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.

Energy transfer and spectroscopic characterization of a perylenetetracarboxylic diimide (PDI) hexamer

“…20,21 Briefly, a regeneratively amplified Ti:sapphire laser (Coherent Legend Elite) produces 40 fs, 1 mJ pulses at a 500 Hz repetition rate with a spectrum centered at 800 nm and a bandwidth of 40 nm (FWHM). The output from the amplifier is split by a 90/10 beamsplitter into pump and probe beams.…”

A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

“…The photophysics of the cluster were recently cemented by Zhu and coworkers [8] with an in-depth structure-property relationship study of it and the related framework [Ag 62 S 12 (S t Bu) 32 ] 2+ , which contains a "metallic" core. These studies complement recent findings showing how silver-thiolate surfaces can stabilize larger Ag cores in atomically precise nanoclusters.…”

[Ag115S34(SCH2C6H4tBu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster

“…Only a very few 1 H NMR but no heteronuclear measurements were reported. 8 In general, these studies give only little insight into the properties of coinage metal chalcogenide clusters in solution.…”