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

Four silver thiolate clusters, [H O][(Ag S )(BF )@Ag (tBuS) (hfac) H O]⋅H O (1; hfac = hexafluoroacetylacetone), [(Ag S )(CF CO )@Ag (tBuS) (CF CO ) (CH CN) ]⋅CF CO ⋅4 CH CN (2), [(Ag S )(MoO )@Ag (tBuS) (CF CO ) (CH CN) ]⋅2 CH CN (3), and [(Ag S )(CrO )@Ag (tBuS) (CF CO ) (CH CN) ]⋅4 CH CN (4), were isolated. They have similar nestlike structures assembled by an [Ag S ] template together with one of the BF , CF CO , MoO , or CrO 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 CF CO to MoO and to CrO , 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.