Ag13-Centered Cuboctahedral Architecture in Inorganic Cluster Chemistry: A DFT Investigation
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- 作者：Samia Kahlal ; C. W. LiuJean-Yves Saillard
- 刊名：Inorganic Chemistry
- 出版年：2017
- 出版时间：February 6, 2017
- 年：2017
- 卷：56
- 期：3
- 页码：1209-1215
- 全文大小：437K
- ISSN：1520-510X
文摘
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 AgI 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 [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 a1g HOMO 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.