Crystal Structure and Optical Properties of the [Ag62S12(SBut)32]2+ Nanocluster with a Complete Face-Centered Cubic Kernel

详细信息    查看全文

• 作者：Shan Jin ; Shuxin Wang ; Yongbo Song ; Meng Zhou ; Juan Zhong ; Jun Zhang ; Andong Xia ; Yong Pei ; Man Chen ; Peng Li ; Manzhou Zhu
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：November 5, 2014
• 年：2014
• 卷：136
• 期：44
• 页码：15559-15565
• 全文大小：449K
• ISSN：1520-5126

文摘

The crystal structure of the [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ nanocluster (denoted as NC-I) has been successfully determined, and it shows a complete face-centered-cubic (FCC) Ag₁₄ core structure with a Ag₄₈(SBu^t)₃₂ shell configuration interconnected by 12 sulfide ions, which is similar to the [Ag₆₂S₁₃(SBu^t)₃₂]⁴⁺ structure (denoted as NC-II for short) reported by Wang. Interestingly, NC-I exhibits prominent differences in the optical properties in comparison with the case of the NC-II nanocluster. We employed femtosecond transient absorption spectroscopy to further identify the differences between the two nanoclusters. The results show that the quenching of photoluminescence in NC-I in comparison to that of NC-II is caused by the free valence electrons, which dramatically change the ligand to metal charge transfer (LMCT, S 3p 鈫?Ag 5s). To get further insight into these, we carried out time-dependent density functional theory (TDDFT) calculations on the electronic structure and optical absorption spectra of NC-I and NC-II. These findings offer a new insight into the structure and property evolution of silver cluster materials.