Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>
Xinyi Zhou,
Yang-Rong Yao,
Yajing Hu,
Le Yang,
Shaoting Yang,
Yilu Zhang,
Qianyan Zhang,
Ping Peng,
Peng Jin,
Fang-Fang Li
Affiliations
Xinyi Zhou
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Yang-Rong Yao
CAS Key Laboratory of Materials for Energy Conversion, Anhui Laboratory of Advanced Photon Science and Technology, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China
Yajing Hu
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Le Yang
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China
Shaoting Yang
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Yilu Zhang
State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Qianyan Zhang
State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Ping Peng
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Peng Jin
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China
Fang-Fang Li
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
The reactivity of the open-shell Gd@C2v-C82 with different charge states towards benzyl bromide was investigated. [Gd@C2v-C82]3− exhibited enhanced activity relative to Gd@C2v-C82 and [Gd@C2v-C82]−. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@C2v-C82. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@C2v-C82. Theoretical studies demonstrate that only [Gd@C2v-C82]3− has a HOMO energy level that matches well with the LUMO energy level of the PhCH2 radical, providing a rationalization for the observed significantly different reactivity.
