title: Ag13-Centered Cuboctahedral Architecture in Inorganic Cluster Chemistry: A DFT Investigation.
abstract: The bonding in the [Ag13{μ3-Fe(CO)4}8]3-/5-clusters, which exhibit an Ag13-centered cuboctahedral core, has been analyzed and rationalized by DFT calculations. Not considering the interaction with its encapsulated atom, the empty [Ag12{μ3-Fe(CO)4}8]4-cage can be considered as the assembly of 12 linearly coordinated 14-electron AgImetal 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 [Ag13{μ3-Fe(CO)4}8]5-a superatom with two jellium (5s-type) electrons. TDDFT calculations predict near-IR absorption for this penta-anion, because of the presence of an a1gHOMO in the middle of an energy gap. Luminescence in the same optical range is also suggested. Other related cubococtahedral species, such as [Ag23(SH)16]-, a model for the known 8-electron [Au23(SR)16]-species which exhibits a bicapped centered dodecahedral kernel structure, have also been investigated.
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1 , 3502 Rennes Cedex, France.
authors.forename: Samia
authors.initials: S
authors.lastname: Kahlal
authors.affiliation: Department of Chemistry, National Dong Hwa University , Number 1, Section 2, Da Hsueh Road, Shoufeng, Hualien 97401, Taiwan, Republic of China.
authors.forename: C W
authors.identifier: http://orcid.org/0000-0003-0801-6499
authors.initials: CW
authors.lastname: Liu
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1 , 3502 Rennes Cedex, France.
authors.forename: Jean-Yves
authors.identifier: http://orcid.org/0000-0003-4469-7922
authors.initials: JY
authors.lastname: Saillard