Photoreactions of Sc3N@C80 with Disilirane, Silirane, and Digermirane: A Photochemical Method to Separate Ih and D5h Isomers.

Autor: Masahiro Kako, Kyosuke Miyabe, Shinpei Fukazawa, Shinji Kanzawa, Masanori Yasui, Michio Yamada, Yutaka Maeda, Zdeněk Slanina, Uhlík, Filip, Adamowicz, Ludwik, Papadopoulos, Ilias, Guldi, Dirk M., Makoto Furukawa, Shigeru Nagase, Takeshi Akasaka
Předmět:
Zdroj: Photochem; Mar2022, Vol. 2 Issue 1, p122-137, 16p
Abstrakt: Under photoirradiation, Sc3N@Ih-C80 reacted readily with disilirane 1, silirane 4, and digermirane 7 to afford the corresponding 1:1 adducts, whereas Sc3N@D5h-C80 was recovered without producing those adducts. Based on these results, we described a novel method for the exclusive separation of Ih and D5h isomers of Sc3N@C80. The method includes three procedures: selective derivatization of Sc3N@Ih-C80 using 1, 4, and 7, facile HPLC separation of pristine Sc3N@D5h-C80 and Sc3N@Ih-C80 derivatives, and thermolysis of Sc3N@Ih-C80 derivatives to collect pristine Sc3N@Ih-C80. In addition, laser flash photolysis experiments were conducted to elucidate the reaction mechanism. Decay of the transient absorption of 3Sc3N@Ih-C80 * was observed to be enhanced in the presence of 1, indicating the quenching process. When Sc3N@D5h-C80 was used, the transient absorption was much less intensive. Therefore, the quenching of 3Sc3N@D5h-C80 * by 1 could not be confirmed. Furthermore, we applied time-dependent density functional theory (TD-DFT) calculations of the photoexcited states of Sc3N@C80 to obtain insights into the reaction mechanism. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index