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

Abstract

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.