Ligand-dictated cluster core characteristics in Au8Se2 gold selenido. Insights from relativistic DFT

Tatiana Gómez, Alvaro Muñoz-Castro*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Size and shape determination of ultrasmall gold superatoms passivated by protecting ligands, is a fundamental concern towards the obtention of efficient tunable building blocks. In this report, we pursue a further understanding of the energetic terms ruling the core-shape determination in the first two 2-cluster electron gold selenido clusters reported to date. Our results show that the ultrasmall [Au8Se2(L)4]2+ series featuring an Au4 tetrahedron with two separated exo Au2Se units (core type a), and a Au4 tetrahedron with two connected Au2Se units resulting in a distorted hexagonal Au6 ring (core type b), obtained for L = PPh2CH2PPh2 (dppm) and L = PPh2(CH2)2PPh2 (dppe), respectively. The more favorable adppm arrangement by 5.7 kcal·mol−1 over bdppm, by the less repulsive Pauli repulsion term by 13.9 kcal·mol−1, and the more stabilizing electrostatic character (29.4 kcal·mol−1), and London dispersion (12.4 kcal·mol−1), despite the more favorable contribution from orbital interactions and solvation (−46.4 kcal·mol−1, and, −3.6 kcal·mol−1, respectively) in the later. For bdppe arrangement, a more favorable situation is found by 11.5 kcal·mol−1 in comparison to adppe, determined by the leads to a more stabilizing contribution from electrostatic (31.5 kcal·mol−1), orbital (1.8 kcal·mol−1), London dispersion (11.9 kcal·mol−1) contributions, despite to offer a more steric hindered situation. Such structural preference is in line with experimental findings, allowing comparison of the relative stability of clusters bearing different ligand layers, enabling further shape-property relationship exploration in gold clusters. In addition, optical spectrum features are evaluated. Lastly, sulfido and tellurido hypothetical counterparts denote similar structural preferences.

Original languageEnglish
Article number121149
JournalInorganica Chimica Acta
Volume542
DOIs
StatePublished - 2022

Bibliographical note

Funding Information:
This work was supported by FONDECYT 1221676.

Publisher Copyright:
© 2022 Elsevier B.V.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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