Gam, Franck Arratia-Pérez, Ramiro Kahlal, Samia Saillard, Jean-Yves Muñoz-Castro, Alvaro [M<sub>16</sub>Ni<sub>24</sub>(CO)<sub>40</sub>]<sup>4–</sup>: Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au<sub>20</sub> Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations Characterization of the tetrahedral Au<sub>20</sub> structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M<sub>16</sub>Ni<sub>24</sub>(CO)<sub>40</sub>]<sup>4–</sup> (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au<sub>20</sub>, owing that such species share a common tetrahedral [M<sub>16</sub>]<sup>4–</sup> central core with a 1S<sup>2</sup>1P<sup>6</sup>1D<sup>10</sup>2S<sup>2</sup> jellium configuration. In the case of Au<sub>20</sub>, the [Au<sub>16</sub>]<sup>4–</sup> core is capped by four Au<sup>+</sup> ions, whereas in [M<sub>16</sub>Ni<sub>24</sub>(CO)<sub>40</sub>]<sup>4–</sup> it is capped by four Ni<sub>6</sub>(CO)<sub>10</sub> units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M<sub>16</sub>]<sup>4–</sup> species must be capped for further stabilization. It follows that the Ni<sub>6</sub>(CO)<sub>10</sub> units in [M<sub>16</sub>Ni<sub>24</sub>(CO)<sub>40</sub>]<sup>4–</sup> should not be considered as external ligands as their bonding with the [M<sub>16</sub>]<sup>4–</sup> core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M<sub>16</sub>Ni<sub>24</sub>(CO)<sub>40</sub>]<sup>4–</sup> species can be seen as the solution version of tetrahedral M<sub>20</sub> clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization. tetrahedral M 20 clusters;surface section structures;20 jellium electrons;Relativistic DFT Calculations Characterization;solution;1 S 2 1 P 6 1 D 10 2 S 2 jellium configuration;gold cluster chemistry;20- electron superatom;M 16;core;10 units;CO;Cu;species;M 16 Ni 24;Coinage Metal Tetrahedral Superatoms;Useful Building Blocks Related;Ni 6;Ag 2018-02-05
    https://acs.figshare.com/articles/journal_contribution/_M_sub_16_sub_Ni_sub_24_sub_CO_sub_40_sub_sup_4_sup_Coinage_Metal_Tetrahedral_Superatoms_as_Useful_Building_Blocks_Related_to_Pyramidal_Au_sub_20_sub_Clusters_M_Cu_Ag_Au_Electronic_and_Bonding_Properties_from_Relativistic_DFT_Calculations/5895628
10.1021/acs.jpcc.8b00227.s001