title: Crystal structure and optical properties of the [Ag62S12(SBu(t))32](2+) nanocluster with a complete face-centered cubic kernel.
abstract: 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 → 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.
authors.affiliation: Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Anhui University , Hefei, Anhui 230601, People's Republic of China.
authors.forename: Shan
authors.initials: S
authors.lastname: Jin
authors.forename: Shuxin
authors.initials: S
authors.lastname: Wang
authors.forename: Yongbo
authors.initials: Y
authors.lastname: Song
authors.forename: Meng
authors.initials: M
authors.lastname: Zhou
authors.forename: Juan
authors.initials: J
authors.lastname: Zhong
authors.forename: Jun
authors.initials: J
authors.lastname: Zhang
authors.forename: Andong
authors.initials: A
authors.lastname: Xia
authors.forename: Yong
authors.initials: Y
authors.lastname: Pei
authors.forename: Man
authors.initials: M
authors.lastname: Chen
authors.forename: Peng
authors.initials: P
authors.lastname: Li
authors.forename: Manzhou
authors.initials: M
authors.lastname: Zhu
mesh_terms: D018360:Crystallography, X-Ray; D015394:Molecular Structure; D049329:Nanostructures; D066244:Proton Magnetic Resonance Spectroscopy; D018030:Silver Compounds / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013057:Spectrum Analysis / Q000379:methods*
chemical_list: D018030:Silver Compounds