Nestlike Silver(I) Thiolate Clusters with Tunable Emission Color Templated by Heteroanions.

Four silver thiolate clusters, [H3 O][(Ag3 S3 )(BF4 )@Ag27 (tBuS)18 (hfac)6 H2 O]⋅H2 O (1; hfac = hexafluoroacetylacetone), [(Ag3 S3 )(CF3 CO2 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅CF3 CO2 ⋅4 CH3 CN (2), [(Ag3 S3 )(MoO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅2 CH3 CN (3), and [(Ag3 S3 )(CrO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅4 CH3 CN (4), were isolated. They have similar nestlike structures assembled by an [Ag3 S3 ]3- template together with one of the BF4 - , CF3 CO2 - , MoO4 2- , or CrO4 2- anions. Interestingly, the solid-state emissions of 2-4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF3 CO2 - to MoO4 2- and to CrO4 2- , and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties.

Oxometalate and phosphine ligand co-protected silver nanoclusters: Ag28(dppb)6(MO4)4 and Ag32(dppb)12(MO4)4(NO3)4.

Thiols, alkynyls and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters, while oxometalates as inorganic ligands have almost been neglected in this field. Here, we used oxometalates (e.g., MoO42- and WO42-) as protecting ligands along with phosphines, such as 1,4-bis(diphenylphosphino)butane (dppb), to design and synthesize a new class of silver nanoclusters including Ag28(dppb)6(MoO4)4, Ag28(dppb)6(WO4)4 and Ag32(dppb)12(MoO4)4(NO3)4. Each cluster consists of a two-shell Ag4@Ag24 core protected by 4 oxometalates. These clusters exhibit similar optical absorption and photoluminescence properties that are not dependent on surface ligands. Furthermore, the electronic structure analysis shows that the clusters are 20-electron "superatoms". This work demonstrates that oxometalates can play a key role in the formation of silver nanoclusters, and the effect of oxometalates should be considered in the design and synthesis of metal nanoclusters.

An atomically precise all-tert-butylethynide-protected Ag51 superatom nanocluster with color tunability.

The tert-butylethynide ligand has been employed to construct an atomically precise all-tert-butylethynide-protected silver superatom nanocluster, Ag51(tBuC[triple bond, length as m-dash]C)32 (hereafter denoted as Ag51). The identity of Ag51 is confirmed by high resolution ESI-MS and elemental analysis. Single crystal X-ray analysis revealed that the structure of Ag51 features a three-shell arrangement, Ag@Ag8/Ag6@Ag36@C24/C8. Ag51 exhibits a strong solvatochromic effect, and the emissions are strongly dependent on the solvent polarity and are tunable from blue to red by changing the solvent from less polar dichloromethane to highly polar methanol.

High-Nuclearity Heterometallic tert-Butylethynide Clusters Assembled with tert-Butylphosphonate.

tert-Butylphosphonic acid and lanthanide precursors were employed to construct two high-nuclearity hybrid silver(I)-ytterbium(III) phosphonate clusters: compound 1 consists of a Ag16 ethynide cluster fused with a trinuclear hydroxoytterbium phosphonate cluster, whereas compound 2 is composed of two Ag16 ethynide clusters bridged by a hexanuclear oxo/hydroxoytterbium phosphonate cluster. Using transition-metal-substituted lacunary polyoxotungstates in place of the lanthanide reactant, new phosphonate-functionalized silver(I)-copper(II) ethynide clusters [Ag34 Cu6 (3) and Ag37 Cu6 (4)] and silver(I) ethynide clusters [Ag51 (5) and Ag72 (6)] were obtained. The structures of complexes 3-6 feature core-shell arrangements, in which silver(I)-copper(II) or silver(I) ethynide cluster shells stabilized by peripheral phosphonate ligands enclose different kinds of tungstate core templates.

Structure-Directing Role of Phosphonate in the Synthesis of High-Nuclearity Silver(I) Sulfide-Ethynide-Thiolate Clusters.

Phosphonate ligands as structure-directing components have been employed to construct four new high-nuclearity silver(I) sulfide-ethynide-thiolate clusters, in which silver(I) aggregates tBuC≡C⊃Ag3, tBuC≡C⊃Ag4, and 2tBuC≡C⊃Ag7 are bridged by tBuS- ligands to engender respective silver(I) ethynide-thiolate clusters functioning as integral shell components, which are supported by phosphonate ligands. In each silver(I) sulfide-ethynide-thiolate cluster, a different encapsulated silver sulfide cluster serves as a core template.