmu.edu
Received Date: 9 November 2017
Revised Date: 12 January 2018
Accepted Date: 12 January 2018
Available Online: 19 July 2018
Fund Project: the U.S. National Science Foundation DMREF-0903225The project was supported by the Air Force Office of Scientific Research (FA9550-15-1-0154) and the U.S. National Science Foundation (DMREF-0903225)The project was supported by the Air Force Office of Scientific Research FA9550-15-1-0154

Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic size" nanoclusters revealed a variety of unique structures such as decahedron, icosahedron, as well as hexagonal close packing (hcp) and body-centered cubic (bcc) packing arrangements in gold nanoclusters, which are largely different from the face-centered cubic (fcc) structure in conventional gold nanoparticles. The characteristic geometrical structures enable the nanoclusters to exhibit interesting properties, and these properties are in close correlation with their atomic structures according to the recent studies. Experimental and theoretical analyses have been applied in the structural identification aiming to clarify the universal principle in the structural evolution of nanoclusters. In this mini-review, we summarize recent studies on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibit one-dimensional growth along the [001] direction in a layer-by-layer manner from Au₂₈(TBBT)₂₀ to Au₃₆(TBBT)₂₄, Au₄₄(TBBT)₂₈, and to Au₅₂(TBBT)₃₂ (TBBT: 4-tert-butylbenzenethiolate). The optical properties of these nanoclusters also evolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth from Au₄₄(TBBT)₂₈ toward both [100] and [010] directions leads to the Au₉₂(TBBT)₄₄ nanocluster, and the recently reported Au₅₂(PET)₃₂ (PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au₆₀(SCH₃)₃₆, Au₆₈(SCH₃)₄₀, Au₇₆(SCH₃)₄₄, etc, for the continuation of 1D growth pattern, as well as Au₆₈(SR)₃₆ mediating the 2D growth pattern from Au₄₄(TBBT)₂₈ to Au₉₂(TBBT)₄₄. Overall, this mini-review provides guidelines on the rules of structural evolution of fcc gold nanoclusters based on 1D, 2D and 3D growth patterns.
- Gold,
- Nanoclusters,
- Thiolate,
- Face-centered-cubic,
- Layer-by-layer growth
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