摘要
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 Au_(23)(TBBT)_(20) to Au_(36)(TBBT)_(24),Au_(44)(TBBT)_(28), and to Au_(52)(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 Au_(44)(TBBT)_(28) toward both [100] and [010] directions leads to the Au_(92)(TBBT)_(44) nanocluster, and the recently reported Au_(52)(PET)_(32)(PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au_(60)(SCH_3)_(36), Au_(68)(SCH_3)_(40), Au_(76)(SCH_3)_(44), etc, for the continuation of 1 D growth pattern, as well as Au_(68)(SR)_(38)mediating the 2 D growth pattern from Au_(44)(TBBT)_(28) to Au_(92)(TBBT)_(44). Overall, this mini-review provides guidelines on the rules of structural evolution o
Recent progress in the research of atomically-precise metal nanoclustershas identified a series of exceptionally stable nanoclusters with specific chemicalcompositions. Structural determination on such ＂magic size＂ nanoclusters revealed avariety of unique structures such as decahedron, icosahedron, as well as hexagonalclose packing （hcp） and body-centered cubic （bcc） packing arrangements in goldnanoclusters, which are largely different from the face-centered cubic （fcc） structure inconventional gold nanoparticles. The characteristic geometrical structures enable thenanoclusters to exhibit interesting properties, and these properties are in closecorrelation with their atomic structures according to the recent studies. Experimentaland theoretical analyses have been applied in the structural identification aiming to on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibitone-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 alsoevolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth fromAu44（TBBT）28 toward both [100] and [010] directions leads to the Aug2（TBBT）44 nanocluster, and the recently reportedAu52（PET）32 （PET： 2-phenylethanethiol） also follows this growth pattern with partial removal of the layer. Theoreticalpredictions of relevant fcc nanoclusters include Au60（SCH3）36, Au68（SCH3）40, Au76（SCH3）44, etc, for the continuation of 1Dgrowth pattern, as well as Au68（SR）36 mediating the 2D growth pattern from Au44（TBBT）28 to Au92（TBBT）44. Overall, thismini-review provides guidelines on the rules of structural evolution of fcc gold nanoclusters based on 1D, 2D and 3Dgrowth patterns.
作者
HIGAKI Tatsuya
JIN Rongchao
HIGAKI Tatsuya, JIN Rongchao ＊(Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States)
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2018年第7期755-761,共7页
Acta Physico-Chimica Sinica
基金
The project was supported by the Air Force Office of Scientific Research (FA9550-15-1-0154) and the U.S. National Science Foundation (DMREF-0903225).
