Dimerization of Metallofullerenes to Obtain Materials with Enhanced Nonlinear Optical Properties
Dimerization of Metallofullerenes to Obtain Materials with Enhanced Nonlinear Optical Properties
复制标题
金属富勒烯二聚以获得具有增强非线性光学性能的材料
DOI：
10.1002/cphc.201800797
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发表时间：
2018
期刊：
影响因子：
2.9
通讯作者：
Zhiyong Wang
中科院分区：
文献类型：
--
作者：
Yuhang Jiang;Dongsheng Wang;Dan Xu;Jinying Zhang;Zhiyong Wang
在这项工作中，我们从理论上设计了一类新的富勒烯衍生物，金属富勒烯异二聚体，通过金属富勒烯单体的交叉二聚Li@C60， Y@C82and Y2@C80。利用密度泛函理论计算研究了异二聚体的分子结构、电子结构、线性和非线性光学性质。我们发现两个富勒烯笼通过一个相对较弱的碳-碳单键连接。在异源二聚体中，由于金属富勒烯部分不同的电子接受能力而发生笼间电子转移。由于二聚化作用，金属富勒烯的第一超极化率显著提高。时间相关密度泛函理论计算表明，二聚体的第一超极化率的增强与电荷转移跃迁有关。研究表明，共价二聚化是改善金属富勒烯非线性光学响应的有效手段。
In this work, we theoretically designed a new class of fullerene derivatives, metallofullerene heterodimers, through cross dimerization of metallofullerene monomers Li@C60, Y@C82and Y2@C80. The molecular structures, electronic structures, linear and nonlinear optical properties of the heterodimers were studied by using density functional theory calculations. We found that two fullerene cages are connected through a relatively weak carbon‐carbon single bond. Inter‐cage electron transfer takes place in the heterodimers because of the different electron accepting abilities of the metallofullerene moieties. The first hyperpolarizability of the metallofullerenes increases remarkably as a result of dimerization. Time‐dependent density functional theory calculations reveal that the enhanced first hyperpolarizability of the dimer is associated with charge‐transfer transitions. This study demonstrates that covalent dimerization is an efficient means to improve the nonlinear optical response of metallofullerenes.