Molecular electron-transfer properties of Au38 clusters

被引:76
作者
Antonello, Sabrina [1 ]
Holm, Allan H. [1 ]
Instuli, Emanuele [1 ]
Maran, Flavio [1 ]
机构
[1] Univ Padua, Dept Chem, I-35131 Padua, Italy
关键词
D O I
10.1021/ja071191+
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The electron transfer (ET) properties of Au-38 clusters protected by a phenylethanethiolate monolayer, Au-38(SR)(24), were studied in N,N-dimethylformamide and dichloromethane. The kinetic parameters of the first oxidation steps (+1/0 and +2/+1) and the first reduction step (0/-1) were obtained by electrochemical methods. The anion electrogenerated from Au-38(SR)(24) was employed in homogeneous redox catalysis experiments, using diphenyl disulfide and benzyl bromide as the acceptors. Both the heterogeneous and the homogeneous analyses pointed to the fast ET behavior typical for the formation and reactivity of delocalized ionic species with small intrinsic barriers. The results show that Au-38 clusters are in all respects efficient redox molecules.
引用
收藏
页码:9836 / +
页数:3
相关论文
共 25 条
[1]   HOMOGENEOUS REDOX CATALYSIS OF ELECTROCHEMICAL REACTIONS - ELECTRON TRANSFERS FOLLOWED BY A VERY FAST CHEMICAL STEP [J].
ANDRIEUX, CP ;
SAVEANT, JM .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1986, 205 (1-2) :43-58
[2]   Gold nanoelectrodes of varied size: Transition to molecule-like charging [J].
Chen, SW ;
Ingram, RS ;
Hostetler, MJ ;
Pietron, JJ ;
Murray, RW ;
Schaaff, TG ;
Khoury, JT ;
Alvarez, MM ;
Whetten, RL .
SCIENCE, 1998, 280 (5372) :2098-2101
[3]   Electron self-exchange between Au140+/0 nanoparticles is faster than that between Au38+/0 in solid-state, mixed-valent films [J].
Choi, Jai-Pil ;
Murray, Royce W. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (32) :10496-10502
[4]   Investigation of the direct and indirect reduction processes of some disulfides by electrochemical means [J].
Christensen, TB ;
Daasbjerg, K .
ACTA CHEMICA SCANDINAVICA, 1997, 51 (03) :307-317
[5]   THE NUCLEOPHILICITY OF SUPEROXIDE TOWARDS DIFFERENT ALKYL-HALIDES ESTIMATED FROM KINETIC MEASUREMENTS [J].
DAASBJERG, K ;
LUND, H .
ACTA CHEMICA SCANDINAVICA, 1993, 47 (06) :597-604
[6]   Gold nanoparticles: Assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology [J].
Daniel, MC ;
Astruc, D .
CHEMICAL REVIEWS, 2004, 104 (01) :293-346
[7]   Synthesis and isolation of the molecule-like cluster Au38(PhCH2CH2S)24 [J].
Donkers, RL ;
Lee, D ;
Murray, RW .
LANGMUIR, 2004, 20 (05) :1945-1952
[8]  
F Allen J Bard L.R., 2001, Electrochemical Methods: Fundamentals and Applications
[9]   SECM measurement of the fast electron transfer dynamics between Au381+ nanoparticles and aqueous redox species at a liquid/liquid interface [J].
Georganopoulou, DG ;
Mirkin, MV ;
Murray, RW .
NANO LETTERS, 2004, 4 (09) :1763-1767
[10]   Substituent effects on redox potentials and optical gap energies of molecule-like Au38(SPhX)24 nanoparticles [J].
Guo, R ;
Murray, RW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (34) :12140-12143