大碳笼空心及内嵌富勒烯的功能化研究

发布时间：2018-05-08 14:15

  本文选题：富勒烯 + 大碳笼富勒烯　； 参考：《中国科学技术大学》2016年博士论文

【摘要】：富勒烯由于独特的结构和性质,在生物医学、有机光伏和纳米材料等领域具有潜在的应用,引起了人们广泛的研究兴趣。通过对富勒烯进行功能化,一方面有利于富勒烯的结构表征,特别是对于产率低、异构体多的大碳笼富勒烯;另一方面还可以对富勒烯的化学性质进行研究,为富勒烯的应用奠定基础。本论文主要集中于通过对大碳笼空心及内嵌富勒烯进行功能化,加深对富勒烯的结构和性质的认识,主要开展了以下几方面的工作：1)首先通过直流电弧放电法合成了空心富勒烯混合物,并结合高效液相色谱分别分离出大碳笼富勒烯含C88和C98的初组分,然后使用氯化试剂(VCl4和SbCl5)进行氯化反应,利用同步辐射X射线单晶衍射确定出氯化衍生物的结构。C88氯化产物为C88(7)Cl12/24, C88(17)Cl22和C88(33)Cl12/14,其中C88(7)Cl12,C88(7)Cl24和C88(33)Cl12中氯原子显示出不寻常的加成模式：当氯原子为12甚至是24个时,仍然有五元环上没有氯原子加成,而C88(7)Cl12中有一个氯原子加成在3个六元环的连接处。C98氯化衍生物为C98Cl22和C98Cl20分别对应于异构体C98(248)和C98(116),均为C98首次报道的异构体,其中前者为理论计算预测的C98最稳定的异构体,而后者则为理论计算中稳定性较差的异构体。2)利用高效液相色谱从空心富勒烯混合物中分离出质谱纯的C100初组分,然后使用氯化试剂(VCl4和SbCl5)对其进行氯化反应,结合X射线单晶衍射确定了氯化衍生物的结构。意外地发现氯化衍生物为C96Cl20,其碳笼为含有3个七元环的非经典的碳笼。同时,该碳笼还含有相邻五元环和三顺连/稠连的五元环结构。3个七元环的形成是通过两次C2丢失和一个Stone-Wales重排实现的。根据结构重构我们推测C96Cl20是由C2-C100(18)作为起始原料得到的。3)利用高效液相色谱从空心富勒烯混合物中分离了一系列含巨富勒烯C100、C102、C104、C106和C108的组分。利用氯化试剂(VCl4和SbCl5)对各个组分进行氯化反应,并利用同步辐射X射线单晶衍射的方法对氯化衍生物的结构进行了系统研究。其中,C100的氯化衍生物中Cr-C100(425)Cl22和C2-C100(18)Cl28/30和Cs-C100(417)Cl28分别对应于C100(425)、C100(18)和C100(417)异构体原料。而氯化衍生物C：C100(417)Cl28可以通过碳笼骨架的转变(失去一个C2单元)形成含有七元环的非经典(NC富勒烯C1-C98(NC)Cl26。通过氯化衍生物C102(603)Cl18/20和C104(234)C116-22的表征,我们首次在实验上确认了理论计算预测的C102和C104最稳定的异构体C102(603)和C104(234)。此外,我们首次从实验上报道了巨富勒烯C106和C108的异构体,分别对应氯化衍生物C106(1155)Cl24和C108(1771)Cl12。值得一提的是,C106(1155)C124和C104 (NC)Cl24形成了共结晶,其中C104(NC)为非经典富勒烯。4)合成并表征了基于大碳笼的混合金属氮化物原子簇富勒烯(MMNCF) YiY2N@Ih-C80的Bingel-Hirsch衍生物,通过质谱表征确定其为单加成产物TiY2N@C80-Mono。而X射线单晶衍射研究则表明TiY2N@C80-Mono中加成基团为单键加成模式,这和文献中的报道的基于单一稀土金属的氮化物原子簇富勒烯(NCF)通常所得到的环丙烷型的Bingel-Hirsch衍生物完全不同。另外,对比研究表明TiY2N@Ih-C80的Bingel-Hirsch反应活性明显高于Y3N@Ih-C80,而YiY2N@C80-Mono的区域选择性也比类似的MMNCF TiSc2N@C80更高。UV-vis-NIR光谱研究表明单键加成模式对TiY2N@Ih-C80电了结构产生很大的改变。根据理论计算,我们提出了TiY2N@C80-Mono单键加成产物的形成机理。通过用Ti原子取代Y3N@Ih-C80中一个Y原子,不仅提高了Bingel-Hirsch反应活性,而且衍生物由环丙烷结构变成了单键加成产物,这表明通过一个内嵌金属原子的取代可以操纵NCF的反应活性和加成模式。
[Abstract]:Due to its unique structure and properties, fullerenes have potential applications in the fields of biomedicine, organic photovoltaic and nanomaterials. The functionalization of fullerenes is beneficial to the structural characterization of fullerenes, especially for the large carbon cage fullerenes with low yields and many isomers; on the other hand, the fullerenes have a wide range of interest. The chemical properties of fullerenes can also be studied in order to lay the foundation for the application of fullerenes. This paper focuses on the functionalization of hollow and embedded fullerenes in large carbon cages to deepen the understanding of the structure and properties of fullerenes. The main work was carried out in the following aspects: 1) first, it was synthesized by DC arc discharge method. The mixture of hollow fullerenes and high performance liquid chromatography were used to separate the initial fractions containing C88 and C98 in large carbon cage fullerenes, and then chlorination reagents (VCl4 and SbCl5) were used to chlorination. The structure of the chlorinated derivatives of the chlorinated derivatives was determined by the synchrotron radiation X ray diffraction. The chlorination products of the chlorinated derivatives were C88 (7) Cl12/24, C88 (17) Cl22 and C88 (33) Cl12/14. The chlorine atoms in C88 (7) Cl12, C88 (7) Cl24 and C88 (33) Cl12 show an unusual addition mode: when the chlorine atom is 12 or even 24, there is still no chlorine addition on the five membered ring, while a chlorine atom in the C88 (7) Cl12 is added to the 3 six membered ring with the.C98 chlorination derivative corresponding to the isomer for C98Cl22 and C98Cl20, respectively. C98 (248) and C98 (116) are the isomers for the first time reported by C98, the former is the most stable isomer of the predicted