Au25(SEt)18, a Nearly Naked Thiolate-Protected Au25 Cluster: Structural Analysis by Single Crystal X-ray Crystallography and Electron Nuclear Double Resonance

被引:136
作者
Dainese, Tiziano [1 ]
Antonello, Sabrina [1 ]
Gascon, Jose A. [2 ]
Pan, Fangfang [4 ]
Perera, Neranjan V. [2 ]
Ruzzi, Marco [1 ]
Venzo, Alfonso [1 ,3 ]
Zoleo, Alfonso [1 ]
Rissanen, Kari [4 ]
Maran, Flavio [1 ]
机构
[1] Univ Padua, Dept Chem, I-35131 Padua, Italy
[2] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA
[3] Univ Padua, Dept Chem, IENI CNR, I-35131 Padua, Italy
[4] Univ Jyvaskyla, Nanosci Ctr, Dept Chem, Jyu 40014, Finland
基金
芬兰科学院; 美国国家科学基金会;
关键词
gold nanoclusters; Au-25; Au-25(SEt)(18); X-ray crystallography; ENDOR; paramagnetism; GOLD NANOPARTICLE; AU-38; NANOPARTICLES; MAGNETIC-RESONANCE; OPTICAL-PROPERTIES; MASS-SPECTROMETRY; PROGRAM SYSTEM; CHARGE-STATE; NANOCLUSTER; RESOLUTION; AU-130;
D O I
10.1021/nn500805n
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
X-ray crystallography has been fundamental in discovering fine structural features of ultrasmall gold clusters capped by thiolated ligands. For still unknown structures, however, new tools capable of providing relevant structural information are sought. We prepared a 25-gold atom nanocluster protected by the smallest ligand ever used, ethanethiol. This cluster displays the electrochemistry, mass spectrometry, and UV-vis absorption spectroscopy features of similar Au-25 clusters protected by 18 thiolated ligands. The anionic and the neutral form of Au-25(SEt)(18) were fully characterized by H-1 and C-13 NMR spectroscopy, which confirmed the monolayer's properties and the paramagnetism of neutral Au-25(SEt)(18)(0). X-ray crystallography analysis of the latter provided the first known structure of a gold cluster protected by a simple, linear alkanethiolate. Here, we also report the direct observation by electron nuclear double resonance (ENDOR) of hyperfine interactions between a surface-delocalized unpaired electron and the gold atoms of a nanocluster. The advantages of knowing the exact molecular structure and having used such a small ligand allowed us to compare the experimental values of hyperfine couplings with DFT calculations unaffected by structure's approximations or omissions.
引用
收藏
页码:3904 / 3912
页数:9
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