Anion-templated nanosized silver clusters protected by mixed thiolate and diphosphine

• Published in: Nanoscale 2017-03, Vol.9 (10), p.3601-3608
• Main Authors: Li, Xiao-Yu, Wang, Zhi, Su, Hai-Feng, Feng, Sheng, Kurmoo, Mohamedally, Tung, Chen-Ho, Sun, Di, Zheng, Lan-Sun
• Format: Article
• Language: English
• Subjects: Buildings; Clusters; Construction materials; Ligands; Molecular structure; Nanostructure; Stability analysis; Thermochromism
• ISSN: 2040-3364; 2040-3372
• DOI: 10.1039/c6nr09632h

S , MoO , and Mo O were successfully employed as templates in the formation of six high-symmetry polynuclear silver clusters as exemplified in the single-crystal X-ray structures of [S@Ag ( BuC H S) (dppp) ]·DMF·5CH CN·3CH OH (1), [MoO @Ag (MeC H S) (dppm) (MoO ) ]·2BF ·C H NO (2), [MoO @Ag (MeC H S) (dppm) (MoO ) ]·2CF SO (3), [MoO @Ag (MeC H S) (dppf) (MoO ) ]·2CF SO (4), [MoO @Ag (MeC H S) (dppb) (MoO ) ]·2CF SO (5) and [Mo O @Ag ( BuC H S) (dppm) (CH CN) ]·6CF SO (6) (dppp = 1,3-bis(diphenylphosphino)propane, dppm = bis(diphenylphosphino)methane, dppf = 1,1'-bis(diphenylphosphino)ferrocene and dppb = 1,4-bis(diphenylphosphino)butane). Cluster 1 is a S -centered octadecanuclear banana-shaped molecule. Clusters 2-5 have similar structures consisting of a tetrahedron of a MoO core and four MoO where three silver atoms cap each face and a pair sits on each edge, giving tetraicosanuclear ball-shaped molecules. Although different diphosphine ligands and silver salts were used in the syntheses, 2-5 contain a common building cluster unit with similar geometry and nuclearity. With (Bu N) Mo O as a template, a giant 46-silver-atom cluster encapsulates an in situ modified Mo O unit. The nuclearity and geometry depend on the size and shape of the templates. High-resolution electrospray mass spectrometry (HR-ESI-MS) analyses of 4 indicate its exceptionally high stability in acetonitrile. The solid-state luminescence of 1 as a function of the temperature exhibits thermochromism from red to yellow due to the different intensities of the two bands. This work established a new strategy for the construction of polynuclear silver clusters using an anionic template and mixed S- and P-donor ligands where a promising approach for building novel dual emissive materials is unraveled.