Oxocarbon Anions Templated in Silver Clusters

Abstract

Three types of oxocarbon anions as templates were used to synthesize high-nuclear silver clusters, [Ag16(C2O4)­{S2P­(OEt)2}12]2(PF6)4 (1), [Ag16(C4O4)­{S2P­(OEt)2}12]2(PF6)4 (2), and [Ag32(S)2(C5O5)2{S2P­(OEt)2}22]­(PF6)2 (3), and characterized by multi-NMR spectroscopy and X-ray crystallography. As the template size increases, the shape and size of the clusters change accordingly. The template effect in high-nuclear silver clusters has been investigated in this work.

Recent progress in dichalcophosphate coinage metal clusters and superatoms

“…For example, the action of [C 2 O 4 ] 2− or [C 4 O 4 ] 2− anions to the generated in situ polymer resulted in the assembly of anion-templated clusters [Ag 16 (C n O 4 ){S 2 P(OEt) 2 } 12 ] 2 (PF 6 ) 4 ( n = 2 or 4), while a bigger [C 5 O 5 ] 2− anion produced another cluster [Ag 32 (S) 2 (C 5 O 5 ) 2 {S 2 P(OEt) 2 } 22 ](PF 6 ) 2 . 135 The cluster [Ag 16 (C n O 4 )L 12 ] 2 (PF 6 ) 4 has a dimeric structure built from two anion-centred tetracapped distorted icosahedrons, the size of which is larger in the case of a larger [C 4 O 4 ] 2− anion (Fig. 17).…”

“…Fig. 17 Cationic structures of (a) [Ag 16 (C 2 O 4 ){S 2 P(OEt) 2 } 12 ] 2 (PF 6 ) 4 , (b) [Ag 16 (C 4 O 4 ){S 2 P(OEt) 2 } 12 ] 2 (PF 6 ) 4 , and (c) [Ag 32 (S) 2 (C 5 O 5 ) 2 {S 2 P(OEt) 2 } 22 ](PF 6 ) 2 .Reproduced with permission 135. Copyright 2022, American Chemical Society.…”

Heterometallic AuI6AgI6 Macrocyclic Cluster Templated by a Supramolecular Melamine Dimer

“…[11] Non-covalent interactions between the peripheral ligand shells of coinage-metal clusters are often found important for the stability of the clusters. [12] Based on our previous effort on the assembly of silver clusters with planar organic anion templates such as squarate (C 4 O 4 2À ) [13] and croconate (C 5 O 5 2À ), [14] which showed non-negligible π interactions in the clusters, we paid our attention to melamine that has symmetric binding sites and the potential to form supramolecular interactions between melamines (Scheme 1). Our attempts led to the unexpected formation of an interesting supramolecular melamine dimer inside the cluster, which is important for the construction of heterometallic coinage-metal clusters.…”

Carboxylate Ligand‐supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

“…2À , [39,40] CO 3 2À , [41][42][43][44][45][46][47][48][49][50] NO 3 À , [51] MoO 4 2À , [35] [Mn III Mn IV 2 Mo 14 O 56 ] 17À , [52] Mo 6 O 22 8À , [53] [Mo 20 O 66 ] 12À , [54] [EuW 10 O 36 ] 9À , [55] VO 4 3À , [56] AsO 4 3À , [57] SO 4 2À , [58,59] P 5 W 30 , [60] [V 10 O 28 ] 6À [61] ), and organic anions (C 4 O 4 2À , [62] C 2 O 4 2À [63] ), etc. Among them, the carbonate ion (CO 3 2À ) is a perfect anion template.…”