Johnson Solids: Anion‐Templated Silver Thiolate Clusters Capped by Sulfonate

Sulfonates were incorporated into six novel high‐nuclearity silver(I) thiolate clusters under the guidance of anion templates varied from S2−, SO42−, α‐[Mo5O18]6−, β‐[Mo5O18]6−, [Mo2O8]4−, to [Mo4O14(SO4)]6−. Single crystal X‐ray analysis revealed that SD/Ag1, SD/Ag3, SD/Ag5, and SD/Ag6 are discrete [S@Ag60], [α‐Mo5O18@Ag36], [Mo2O8@Ag30]2, and [Mo4O14(SO4)@Ag73] clusters, respectively, whereas SD/Ag2 and SD/Ag4 are one‐dimensional (1D) chains based on the [SO4@Ag20] and [β‐Mo5O18@Ag36] cluster subunits, respectively. Their silver skeletons are protected exteriorly by thiolates and sulfonates and interiorly supported by diverse anions as templates. Structurally, cluster SD/Ag1 is a typical core–shell structure comprised of an inner Ag12 cuboctahedron and an outer Ag48 shell. The sulfate‐templated drum‐like Ag20 cluster subunits are bridged by PhSO3− to give a 1D chain of SD/Ag2. Complex SD/Ag3 and SD/Ag4 are spindle‐like Ag36 clusters with isomeric [Mo5O18]6− inside, and the latter is further extended to a 1D chain through PhSO3− bridges. A pair of [Mo2O8]4− templated gourd‐like Ag30 clusters are dimerized in a head‐to‐head fashion to form SD/Ag5. Complex SD/Ag6 is the largest cluster in this family and doubly templated by unprecedented [Mo4O14(SO4)]6− anions. Geometrically, the silver shells of SD/Ag1–SD/Ag5 show the polyhedral features of Johnson solids, instead of the usual Platonic or Archimedean solids. Solution behaviors and luminescent properties were also investigated in detail. Solid silver: The sulfonates were successfully incorporated into six novel high‐nuclearity silver(I) thiolate clusters under the guidance of diverse anion templates. Their silver shells show the polyhedral features of Johnson solids instead of usual Platonic or Archimedean solids.