A platonic solid templating Archimedean solid: an unprecedented nanometre-sized Ag₃₇cluster

Abstract

The spontaneous formation of discrete spherical nanosized molecules is prevalent in nature, but the authentic structural mimicry of such highly symmetric polyhedra from edge sharing of regular polygons has remained elusive. Here we present a novel ball-shaped {(HNEt3)[Ag37S4(SC6H4(t)Bu)24(CF3COO)6(H2O)12]} cluster () that is assembled via a one-pot process from polymeric {(HNEt3)2[Ag10(SC6H4(t)Bu)12]}n and CF3COOAg. Single crystal X-ray analysis confirmed that is a Td symmetric spherical molecule with a [Ag36(SC6H4(t)Bu)24] anion shell enwrapping a AgS4 tetrahedron. The shell topology of belongs to one of 13 Archimedean solids, a truncated tetrahedron with four edge-shared hexagons and trigons, which are supported by a AgS4 Platonic solid in the core. Interestingly, the cluster emits green luminescence centered at 515 nm at room temperature. Our investigations have provided a promising synthetic protocol for a high-nuclearity silver cluster based on underlying geometrical principles.

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

“…All the Ag atoms on the ends are four-coordinated with at etrahedral geometry,w hereas the Ag atoms at the waist are linear two-coordination. The AgÀSb ond lengths rangesa re 2.414(2)-2.798(4), 2.4076(13)-2.6282 (12), 2.394(5)-2.667 (5), and 2.434(12)-2.918(3) i nc ompounds 1-4,r espectively.A ll the bond lengths anda ngles are within the range found for some other related clusters. [16] The averageA g···Ag short contacts (< 3.44 ) in compounds 1-4 are 3.14, 3.05, 3.17, and 3.10 , respectively,i ndicating the important signifi-Scheme1.Schematicrepresentation of the assembly of C 3 -symmetric Ag 9 twistedt rigonal-prisms.…”

“…Synthesis of compounds 1a nd 2:Am ixture of {(HNEt 3 ) 2 -[Ag 10 (SC 6 H 4 tBu) 12 ]} n (0.05 mmol, 13.7 mg), AgCF 3 SO 3 (0.07 mmol, 18.0 mg), and dpph (0.07 mmol, 31.8 mg) was dissolved in am ixture of DMF/CH 2 Cl 2 /CH 3 OH (4 mL, v/v/v = 1:1:1). The reaction mixture was sealed in a2 5mLT eflon-lined reaction vessel and heated to 65 8Cf or 5h,k ept at 65 8Cf or 33 h, and then slowly cooled to 30 8Cf or 13 h. Then the solution was filtered and the filtrate was evaporated slowly in darkness at room temperature.…”

“…Thus, how to assemble ah igh-symmetric silver-sulfur clusteri sap aramount challenge in synthetic chemistry.R ecently,w ee mployed au nderlying geometrical principle, Platonic and Archimedeans olids, [11] to assemblet he T d -symmetric [Ag 36 (SC 6 H 4 tBu) 24 ] À cluster,w hich is characterized as the first silver Keplerate formed by Platonic solid-templated Archimedeanb ody to date. [12] Its formation pavesapromising synthetic avenuef or high-symmetric clus-ters by direction of principles of solid geometry.F ollowing this work, we further explore the assembly strategy including Polyoxometalate templation to obtained new high-symmetric and high-nuclearity silver-sulfur clusters, [13] and herein, we developed ageneral route, that is, asynergetic high steric-hindrance capping ligand and al ong diphosphine bridge, to isolate four similar C 3 -symmetric Ag 9 clusters with at wisted trigonal-prism characteristic (Scheme1). This underlying principle is well-understoodb ys everal other single-crystal structures of new silver-sulfur clusters incorporating alteredc apping thiolate ligands and diphosphine bridges.T he temperature-dependent photoluminescence and electrochemistry properties are also discussed.…”

Three Silver Nests Capped by Thiolate/Phenylphosphonate

“…[12] However,s ilver-centered silver thiolate nests like SD/Ag73a are rare and only observed in af ew examples, such as our previously reported [Ag 1 @S 4 @Ag 36 ]. [13] The different innermost ionic species( Ag + vs. S 2À )i ns uch multishell structures may suggest different growth routes in solution.…”

“…The ESI-MS of SD/Ag66a shows two dominant fragment peaks centered at m/z 5486.850a nd 5460.330 in the m/z range of 5200-5800, which can be assigned to [Ag 63 S 6 (tBuS) 20 (PPA) 13 (CN) 3 (CH 3 OH) 3 ] 2 + (2a,c alcd m/z 5486.875) and [Ag 63 S 6 (tBuS) 21 (PPA) 12 (CN) 4 (CH 3 OH) 2 (H 2 O)] 2 + (2b,c alcd m/z 5460.391), respectively (Figure 4b). These resultsd emonstrate that the 1D Ag 64 nest-based structure of SD/Ag66 a decomposes to the discrete nest nodes with the loss of one silver atom when dissolved in methanol.…”