Synthesis and electronic and magnetic properties of new endohedral fullerenes with hybrid lanthanidetransition metal clusters

该项目的重点是通过设计和调节面体内原子之间以及面体内物种与碳笼之间的特定相互作用，合成和表征具有新的电子、光学和磁性的面体内金属富勒烯(EMF，内部具有金属原子或团簇的富勒烯)。利用反应气氛法和不同的活性气体，将多种4f以及3d和4f金属原子结合到一个分子中，合成出新的电动势。利用提高~(13)C同位素含量的试剂，研究了弧光放电合成中电动势的形成机理。电动势的电子结构将通过多种电化学和光谱技术以及量子化学计算来研究。发光性质以及光激发态中的电荷和能量转移将用时间分辨发光光谱来研究。这些数据将伴随着不同带电状态的电动势的电化学和原位VIS-NIR、ESR和核磁共振光谱电化学研究。我们将研究4f和3d-4f电动势的磁性，以揭示磁性金属原子对碳笼的影响，以及团簇中金属-金属交换作用的本质。具体研究了电荷转移对磁性的影响。对实验结果的解释将基于对可能的分子结构、内面体原子的光谱性质和动力学以及自旋密度分布的密度泛函计算。

The project is focused on the synthesis and characterization of endohedral metallofullerenes (EMFs, the fullerenes with metallic atoms or clusters in their inner space) with new electronic, optical and magnetic properties by designing and tuning specific interactions within the endohedral clusters and between the endohedral species and the carbon cages. New EMFs combining various 4f as well as 3d and 4f metal atoms in one molecule will be synthesized using reactive atmosphere method and different active gases. Mechanism of the EMF formation in the arc-discharge sythesis will be studied using the reagents with enhanced content of 13C isotope. The electronic structure of EMFs will be studied by multiple electrochemical and spectroscopic techniques and quantum-chemical calculations. Luminescent properties as well as charge and energy transfer in photoexcited states will be studied by time-resolved luminescence spectroscopy. These data will be accompanied by electrochemical and in situ Vis-NIR, ESR, and NMR spectroelectrochemical studies of the different charged states of EMFs. Magnetic properties of 4f and 3d-4f EMFs will be studied to reveal the influence of magnetic metal atoms on the carbon cage, the nature of the metal-metal exchange interactions in the cluster. The influence of the charge transfer on the magnetic properties will be specifically studied. Interpretation of the experimental results will be based on the DFT computations of the possible molecular structures, spectroscopic properties and dynamics of endohedral atoms and spin density distribution.