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-, alpha-[Mo5O18](6-), beta-[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@Ag-60], [-Mo5O18@Ag-36], [Mo2O8@Ag-30](2), and [Mo4O14(SO4)@Ag-73] clusters, respectively, whereas SD/Ag2 and SD/Ag4 are one-dimensional (1D) chains based on the [SO4@Ag-20] and [-Mo5O18@Ag-36] 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 Ag-12 cuboctahedron and an outer Ag-48 shell. The sulfate-templated drum-like Ag-20 cluster subunits are bridged by PhSO3- to give a 1D chain of SD/Ag2. Complex SD/Ag3 and SD/Ag4 are spindle-like Ag-36 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 Ag-30 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.