Structure of the ligated Ag60 nanoparticle [{Cl@Ag12}@Ag48(dppm)12] (where dppm=bis(diphenylphosphino)methane)

Abstract

A novel bisphosphine ligated Ag60 nanocluster, [{Cl@Ag12}@Ag48(dppm)12], has been discovered and characterized by X-ray crystallography. It consists of a central chloride located inside an icosahedral silver core layer, which is further encased by a second shell of 48 silver atoms/ions, which are capped with 12 bis(diphenylphosphino)methane (dppm) ligands. Due to lack of sufficient material the cluster could not be further characterized by other methods. DFT calculations were carried out on the cation [{Cl@Ag12}@Ag48(dppm)12]+ to determine if it corresponds to a superatom with a core count of n=58. The DFT optimized structure is in agreement with X-ray findings, but the low value of the HOMO-LUMO gap does not support superatom stability.

Recent progress in dichalcophosphate coinage metal clusters and superatoms

“…It should be remarked that the Ag 12 (μ 12 -Br) pattern is unprecedented, and μ 12 -X coordination is overall very uncommon in the literature. Apart from the above-discussed clusters, it was found only in [(μ 12 -Cl)@Ag 12 @Ag 48 (dppm) 12 ] 129 and [{TpMo(μ 3 -S) 4 Cu 3 } 4 (μ 12 -I)] − . 130…”

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

“…photoluminescence 35. A deeper understanding of the electronic structure is required for practical applications using their size-specific physicochemical properties.36−38 In this study, we synthesized three new anion-templated Ag NCs (1−3) containing a sulfide ion (S 2− )39 or a chloride ion (Cl − )40 as template anions by controlling the amount of thiol, reduction time, or the presence of countercations during synthesis. Single-crystal X-ray diffraction (SC-XRD) and electron spin resonance (ESR) spectroscopy revealed that clusters 1−3 have the chemical compositions [S@Ag 17 (S-4CBM) 15 (PPh 3 ) 5 ] 0 [1; S-4CBM = 4-chlorobenzene methanethiolate (Scheme S1a)], [S@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ] 0 (2), and [Cl@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ][PPh 4 ] (3) (Table1).…”

Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

“…Br–Cu: 2.977 Å (R = n Bu, R′ = C 2 Ph)), 14 [(μ 12 -Cl)@Ag 12 @Ag 48 (dppm) 12 ] (avg. Cl–Ag: 2.917 Å), 19 and [{TpMo(μ 3 -S) 4 Cu 3 } 4 (μ 12 -I)] − (avg. I–Cu: 3.195 Å).…”