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

在这个项目中，我们将识别和彻底表征表现出内嵌氧化还原活性的内嵌金属富勒烯（EMF），即金属富勒烯，其中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。具有潜在的内嵌氧化还原活性的EMF（双金属富勒烯，与Ti、Ce等的混合金属EMF）将被合成。他们的电化学性能将被彻底研究，并在溶液中产生的带电状态将通过原位可见-近红外，EPR和NMR光谱电化学技术进行表征。电子结构的电磁场在固态（薄膜和单晶）将研究的价带和核心水平的光电子能谱和电子能量损失谱。制备了具有强电子受体的电磁场（F_4TCNQ、F_2TCNQ和TCNQ）混合膜，并用PES和EELS进行了研究。然后，最强的受体F4 TCNQ和具有低氧化电位的EMF之间的良好有序的界面将被制备和电荷转移化合物中的电荷转移和电子激发将被研究的固态光谱方法。对于具有最大电荷转移的化合物，将生长单晶。固态光谱研究的结果将进行比较，通过溶液电化学和光谱电化学。实验结果的解释将基于DFT计算。最后，结果将使建立电磁场，可以切换电子和磁性的接口或特殊表面上的外部手段，如电荷转移。

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.