Strong Effect of Organic Ligands on the Electronic Structure of Metal-Chalcogenide Clusters.
J Phys Chem A
; 122(28): 6014-6020, 2018 Jul 19.
Article
en En
| MEDLINE
| ID: mdl-29953818
ABSTRACT
It is shown that multiple ionization energies of metal-chalcogenide clusters can be substantially reduced by adding ligands that form charge transfer complexes. We demonstrate this intriguing phenomenon by considering metal-chalcogenide clusters including cases where a cluster has a filled electronic shell with a large gap between the occupied and unoccupied states reminiscent of stable species. The studies include a Co6Se8 core ligated with tri-ethylphosphine (PEt3) ligands forming a stable Co6Se8(PEt3)6 species. All of the ligated clusters have a first ionization energy in the range for alkali atoms and multiple ionization energies that are considerably lower than those for the non-ligated clusters. The change in electronic behavior upon ligation can be associated with a shift in the electronic spectrum via a crystal field like effect due to attaching ligands that form charge transfer complexes. We also show that metal-chalcogenide species can be programmed by proper ligand replacement to promote dimerization by first forming the Co6Se8(PEt3) n(CO)6- n ( n = 0-6) clusters where the CO ligands could be replaced by diisocyanide (CNC6H4NC) ligands. The diisocyanide ligand acts as a rigid linker between the metallic cores, enabling the formation of a Co6Se8(PEt3)5(CNC6H4NC)Co6Se8(PEt3)5 superatomic molecule (SM), and we examine the electronic and magnetic properties of the recently synthesized SM via studies on an analogous SM with smaller ligands.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Asunto de la revista:
QUIMICA
Año:
2018
Tipo del documento:
Article
País de afiliación:
Estados Unidos