Silver Clusters Coprotected by Different Diphosphine and Thiol Ligands

Abstract

The diphosphine ligands can act as auxiliary ligands for the thiol ligands to generate novel silver clusters. Here, we report five silver thiolated clusters protected by diphosphine ligands, namely, [Ag 11 ( i PrS) 9 (dppm) 3 ](BPh 4 ) 2 (1, dppm = bis-(diphenylphosphino)methane), S@Ag 26 ( i PrS) 16 (CF 3 COO) 8 (dpph) 2 •3DMF (2, dpph = 1,6-bis(diphenylphosphino)hexane), S@Ag 26 ( i PrS) 16 (CF 3 COO) 8 (dpppe) 2 •2DMF (3, dpppe = 1,5-bis(diphenylphosphino)pentane), AgS 2 @Ag 24 ( t BuS) 18 (dpppe) 2 (BF 4 ) 3 (4), and [SO 4 @Ag 20 ( i PrS) 10 (CF 3 COO) 8 (dpphS 2 ) 2 ] n (5, dpphS 2 = 1,6-bis(diphenylphosphino)hexane disulfide). Their structures were characterized by single-crystal X-ray diffraction, which revealed that 1 presents a triangular structure covered by three diphosphine ligands, and there are strong C−H•••π interactions between clusters and between clusters and counterions. Clusters 2 and 3 are olive-shaped structures, and cluster 4 is a box-type structure. Clusters 2−4 all have two diphosphine ligands at both ends. Cluster 5 is a chainlike structure connected by dpphS 2 . Among them, cluster 1 exhibits photoluminescence (PL) properties, and the emission of its solution phase is red-shifted compared to the crystalline state.

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.…”

“…Anions, as opposed to cations and neutral templates, have attracted the attention of more and more scientists in recent decades, using them to regulate the formation of cluster compounds and to determine the size and shape of the resulting clusters [37] . The anion mainly contains halogen ions, [38] oxyacid anions/polyanions (such as CrO 4 2− , [39,40] CO 3 2− , [41–50] NO 3 − , [51] MoO 4 2− , [35] [Mn III Mn IV 2 Mo 14 O 56 ] 17− , [52] Mo 6 O 22 8− , [53] [Mo 20 O 66 ] 12− , [54] [EuW 10 O 36 ] 9− , [55] VO 4 3− , [56] AsO 4 3− , [57] SO 4 2− , [58,59] P 5 W 30 , [60] [V 10 O 28 ] 6−[61] ), and organic anions (C 4 O 4 2− , [62] C 2 O 4 2−[63] ), etc. Among them, the carbonate ion (CO 3 2− ) is a perfect anion template.…”