Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

Xinyi Zhou; Yang-Rong Yao; Yajing Hu; Le Yang; Shaoting Yang; Yilu Zhang; Qianyan Zhang; Ping Peng; Peng Jin; Fang-Fang Li

doi:10.3390/inorganics11090349

Inorganics (Aug 2023)

Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82

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

DOI: https://doi.org/10.3390/inorganics11090349
Journal volume & issue: Vol. 11, no. 9
p. 349

Abstract

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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.

Published in Inorganics

ISSN: 2304-6740 (Online)
Publisher: MDPI AG
Country of publisher: Switzerland
LCC subjects: Science: Chemistry: Inorganic chemistry
Website: http://www.mdpi.com/journal/Inorganics

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