开壳层金属富勒烯磁学性质的理论研究

In this project, density functional theory (DFT) is employed to study the properties of the considered opened-shell endohedral metallofullerenes (EMFs), including their geometries, and electronic structures to the questions that current difficult in researching paramagnetic property of opened-shell EMFs by experimental measures, and to elucidate the relationship between the encapsuled metal, non-metal clusters as well as the exohedral chemical modification and the paramagnetic property of the opened-shell EMFs. The project proceeds in two steps: first, the influence on the paramagnetic property of these metallofullerenes is investigated by modifying the number and type of the encapsuled rare-earth metal in MnSc(3-n)N@C80, MnSc(3-n)NC@C80 and MnSc(3-n)C2@C80 (M = Y、Gd、Lu, n = 1, 2, 3). Second, the relationship between the addition site and number of exohedral modification and the paramagnetic property of these opened-shell EMFs will be then studied. This project will contribute to the understanding the relationship between the encapsulated moieties and the molecular magnetic properties of opened-shell EMFs, and to unravel the influence of exohedral modification on their ESR parameters at the molecular level. The outcome of the project will provide support and guidance to the application of EMFs in the development of photoelectric devices and single molecular magnets.

本项目针对目前实验中开展金属内嵌富勒烯磁性质研究困难的问题，采用密度泛函理论研究开壳层金属内嵌富勒烯体系的几何和电子性质，阐释内嵌稀土原子的种类和数量、内嵌非金属基团的种类以及笼外化学修饰对开壳层金属内嵌富勒烯顺磁性质的影响，具体工作如下：（1）通过调变MnSc(3-n)N@C80、MnSc(3-n)NC@C80和MnSc(3-n)C2@C80（M = Y、Gd、Lu, n = 1, 2, 3）中内嵌稀土原子的种类和数目来研究内嵌团簇对开壳层金属内嵌富勒烯顺磁性质的影响；（2）在本体金属内嵌富勒烯碳笼外部加上外接基团，并调变外接基团的加成位点和数目，研究化学修饰对开壳层金属内嵌富勒烯顺磁性质的调控。项目从分子层面上解释内嵌基团中金属、非金属元素和分子磁性的关系，揭示外接基团的加位点和数目对分子ESR 参数的影响，为开发金属内嵌富勒烯分子在光电器件、单分子磁体中的应用提供理论支持。

本项目采用密度泛函理论研究开壳层金属内嵌富勒烯体系的几何和电子性质，阐释内嵌稀土原子的种类和数量、内嵌非金属基团的种类以及外界环境对开壳层金属内嵌富勒烯顺磁性质的影响。研究内容包括通过调变MnSc(3-n)N@C80中内嵌稀土原子的种类和数目来研究内嵌团簇对开壳层金属内嵌富勒烯顺磁性质的影响；在本体金属内嵌富勒烯碳笼外部加上外接基团，研究化学修饰对开壳层金属内嵌富勒烯顺磁性质的调控。发现MOF孔笼限域对Dy金属富勒烯单分子磁体性能的影响。探索了笼外氮氧自由基对Dy基金属富勒烯的灵敏感应。项目从分子层面上解释内嵌基团中金属、非金属元素和分子磁性的关系，为开发金属内嵌富勒烯分子在光电器件、单分子磁体中的应用提供理论支持。项目发表SCI论文三篇。