A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride.

Authors :: Zhong YJ
Liao JH
Chiu TH
Kahlal S
Lin CJ
Saillard JY
Liu CW
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 Jun 01; Vol. 60 (23), pp. 12712-12716. Date of Electronic Publication: 2021 Apr 16.
Publication Year :: 2021
Abstract: 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, Ag <subscript>10</subscript> {S <subscript>2</subscript> P(O <superscript>i</superscript> Pr) <subscript>2</subscript> } <subscript>8</subscript> (1), is isolated via a self-redox reaction of Ag <subscript>7</subscript> (H){S <subscript>2</subscript> P(O <superscript>i</superscript> Pr) <subscript>2</subscript> } <subscript>6</subscript> without adding extra reducing agents. The metal framework of Ag <subscript>7</subscript> , a bicapped trigonal bipyramid, is highly correlated to that of Ag <subscript>10</subscript> , suggesting Ag <subscript>7</subscript> (H){S <subscript>2</subscript> P(O <superscript>i</superscript> Pr) <subscript>2</subscript> } <subscript>6</subscript> 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 1P <subscript>x</subscript> →1S nature.<br /> (© 2021 Wiley-VCH GmbH.)

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