ja506773d_si_002.cif (2.99 MB)

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

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posted on 05.11.2014, 00:00 by Shan Jin, Shuxin Wang, Yongbo Song, Meng Zhou, Juan Zhong, Jun Zhang, Andong Xia, Yong Pei, Man Chen, Peng Li, Manzhou Zhu
The crystal structure of the [Ag62S12(SBut)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(SBut)32 shell configuration interconnected by 12 sulfide ions, which is similar to the [Ag62S13(SBut)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 → 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.