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[M16Ni24(CO)(40)](4-) Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au-20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

Abstract : Characterization of the tetrahedral Au-20 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 [M16Ni24(CO)(40)](4-) (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M-16](4-) central core with a 1S(21)P(61)D(10)2S(2) jellium configuration. In the case of Au-20, the [Au-16](4-) core is capped by four Au+ ions, whereas in [M(16N)i(24)(CO)(40)](4-) it is capped by four Ni-6(CO)(10) units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M-16](4-) species must be capped for further stabilization. It follows that the Ni-6(CO)(10) units in [M16Ni24(CO)(40)](4-) should not be considered as external ligands as their bonding with the [M-16](4-) core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)(40)](4-) species can be seen as the solution version of tetrahedral M-20 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.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01771101
Contributor : Laurent Jonchère <>
Submitted on : Thursday, April 26, 2018 - 11:47:10 AM
Last modification on : Thursday, March 5, 2020 - 2:04:20 PM
Long-term archiving on: : Monday, September 24, 2018 - 10:32:24 PM

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Franck Gam, Ramiro Arratia-Perez, Samia Kahlal, Jean-Yves Saillard, Alvaro Munoz-Castro. [M16Ni24(CO)(40)](4-) Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au-20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations. Journal of Physical Chemistry C, American Chemical Society, 2018, 122 (8), pp.4723-4730. ⟨10.1021/acs.jpcc.8b00227⟩. ⟨hal-01771101⟩

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