金属富勒烯多氨基加成衍生物的合成研究

发布时间：2018-07-04 17:58

本文选题：Gd@C_(82) + 吗啉　；参考：《内蒙古大学》2017年硕士论文

【摘要】：内嵌金属富勒烯是一种有金属或者金属簇包含在空心的碳笼内的碳纳米材料,由于在金属与碳笼之间有电子的转移,使它具有独特的结构和一定的电子特性,因此在新材料研究、太阳能光伏以及生物医学方面都有潜在的应用。为了满足金属富勒烯的新兴的应用,有必要对其进行加成的化学修饰。在金属富勒烯衍生化研究中,单键加成是其中一类重要的加成反应。目前含有单键直接加成衍生物的研究主要集中在自由基加成和Bingle-Hirsch反应上面,反应最多可以控制两个位点的选择性,多加成的选择性合成仍具有非常大的挑战。此外,多加成衍生物的确切结构的缺乏,导致外部的多加成产物对内部金属的影响的研究更为困难,特别是丰度最多的M@C82碳笼体系。因此,发展多加成金属富勒烯的选择性合成方法具有重要的意义。本人在NFSI存在下,用Gd@C82和吗啉在邻二氯苯溶剂中合成了第一个Gd@C82的区域选择性的多氨基加成衍生物,X-射线单晶衍射结果表明七个吗啉基团通过1,4-加成的方式加到碳笼上,加成位置由于Gd的影响沿着C2轴远离金属钆的六元环。同样的,多加成也影响了 Gd3+的位置,使Gd3+在碳笼内有新的分布。七加成衍生物进一步通过MALDI-TOF质谱、FTIR和UV-vis-NIR谱进行了表征。DFT计算提出了加成反应的起始位置和金属Gd最稳定的位置,从而进一步证实了 Gd@C82(C4H8NO)7的结构。同时,进一步表征了五加成和九加成衍生物的MALDI-TOF质谱、红外光谱、紫外可见近红外谱和电化学DPV。通过比较三种衍生物的谱图,从而揭示了不同的加成数目对衍生物结构和性质的影响。根据这些结果,Gd@C82的选择性多加成成为一个合理的目标,可能在未来进一步为其它多加成衍生物的合成和表征提供有价值的线索。
[Abstract]:Embedded metal fullerene is a kind of carbon nanomaterials with metal or metal clusters contained in hollow carbon cages. Due to the transfer of electrons between metal and carbon cages, it has a unique structure and certain electronic properties. Therefore, there are potential applications in new materials research, solar photovoltaic and biomedicine. In order to meet the new application of metal fullerenes, it is necessary to modify them by chemical addition. In the study of metal fullerenes, single bond addition is one of the most important addition reactions. At present, the studies of direct addition derivatives with single bond are mainly focused on free radical addition and Bingle-Hirsch reaction, which can control the selectivity of two sites at most. In addition, the lack of the exact structure of the polyadducts makes it more difficult to study the effects of the external polyadducts on the internal metals, especially the M@ C82 carbon cage system, which is the most abundant. Therefore, it is of great significance to develop the selective synthesis of polyadditive metal fullerenes. In the presence of NFSI, I have synthesized the first region-selective polyamino addition derivative of GdC82 with morpholine in o-dichlorobenzene solvent. The results of X-ray single crystal diffraction show that seven morpholine groups are added to the carbon cage by the way of 1o 4- addition. The addition position is due to the influence of Gd along the C2 axis away from the metal gadolinium ring. In the same way, the multiple addition also affects the location of Gd3, which makes Gd3 have a new distribution in the carbon cage. The derivatives were further characterized by FTIR and UV-vis-NIR spectra of MALDI-TOF mass spectrometry. The initial position of the addition reaction and the most stable position of metal Gd were obtained by DFT calculation. The structure of GdR C82 (C _ 4H _ 8NO) _ 7 was further confirmed. At the same time, MALDI-TOF mass spectra, infrared spectra, UV-Vis near infrared spectra and electrochemical DPVs were further characterized. By comparing the spectra of the three derivatives, the effects of different addition numbers on the structure and properties of the derivatives are revealed. Based on these results, the selective multiple addition of Gd@ C82 becomes a reasonable target, which may provide valuable clues for the synthesis and characterization of other multiadditive derivatives in the future.
【学位授予单位】：内蒙古大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3

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