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The first 8‐electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp=S2P(OiPr)2−) 1 and [PdHAg20(dtp)12]+2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg21(dtp)12]+3 via an internal redox reaction, with the system retaining an 8‐electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s1 electron to the superatomic electron count and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λex=448; λem=842), while 1 and 2 are non‐emissive. The catalytic reduction of 4‐nitrophenol is demonstrated with 1–3 at room temperature. [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]

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]