Synthesis, Structural Characterization, and Electronic\nStructure Analysis of F<sub>2</sub>‑type Superatomic Molecules

The\ninvestigation of bonding interactions between superatoms continues\nto be a largely unexplored area of study. In this study, we present\nthe synthesis and characterization of two F<sub>2</sub>-type superatomic\nmolecules [Au<sub>2</sub>Ag<sub>25</sub>(C<sub>7</sub>H<sub>4</sub>NOS)<sub>13</sub>(DPPB)<sub>3</sub>] and [Au<sub>9</sub>Ag<sub>18</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>11</sub>(DPPM)<sub>5</sub>]<sup>2+</sup> (<b>Au<sub>2</sub>Ag<sub>25</sub></b> and <b>Au<sub>9</sub>Ag<sub>18</sub></b> for short, respectively). The overall\nstructures were confirmed via X-ray crystallography, revealing the\nhorizontal expansion of the biicosahedral Au<sub>2</sub>Ag<sub>21</sub> yielding [Au<sub>2</sub>Ag<sub>25</sub>(C<sub>7</sub>H<sub>4</sub>NOS)<sub>13</sub>(DPPB)<sub>3</sub>] and vertical expansion of the\nbiicosahedral Au<sub>8</sub>Ag<sub>15</sub> yielding [Au<sub>9</sub>Ag<sub>18</sub>(C<sub>5</sub>H<sub>4</sub>NS)<sub>11</sub>(DPPM)<sub>5</sub>]<sup>2+</sup>. Furthermore, their electronic structures were\nelucidated through density functional theory (DFT) calculations. Spectroscopic\nanalysis of electronic absorption characteristics, in conjunction\nwith Tamm–Dancoff approximation DFT (TDA-DFT) calculations,\nrevealed that the Au<sub>2</sub>Ag<sub>21</sub><sup>(+9)</sup> and\nAu<sub>8</sub>Ag<sub>15</sub><sup>(+9)</sup> cores were analogues\nof the F<sub>2</sub> molecule in electronic configuration.