Intramolecular Charge Transfer and Solvation Dynamics of Thiolate-Protected Au20(SR)16 Clusters Studied by Ultrafast Measurement

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• 作者：Meng Zhou ; Silvije Vdovi膰 ; Saran Long ; Manzhou Zhu ; Linyin Yan ; Yingying Wang ; Yingli Niu ; Xuefei Wang ; Qianjin Guo ; Rongchao Jin ; Andong Xia
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：October 10, 2013
• 年：2013
• 卷：117
• 期：40
• 页码：10294-10303
• 全文大小：565K
• 年卷期：v.117,no.40(October 10, 2013)
• ISSN：1520-5215

文摘

It is accepted that the monolayer ligand shell in monolayer-protected gold nanoclusters (MPCs) plays an important role in stabilizing the metal core structure. Previous reports have shown that the core and shell do not interact chemically, and very few studies investigating the intramolecular charge transfer (ICT) between the core and ligand shell in clusters have been reported. The underlying excited state relaxation mechanisms about the influence of solvents, the optically excited vibration, and the roles of the core and shell in charge transfer remain unknown to a large extent. Here we report a femtosecond transient absorption study of a Au₂₀(SR)₁₆ (R = CH₂CH₂Ph) cluster in toluene and tetrahydrofuran. The ICT from the outside shell to the inside core upon excitation in Au₂₀(SR)₁₆ is identified. The observed solvation-dependent oscillations in different solvents further confirm the photoinduced ICT formation in Au₂₀(SR)₁₆. The results provide a fundamental understanding of the structure鈥損roperty relationships about the solvation-dependent core鈥搒hell interaction in Au MPCs.