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Two silver-rich M 20 alloy nanoclusters (NCs), [Cu 3.5 Ag 16.5 {S 2 P(O n Pr) 2 } 12 ] ( 1 ) and [Cu 2.5 AuAg 16.5 {S 2 P(O n Pr) 2 } 12 ] ( 2 ), were synthesized and fully characterized by electrospray ionization mass spectrometry, NMR spectroscopy, and X-ray crystallography. Cluster 2 , the first structurally characterized trimetallic M 20 NC, was produced by doping one Au atom into a bimetallic M 20 NC. Structural analyses showed the preferred positions of Group 11 metals in the yielded M 20 NCs. Their antioxidation ability has been investigated, and the time-dependent UV-vis spectrum shows that the presence of Cu I atoms in structures 1 and 2 can improve the antioxidant ability.

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal‐pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed‐valent [AuCu11]10+ metal core, making it a two‐electron superatom. [ABSTRACT FROM AUTHOR]

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate‐stabilized two‐electron silver nanocluster, Ag10{S2P(OiPr)2}8 (1), is isolated via a self‐redox reaction of Ag7(H){S2P(OiPr)2}6 without adding extra reducing agents. The metal framework of Ag7, a bicapped trigonal bipyramid, is highly correlated to that of Ag10, suggesting Ag7(H){S2P(OiPr)2}6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD‐DFT calculations indicate that the emission is of 1Px→1S nature. [ABSTRACT FROM AUTHOR]

A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism. [ABSTRACT FROM AUTHOR]

Inside Back Cover: A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride (Angew. Hydrides, redox reactions, silver, silver nanoclusters, superatoms Keywords: hydrides; redox reactions; silver; silver nanoclusters; superatoms EN hydrides redox reactions silver silver nanoclusters superatoms 13113 13113 1 05/28/21 20210601 NES 210601 B A new methodology b was developed for the preparation of superatomic nanoclusters in a controllable fashion, with an internal redox reaction of Ag SB 7 sb (H)L SB 6 sb leading to the formation of a highly emissive two-electron Ag nanocluster, Ag SB 10 sb L SB 8 sb . [Extracted from the article]

Hydrides, redox reactions, silver, silver nanoclusters, superatoms Keywords: hydrides; redox reactions; silver; silver nanoclusters; superatoms EN hydrides redox reactions silver silver nanoclusters superatoms 13223 13223 1 05/28/21 20210601 NES 210601 B Eine neue Methode b zur kontrollierbaren Herstellung von superatomaren Nanoclustern wurde entwickelt, bei der eine interne Redoxreaktion von Ag SB 7 sb (H)L SB 6 sb zur Bildung eines hochemittierenden Ag-Nanoclusters Ag SB 10 sb L SB 8 sb führt. Innenrücktitelbild: A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride (Angew. [Extracted from the article]