title: Anion-templated nanosized silver clusters protected by mixed thiolate and diphosphine.
abstract: S2-, MoO42-, and Mo6O228-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@Ag18(tBuC6H4S)16(dppp)4]·DMF·5CH3CN·3CH3OH (1), [MoO4@Ag24(MeC6H4S)12(dppm)6(MoO4)4]·2BF4·C2H5NO (2), [MoO4@Ag24(MeC6H4S)12(dppm)6(MoO4)4]·2CF3SO3(3), [MoO4@Ag24(MeC6H4S)12(dppf)6(MoO4)4]·2CF3SO3(4), [MoO4@Ag24(MeC6H4S)12(dppb)6(MoO4)4]·2CF3SO3(5) and [Mo6O22@Ag46(tBuC6H4S)32(dppm)4(CH3CN)8]·6CF3SO3(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 S2--centered octadecanuclear banana-shaped molecule. Clusters 2-5 have similar structures consisting of a tetrahedron of a MoO42-core and four MoO42-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 (Bu4N)2Mo6O19as a template, a giant 46-silver-atom cluster encapsulates an in situ modified Mo6O228-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.
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. dsun@sdu.edu.cn.
authors.forename: Xiao-Yu
authors.initials: XY
authors.lastname: Li
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. dsun@sdu.edu.cn.
authors.forename: Zhi
authors.initials: Z
authors.lastname: Wang
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic ofChina.
authors.forename: Hai-Feng
authors.initials: HF
authors.lastname: Su
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. dsun@sdu.edu.cn.
authors.forename: Sheng
authors.initials: S
authors.lastname: Feng
authors.affiliation: Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS-UMR 7177, 4 rue Blaise Pascal, 67008 Strasbourg Cedex, France.
authors.forename: Mohamedally
authors.initials: M
authors.lastname: Kurmoo
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. dsun@sdu.edu.cn.
authors.forename: Chen-Ho
authors.initials: CH
authors.lastname: Tung
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. dsun@sdu.edu.cn.
authors.forename: Di
authors.identifier: http://orcid.org/0000-0001-5966-1207
authors.initials: D
authors.lastname: Sun
authors.affiliation: Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic ofChina.
authors.forename: Lan-Sun
authors.initials: LS
authors.lastname: Zheng