Synthesis and Crystal Structure of Li+@Fluoreno[60]fullerene: Effect of Encapsulated Lithium Ion on Electrochemistry of Spiroannelated Fullerene
Synthesis and Crystal Structure of Li+@Fluoreno[60]fullerene: Effect of Encapsulated Lithium Ion on Electrochemistry of Spiroannelated Fullerene
复制标题
Li@Fluoreno[60]富勒烯的合成和晶体结构：封装锂离子对螺环富勒烯电化学的影响
DOI：
10.1021/acs.joc.7b01893
复制
发表时间：
2017
期刊：
影响因子：
3.6
通讯作者：
Hiroshi Ueno， Hiroshi Okada， Shinobu Aoyagi， Yutaka Matsuo
中科院分区：
文献类型：
--
作者：
Yue Ma;Kouya Uchiyama;Hiroshi Ueno;Hiroshi Okada;Hiroshi Moriyama;Yutaka Matsuo;Il Jeon， Hiroshi Ueno， Seungju Seo， Kerttu Aitola， Ryosuke Nishikubo， Akinori Saeki， Hiroshi Okada， Gerrit Boschloo， Shigeo Maruyama， Yutaka Matsuo;Hiroshi Okada， Hiroki Kawakami， Shinobu Aoyagi， Yutaka Matsuo;Hiroshi Ueno， Hiroshi Okada， Shinobu Aoyagi， Yutaka Matsuo
[Li+@C60]TFSI–(TFSI = 双(三氟甲磺酰基)亚胺)与9-重氮芴反应直接生成含锂离子的芴[60]富勒烯的[6,6]-加合物，[6,6]-[Li+@C60(芴)]TFSI–，并对其进行了晶体学表征。该化合物的循环伏安法显示-0.51 V（vs Fc/Fc+）处有可逆的单电子还原波，而第二电子则有不可逆的还原波。后者归因于三元环的打开，这是由于封装的 Li+ 所产生的 sp3-碳负离子的强稳定性以及 14π 电子芳香族芴基阴离子的形成。
The reaction of [Li+@C60]TFSI–(TFSI = bis(trifluoromethanesulfonyl)imide) with 9-diazofluorene directly produced a [6,6]-adduct of lithium-ion-containing fluoreno[60]fullerene, [6,6]-[Li+@C60(fluoreno)]TFSI–, which was crystallographically characterized. Cyclic voltammetry of the compound showed a reversible one-electron reduction wave at −0.51 V (vs Fc/Fc+) and an irreversible reduction wave for the second electron. The latter was attributed to opening of the three-membered ring due to strong stabilization of the resulting sp3-carbanion by the encapsulated Li+and formation of a 14π-electron aromatic fluorenyl anion.