Manipulation of the charge and spin state of metal atoms and clusters inside fullerenes

在这个项目中，我们将识别并彻底表征具有内源性氧化还原活性的金属富勒烯（EMFs），即金属原子的自旋和电荷状态由于氧化还原过程而发生变化的金属富勒烯。合成了具有潜在内氧化还原活性的电磁场（二金属富勒烯、含钛、铈的混合金属电磁场等）。他们的电化学性质将被深入研究，并在溶液中产生的带电状态将被原位Vis-NIR， EPR和NMR光谱电化学技术表征。利用价带、核能级光电子能谱和电子能量损失能谱研究固态（薄膜和单晶）中电磁场的电子结构。本文将制备具有强电子受体（F4TCNQ、F2TCNQ和TCNQ）的混合薄膜，并用PES和EELS对其进行研究。然后，制备最强受体F4TCNQ与低氧化势电磁场之间有序的界面，并利用固态光谱方法研究电荷转移化合物中的电荷转移和电子激发。对于具有最大电荷转移的化合物，将生长单晶。固体光谱研究的结果将与溶液电化学和光谱电化学得到的结果进行比较。实验结果的解释将基于DFT计算。最后，研究结果将能够建立能够在界面或特殊表面上通过外部手段（如电荷转移）以电子和磁性方式切换的电磁场。

Within this project we will identify and thoroughly characterize endohedral metallofullerenes (EMFs) exhibiting endohedral redox activity, i.e. metallofullerenes in which the spin and the charge state of metal atoms is changing as a result of a redox process. The EMFs with potential endohedral redox activity (dimetallofullerenes, mixed-metal EMFs with Ti, Ce etc.) will be synthesized. Their electrochemical properties will be thoroughly studied, and the charged states generated in solution will be characterized by in situ Vis-NIR, EPR, and NMR spectroelectrochemical techniques. Electronic structure of EMFs in the solid state (thin films and single crystals) will be studied by valence-band and core-level photoelectron spectroscopy and electron energy-loss spectroscopy. Mixed films of the EMFs with strong electron acceptors (F4TCNQ, F2TCNQ, and TCNQ) will be prepared and studied by PES and EELS. Then, well ordered interfaces between the strongest acceptor F4TCNQ and the EMFs with low oxidation potential will be prepared and the charge transfer and electronic excitations in the charge-transfer compounds will be studied by solid-state spectroscopic approaches. For compounds with the largest charge transfer, single crystals will be grown. Results of the solid-state spectroscopic studies will be compared to those obtained by solution electrochemistry and spectroelectrochemistry. Interpretation of the experimental results will be based on the DFT computations. Finally, the results will enable to establish EMFs that can be switched electronically and magnetically at interfaces or on special surfaces by outside means such as charge transfer.