开壳金属富勒烯阴离子的反应性：苄基化物的合成、晶体结构和电化学性能Gd@C2v-C82

IF 3.1 4区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganics Pub Date : 2023-08-25 DOI:10.3390/inorganics11090349

Xinyi Zhou, Yang-Rong Yao, Yajing Hu, Le Yang, Shaoting Yang, Yilu Zhang, Qianyan Zhang, P. Peng, Peng Jin, Fang‐Fang Li

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引用次数: 0

摘要

开壳的反应性Gd@C2v-C82研究了不同电荷态对苄基溴的影响。[Gd@C2v-C82]3−相对于Gd@C2v-C82以及[Gd@C2v-C82]−。结构表征，包括MALDI-TOF-MS、UV-vis-NIR和单晶X射线衍射，表明形成了Gd@C2v-C82.所有三种单加合物都含有1:1镜像对称的对映体。此外，苄基的添加及其特定位置导致产物与母体相比具有不同的电化学行为Gd@C2v-C82.理论研究表明[Gd@C2v-C82]3−的HOMO能级与PhCH2自由基的LUMO能级匹配良好，为观察到的显著不同的反应性提供了合理化。

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

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.

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来源期刊

Inorganics Chemistry-Inorganic Chemistry

CiteScore

2.80

自引率

10.30%

发文量

193

审稿时长

6 weeks

期刊介绍： Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD