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本文研究了(C_(60))_2-[P(O)(OCH_3)]_2富勒烯双体内的笼间C―C键的热力学性质(该双体的结构详见文献,Chem.Commun.2011,47,6111)。原位、变温电子顺磁共振波谱实验结果表明,该C―C键的键离解能(BDE)为72.4 k J?mol~(-1)(17.3 kcal?mol~(-1)),仅约为常见氢键的两倍,或约为常见有机C―C键的五分之一。因此,该二聚体于较高温度时容易发生均裂反应,形成单体自由基;降温时又容易发生自由基聚合反应。基于该笼间C―C键所具有的这些热力学特性,我们对其可被用于制备有序的富勒烯分子元器件等材料作展开讨论。
In this paper, the thermodynamic properties of C-C intercages in the (C_ (60)) _2- [P (O) (OCH_3)] _2 fullerene binders have been studied (the structure of this isomers is described in detail in the literature, Chem. Commun. 2011, 47, 6111). The in-situ and temperature-swing electron paramagnetic resonance spectroscopy results show that the bond dissociation energy (BDE) of the C-C bond is 72.4 kJ? Mol -1 (17.3 kcal? Mol -1) Twice as common as hydrogen bonds, or about one-fifth of the common organic C-C bonds. Therefore, the dimer is prone to undergo a homolysis reaction at a relatively high temperature to form a monomer radical, and free radical polymerization tends to occur when the dimer is cooled. Based on these thermodynamic properties of C-C bonds in the cage, we discuss the materials that can be used to prepare ordered fullerene molecular devices.