Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 38, Pages 16033-16039Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja3073929
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Funding
- Ministry of Education, Culture, Sports, Science, and Technology of Japan [20108001, 20245006, 24350019, 20036008, 20038007, 22000009]
- Strategic Japanese-Spanish Cooperative Program
- JST
- MICINN
- Grants-in-Aid for Scientific Research [24550145, 20108002, 24750006, 20108001] Funding Source: KAKEN
- Direct For Mathematical & Physical Scien [1011760] Funding Source: National Science Foundation
- Division Of Chemistry [1011760] Funding Source: National Science Foundation
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Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu3N@I-h-C-80 reacts with thermally generated bis(2,6-diethylphenyl)silylene with high selectivity and forms monosilylated derivative 1b. Unexpectedly, 1b undergoes photochemical conversion to afford isomer 1a under ambient light. These adducts were characterized using NMR, visible-near-IR spectroscopy, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Single-crystal X-ray structure determination of 1a reveals a rare example of an open 1,2-adduct at the [5,6]-ring junction of the I-h-C-80 cage. The electrochemical study reveals that the redox potentials of 1a and 1b are shifted cathodically compared to those of pristine Lu3N@I-h-C-80 and that monosilylation is effective to fine-tune the electronic properties of endohedral metallofullerenes as well as empty fullerenes. Density functional theory calculations were also performed, which provide a theoretical basis for the structures and the behavior of the encapsulated Lu3N cluster.
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