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

Abstract

Sulfonates were incorporated into six novel high-nuclearity silver(I) thiolate clusters under the guidance of anion templates varied from S^2- , SO₄^2- , α-[Mo₅ O₁₈ ]^6- , β-[Mo₅ O₁₈ ]^6- , [Mo₂ O₈ ]^4- , to [Mo₄ O₁₄ (SO₄ )]^6- . Single crystal X-ray analysis revealed that SD/Ag1, SD/Ag3, SD/Ag5, and SD/Ag6 are discrete [S@Ag₆₀ ], [α-Mo₅ O₁₈ @Ag₃₆ ], [Mo₂ O₈ @Ag₃₀ ]₂ , and [Mo₄ O₁₄ (SO₄ )@Ag₇₃ ] clusters, respectively, whereas SD/Ag2 and SD/Ag4 are one-dimensional (1D) chains based on the [SO₄ @Ag₂₀ ] and [β-Mo₅ O₁₈ @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 [Mo₅ O₁₈ ]^6- inside, and the latter is further extended to a 1D chain through PhSO₃^- bridges. A pair of [Mo₂ O₈ ]^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 [Mo₄ O₁₄ (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.

Keywords: Johnson solids; luminescence; silver(I) cluster; solution behavior.