Heterometallic copper-aluminum superatom
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| Properties | |
|---|---|
| C156H216Al12Cu43 | |
| Molar mass | 5147.700 g·mol−1 |
| 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 Cluster[clarification needed] 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] Its two distinct features are its large electron count compared to other heterometallic superatoms and its unprecedented electron structure of an open-shell configuration.
This is the very first example of a ligated heterometallic Mackay-type cluster. According to crystallographic and computational analysis, the complex is an icosahedron, with two-shell 20 equilateral triangles composed of the 55 metal atoms, and one pentamethylcyclopentadienyl ligand off each vertex.
Synthesis
[edit]Fischer's lab team designed the material by building compounds made of individual copper and aluminum atoms. For this superatom, a mixture of aluminium atoms complexed with pentamethylcyclopentadiene (Cp*) and copper atoms complexed with mesitylene (Mes) were combined in an inert atmosphere.
- [AlCp*]4 + [CuMes]5 → [Cu43Al12](Cp*)12
After adding a solvent, the copper and aluminum atoms spontaneously separated from the organic compounds and formed the superatom cluster. The exergonic nature of the reaction demonstratesg that this specific arrangement of copper and aluminum atoms is stable.
References
[edit]- ^ 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.