T‐symmetric 40‐nucleus silver clusters assembled by hetero‐anions. Issue 12 (20th May 2020)

• Record Type: Journal Article
• Authors: Liao, Jian‐Hong; Chang, Hao‐Wei; Fang, Ching‐Shiang; Liu, C. W.
• Is Part Of: Journal of the Chinese Chemical Society. Volume 67:Issue 12(2020)
• Page Start: 2163
• Page End: 2170
• Publication Date: 2020-05-20
• Subjects: hetero‐anion -- silver cluster -- T symmetry -- template; Chemistry -- Periodicals; Electronic journals; 540.5
• DOI: 10.1002/jccs.202000071
• Languages: English
• ISSNs: 0009-4536

Abstract

Abstract: We report two anion‐templated Ag40 clusters, [Ag40 (E)4 (SO4 ){S2 P(OEt)2 }24 ](PF6 )6 (E = S, 1 ; Se, 2 ). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag40 clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six‐coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near‐equivalent [Ag10 (E){S2 P(OEt)2 }6 ] 2+ motifs were assembled via the connection of central sulfate anion to construct Ag40 clusters. The cluster cation, [Ag40 (E)4 (SO4 ){S2 P(OEt)2 }24 ] 6+, displayed in T symmetry, is unprecedented in anion‐templated silver clusters. Abstract : Two Ag40 clusters, [Ag40 (E)4 (SO4 ){S2 P(OEt)2 }24 ](PF6 )6 (E = S, 1 ; Se, 2 ), were assembled by multiple hetero‐anions as templates. The central sulfate anion displayed a rare dodecametallic dodecaconnective coordination pattern to connect four [Ag10 (E){S2 P(OEt)2 }6 ] 2+ motifs in the formation of Ag40 clusters of T ‐symmetry.