Heterometallic copper-aluminum superatom
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| Properties | |
|---|---|
| C120H180Al12Cu43 | |
| Molar mass | 4679.016 g·mol−1 |
| Appearance | Black crystals |
| Solubility | Insoluble in benzene |
| Structure | |
| cubic | |
| Im-3 | |
a = 20.2549 at 101 K
| |
Lattice volume (V)
|
8309.8 |
Formula units (Z)
|
2 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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The heterometallic copper-aluminum superatom is a Mackay‐type icosahedral cluster with formula [Cu43Al12](Cp*)12. It is an open‐shell 67‐electron superatom.[1] At the time of its synthesis, it was the largest superatom to be synthesized.[2] It is notable for its large electron count compared to other heterometallic superatoms and its unprecedented electron structure of an open-shell configuration.
Synthesis
[edit]Combining (pentamethylcyclopentadienyl)aluminium(I) with mesitylcopper(I) in benzene at 78 °C under an inert atmosphere for 48 hours, followed by slow cooling, forms black cocrystals of the compound with benzene:
The material is created from single-atom sources of copper and aluminium, which spontaneously separate from the organic compounds to form the superatom cluster. The exergonic nature of the reaction demonstrates that this specific arrangement of copper and aluminum atoms is stable.
Structure
[edit]According to crystallographic and computational analysis, the complex contains a central copper atom surrounded by a first icosahedral shell containing twelve copper atoms, followed by a second icosahedral shell containing twelve aluminium atoms (located at the vertices of the icosahedron) and thirty copper atoms (located at the midpoints of the edges). This central group of metal atoms is surrounded by twelve pentamethylcyclopentadienyl ligands (one attached to each aluminium atom) that assist in protecting it against further reaction.[1] It was the first ligated heterometallic Mackay-type cluster to be discovered.
References
[edit]- ^ a b Weßing, Jana; Ganesamoorthy, Chelladurai; Kahlal, Samia; Marchal, Rémi; Gemel, Christian; Cador, Olivier; Da Silva, Augusto C. H.; Da Silva, Juarez L. F.; Saillard, Jean-Yves; Fischer, Roland A. (2018). "The Mackay-Type Cluster [Cu43 Al12 ](Cp*)12 : Open-Shell 67-Electron Superatom with Emerging Metal-Like Electronic Structure" (PDF). Angewandte Chemie International Edition. 57 (44): 14630–14634. doi:10.1002/anie.201806039. PMID 29981271. S2CID 49714793.
- ^ Technical University of Munich (25 September 2018). "Heterometallic copper-aluminum superatom discovered". ScienceDaily.