Liu Bin, Fang Hongyun, Li Xiaofang, Cai Wenting, Bao Lipiao, Rudolf Marc, Plass Fabian, Fan Louzhen, Lu Xing, Guldi Dirk M
Key Laboratory of Theoretical Chemistry, Molecular Simulation of Ministry of Education, Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China).
Chemistry. 2015 Jan 7;21(2):746-52. doi: 10.1002/chem.201405572. Epub 2014 Nov 11.
Embedding endohdedral metallofullerenes (EMFs) into electron donor-acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3-dipolar cycloaddition reaction of a corrole-based precursor with Sc3 N@C80 to regioselectively form a [5,6]-adduct (1). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]-bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1. In the electronically excited state, which is probed in photophysical assays with 1, a fast electron-transfer yields the radical ion pair state consisting of the one-electron-reduced Sc3 N@C80 and of the one-electron-oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.
由于内嵌金属富勒烯（EMFs）数量有限且其化学性质在很大程度上仍未被探索，将其嵌入电子供体-受体体系仍然是一项具有挑战性的任务。在本研究中，我们使基于卟吩的前体与Sc3N@C80发生1,3-偶极环加成反应，以区域选择性地形成[5,6]-加合物（1）。通过质谱证实了卟吩部分的成功连接。在电子基态下，吸收光谱表明电子受体与电子供体之间存在可观的电子通信。此外，通过对1进行的核磁共振光谱和电化学研究，有力地证明了在[5,6]-键连接处发生的加成模式。在对1进行光物理测定所探测的电子激发态下，快速的电子转移产生了自由基离子对状态，该状态由单电子还原的Sc3N@C80和单电子氧化的卟吩组成，前提是其仅发生光激发。因此，我们的结果为将EMFs用作光伏组件的实际工作提供了新的思路。