C98, and the latter is the.2 of the isomer with poor stability in the theoretical calculation. The pure C100 components are separated from the hollow fullerene mixture by high performance liquid chromatography, and then the chlorination reagent (VCl4 and SbC) is used. L5) the chlorination reaction was carried out and the structure of the chlorinated derivatives was determined with the X ray single crystal diffraction. The chlorination derivative was accidentally found to be C96Cl20, and its carbon cage was a non classical carbon cage containing 3 seven membered rings. At the same time, the cages also contain the adjacent five membered ring and the three CIS link / thickening five membered ring structure of the seven yuan ring formed by two times C2. Loss and a Stone-Wales rearrangement. According to structural reconfiguration, we speculate that C96Cl20 is a.3 derived from C2-C100 (18) as the starting material. A series of components containing meganlfullerene C100, C102, C104, C106 and C108 are separated from hollow fullerenes by high performance liquid chromatography with high performance liquid chromatography. The chlorination reaction was carried out and the structure of the chlorinated derivatives was systematically studied by the method of synchrotron radiation X ray diffraction. The Cr-C100 (425) Cl22 and C2-C100 (18) Cl28/30 and Cs-C100 (417) Cl28 in the chlorinated derivatives of C100 were corresponding to C100 (425), C100 (18) and C100 (417) isomers, respectively, and the chlorinated derivative C:C100 (417) The characterization of the non classical (NC fullerene C1-C98 (NC) Cl26. via the chlorinated derivatives C102 (603) Cl18/20 and C104 (234) C116-22 is formed by the transformation of the carbon cage framework (the loss of a C2 unit). For the first time, we have experimentally confirmed the theoretical calculation of the predicted C102 and C104 most stable isomers C102 (603) and 234. In addition, I The isomers of mega fullerenes C106 and C108 were reported experimentally for the first time, which corresponded to the chloride derivatives C106 (1155) Cl24 and C108 (1771) Cl12. respectively. The C106 (1155) C124 and C104 (NC) Cl24 were co crystallized, and C104 (C104) was a non classical fullerene synthesis and characterized the mixed metal nitride clusters based on large carbon cages. The Bingel-Hirsch derivative of the fullerene (MMNCF) YiY2N@Ih-C80 is identified by mass spectrometry as a single addition product TiY2N@C80-Mono. and the X ray single crystal diffraction study indicates that the addition group in TiY2N@C80-Mono is a single bond addition mode, and this is usually reported in the literature based on the single rare earth metal nitride cluster fullerenes (NCF). The Bingel-Hirsch derivatives of the cyclopropane type are completely different. In addition, the comparative study shows that the Bingel-Hirsch reaction activity of TiY2N@Ih-C80 is obviously higher than that of Y3N@Ih-C80, while the regional selectivity of YiY2N@C80-Mono is higher than that of the similar MMNCF TiSc2N@C80, which shows that the single bond addition mode produces the structure of TiY2N@Ih-C80 electricity. A great change. According to the theoretical calculation, we put forward the formation mechanism of the TiY2N@C80-Mono single bond addition product. By replacing one Y atom in Y3N@Ih-C80 with Ti atoms, the Bingel-Hirsch reaction activity is not only increased, but the derivative of the cyclopropane is transformed into a single bond addition product, which indicates the substitution of an embedded metal atom. The reactivity and addition mode of NCF can be manipulated.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TQ127.11
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本文编号：1861729