A Sodalite‐Type Silver Orthophosphate Cluster in a Globular Silver Nanocluster

Abstract

The synthesis and structure of a giant 102‐silver‐atom nanocluster (NC) 1 is presented. X‐ray structural analysis reveals that 1 features a multi‐shelled metallic core of Ag6@Ag24@Ag60@Ag12. An octahedral Ag6 core is encaged by a truncated octahedral Ag24 shell. The Ag24 shell is composed of a hitherto unknown sodalite‐type silver orthophosphate cluster (SOC) {(Ag3PO4)8}, reminiscent of the Ag3PO4 photocatalyst. The SOC is capped by six interstitial sulfur atoms, giving a unique anionic cluster [Ag6@{(Ag3PO4)8}S6]6−, which functions as an intricate polyhedral template with abundant surface O and S atoms guiding the formation of a rare rhombicosidodecahedral Ag60 shell. An array of 6 linear Ag2 staples further surround this Ag60 shell. [Ag6@{(Ag3PO4)8}S6]6− is an unusual Ag‐based templating anion to induce the assembly of a SOC within silver NC. This finding provides molecular models for bulk Ag3PO4, and offers a fresh template strategy for the synthesis of silver NCs with high symmetry.

Trapping a [W10O32]6− Decatungstate Anion in an Ag44 Nanowheel

“…The absorption peak at 664 nm of the MB solution decreases largely in the presence of 1 as catalyst, namely, the maximal absorbance at 664 nm decreased from 1.76 to 0.15 and turned broadened with prolonging the irradiation time. In addition, compound 1 reduces the MB concentration by 91.5% after irradiation for 420 min [40–41] . For comparison, a blank experiment shows that the photocatalytic decomposition rate of MB can be improved in the presence of compound 1 , and the photocatalytic activity of compound 1 is comparable to ( n Bu 4 N) 4 [W 10 O 32 ].…”

“…In addition, compound 1 reduces the MB concentration by 91.5% after irradiation for 420 min. [40][41] For comparison, a blank experiment shows that the photocatalytic decomposition rate of MB can be improved in the presence of compound 1, and the photocatalytic activity of compound 1 is comparable to ( n Bu 4 N) 4 [W 10 O 32 ]. As observed in many catalytic systems, hypsochromic shifts of the maximum absorption peaks of MB solutions were also observed using ( n Bu 4 N) 4 [W 10 O 32 ] as catalyst (Figure S6), which is attributed to the generation of thionine that is one of the N-demethylated intermediates of MB.…”

Protection of Ag Clusters by Metal‐Oxo Modules

“…Therefore, the conventional organic ligands used to stabilize silver nanoclusters are phosphines, thiolates, alkynyls and some pyridines. [16][17][18][19] Notwithstanding, the instability of such silver clusters has troubled the synthetic chemists and seriously hindered their full characterization and utility. [20] Meanwhile, metal-oxo modules had been largely ignored for a long time in this field due to the hard-base attribute of oxygen atoms.…”

Threefold Collaborative Stabilization of Ag14‐Nanorods by Hydrophobic Ti16‐Oxo Clusters and Alkynes: Designable Assembly and Solid‐State Optical‐Limiting Application

“…[8] Research efforts to enhance Ag cluster stability have been focused on introducing the surface organic ligands,s uch as thiolates,p hosphines, pyridines,a sw ell as some O-donor ligands like carboxylate and calixarene. [9][10][11][12][13] Notwithstanding,t he records of stable atomically precise Ag clusters under ambient conditions remains very limited. [14][15][16][17] In the field of noble metal catalysts,m etal oxides (for example,T iO 2 )h ave been extensively used as substrates to stabilize small noble metal nanoparticles (NPs) owning catalytic sites under long-term catalysis.…”

“…However, the inherent instability of Ag nanoclusters has seriously hindered their full characterization and utility [8] . Research efforts to enhance Ag cluster stability have been focused on introducing the surface organic ligands, such as thiolates, phosphines, pyridines, as well as some O‐donor ligands like carboxylate and calixarene [9–13] . Notwithstanding, the records of stable atomically precise Ag clusters under ambient conditions remains very limited [14–17] …”