Ag13-Centered Cuboctahedral Architecture in Inorganic Cluster Chemistry: A DFT Investigation

Samia Kahlal (1) , C. W. Liu (2) , Jean-Yves Saillard (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 NDHU - National Dong Hwa University

The bonding in the [Ag{μ-Fe(CO)}] clusters, which exhibit an Ag-centered cuboctahedral core, has been analyzed and rationalized by DFT calculations. Not considering the interaction with its encapsulated atom, the empty [Ag{μ-Fe(CO)}] cage can be considered as the assembly of 12 linearly coordinated 14-electron Ag metal centers. Adding a supplementary Ag at the center allows some covalent delocalized bonding which to some extent tends to reduce the electron deficiency of the 14-electron centers. Adding now two electrons strengthens the delocalized bonding between the encapsulated atom and its host, making [Ag{μ-Fe(CO)}] a superatom with two jellium (5s-type) electrons. TDDFT calculations predict near-IR absorption for this penta-anion, because of the presence of an a HOMO in the middle of an energy gap. Luminescence in the same optical range is also suggested. Other related cubococtahedral species, such as [Ag(SH)], a model for the known 8-electron [Au(SR)] species which exhibits a bicapped centered dodecahedral kernel structure, have also been investigated.

Domains: Chemical Sciences

Samia Kahlal, C. W. Liu, Jean-Yves Saillard. Ag13-Centered Cuboctahedral Architecture in Inorganic Cluster Chemistry: A DFT Investigation. Inorganic Chemistry, 2017, 56 (3), pp.1209-1215. ⟨10.1021/acs.inorgchem.6b02207⟩. ⟨hal-01470477⟩