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Isolation and Crystallographic Characterization of Lu
Wang-Qiang Shen1, Li-Piao Bao1, Shuai-Feng Hu1
1State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 430074, P. R. China.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 18, 2018
Summary
The size of internal metal nitride clusters influences the choice of fullerene cages in endohedral metallofullerenes (EMFs). Lutetium (Lu3N) clusters demonstrate this size effect, templating larger cages than smaller scandium (Sc3N) clusters.
Area of Science:
- Supramolecular Chemistry
- Materials Science
- Nanotechnology
Background:
- Endohedral metallofullerenes (EMFs) feature metal clusters encapsulated within fullerene cages.
- The size of the internal metal cluster has been observed to correlate with the size of the fullerene cage.
- Previous studies showed small Sc3N clusters in smaller C2n cages (2n=68-82) and large M3N clusters (M=Y, Gd, Tb, Tm) in larger C2n cages (2n=82-88).
Purpose of the Study:
- To experimentally investigate the size effect of the internal metallic cluster on the selection of the outer fullerene cage in EMFs.
- To utilize lutetium (Lu), an intermediate-sized metal, to bridge the size gap between previously studied Sc and larger M metals.
- To unambiguously determine the structures of novel lutetium-containing EMFs.
Main Methods:
- Synthesis of lutetium-containing EMFs.
- Structure determination using single-crystal X-ray diffraction crystallography.
- Analysis of metal cluster geometry and metal-cage/metal-nitrogen interactions.
Main Results:
- A series of lutetium-containing EMFs were synthesized and structurally characterized: Lu3N@Ih(7)-C80, Lu3N@D5h(6)-C80, Lu3N@C2v(9)-C82, Lu3N@Cs(51365)-C84, Lu3N@D3(17)-C86, and Lu3N@D2(35)-C88.
- The encaged Lu3N cluster consistently adopted a planar geometry in Lu3N@C80-88 isomers, facilitating metal-cage/metal-nitrogen interactions.
- Lu3N preferentially selected the C2v(9)-C82 cage over the Cs(39663)-C82 cage, contrasting with larger M3N clusters.
- Unlike Sc3N, Lu3N was also found to template larger C84-88 cages, confirming the size-dependent cage selection.
Conclusions:
- The size of the internal metal nitride cluster plays a crucial role in determining the size of the fullerene cage in EMFs.
- Lutetium nitride clusters exhibit intermediate behavior, templating both medium and larger fullerene cages.
- This study provides clear experimental evidence for the size effect governing EMF structure and formation.
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