Preparation, Structural Determination, and Characterization of Electronic Properties of Bis‐silylated and Bis‐germylated Lu 3 N@ I h ‐C 80
| Autor: | Kyosuke Miyabe, Yutaka Maeda, Marilyn M. Olmstead, Mitsuaki Suzuki, Shigeru Nagase, Michio Yamada, Kumiko Sato, Takeshi Akasaka, Masahiro Kako, Alan L. Balch, Wei-Wei Wang, Naomi Mizorogi |
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| Rok vydání: | 2015 |
| Předmět: | |
| Zdroj: | Chemistry – A European Journal. 21:16411-16420 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201502511 |
| Popis: | Bis-silylated and bis-germylated derivatives of Lu3 N@Ih -C80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1 a, 1 b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1 a and 1 b because of its good electron-donor properties and lower steric hindrance around the Ge-Ge bond. The 1,4-adduct structures of 3, 4, 5 were unequivocally established by single-crystal X-ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4-adducts are remarkably smaller than those of Lu3 N@Ih -C80 , because the electron-donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron-donating than the silyl groups on the basis of the redox properties and the HOMO-LUMO energies of 4 and 5. Bis-silylation and bis-germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes. |
| Databáze: | OpenAIRE |
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