本文選題：富勒烯 + 大碳籠富勒烯　； 參考：《中國科學(xué)技術(shù)大學(xué)》2016年博士論文

【摘要】：富勒烯由于獨特的結(jié)構(gòu)和性質(zhì),在生物醫(yī)學(xué)、有機(jī)光伏和納米材料等領(lǐng)域具有潛在的應(yīng)用,引起了人們廣泛的研究興趣。通過對富勒烯進(jìn)行功能化,一方面有利于富勒烯的結(jié)構(gòu)表征,特別是對于產(chǎn)率低、異構(gòu)體多的大碳籠富勒烯;另一方面還可以對富勒烯的化學(xué)性質(zhì)進(jìn)行研究,為富勒烯的應(yīng)用奠定基礎(chǔ)。本論文主要集中于通過對大碳籠空心及內(nèi)嵌富勒烯進(jìn)行功能化,加深對富勒烯的結(jié)構(gòu)和性質(zhì)的認(rèn)識,主要開展了以下幾方面的工作：1)首先通過直流電弧放電法合成了空心富勒烯混合物,并結(jié)合高效液相色譜分別分離出大碳籠富勒烯含C88和C98的初組分,然后使用氯化試劑(VCl4和SbCl5)進(jìn)行氯化反應(yīng),利用同步輻射X射線單晶衍射確定出氯化衍生物的結(jié)構(gòu)。C88氯化產(chǎn)物為C88(7)Cl12/24, C88(17)Cl22和C88(33)Cl12/14,其中C88(7)Cl12,C88(7)Cl24和C88(33)Cl12中氯原子顯示出不尋常的加成模式：當(dāng)氯原子為12甚至是24個時,仍然有五元環(huán)上沒有氯原子加成,而C88(7)Cl12中有一個氯原子加成在3個六元環(huán)的連接處。C98氯化衍生物為C98Cl22和C98Cl20分別對應(yīng)于異構(gòu)體C98(248)和C98(116),均為C98首次報道的異構(gòu)體,其中前者為理論計算預(yù)測的C98最穩(wěn)定的異構(gòu)體,而后者則為理論計算中穩(wěn)定性較差的異構(gòu)體。2)利用高效液相色譜從空心富勒烯混合物中分離出質(zhì)譜純的C100初組分,然后使用氯化試劑(VCl4和SbCl5)對其進(jìn)行氯化反應(yīng),結(jié)合X射線單晶衍射確定了氯化衍生物的結(jié)構(gòu)。意外地發(fā)現(xiàn)氯化衍生物為C96Cl20,其碳籠為含有3個七元環(huán)的非經(jīng)典的碳籠。同時,該碳籠還含有相鄰五元環(huán)和三順連/稠連的五元環(huán)結(jié)構(gòu)。3個七元環(huán)的形成是通過兩次C2丟失和一個Stone-Wales重排實現(xiàn)的。根據(jù)結(jié)構(gòu)重構(gòu)我們推測C96Cl20是由C2-C100(18)作為起始原料得到的。3)利用高效液相色譜從空心富勒烯混合物中分離了一系列含巨富勒烯C100、C102、C104、C106和C108的組分。利用氯化試劑(VCl4和SbCl5)對各個組分進(jìn)行氯化反應(yīng),并利用同步輻射X射線單晶衍射的方法對氯化衍生物的結(jié)構(gòu)進(jìn)行了系統(tǒng)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分別對應(yīng)于C100(425)、C100(18)和C100(417)異構(gòu)體原料。而氯化衍生物C：C100(417)Cl28可以通過碳籠骨架的轉(zhuǎn)變(失去一個C2單元)形成含有七元環(huán)的非經(jīng)典(NC富勒烯C1-C98(NC)Cl26。通過氯化衍生物C102(603)Cl18/20和C104(234)C116-22的表征,我們首次在實驗上確認(rèn)了理論計算預(yù)測的C102和C104最穩(wěn)定的異構(gòu)體C102(603)和C104(234)。此外,我們首次從實驗上報道了巨富勒烯C106和C108的異構(gòu)體,分別對應(yīng)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形成了共結(jié)晶,其中C104(NC)為非經(jīng)典富勒烯。4)合成并表征了基于大碳籠的混合金屬氮化物原子簇富勒烯(MMNCF) YiY2N@Ih-C80的Bingel-Hirsch衍生物,通過質(zhì)譜表征確定其為單加成產(chǎn)物TiY2N@C80-Mono。而X射線單晶衍射研究則表明TiY2N@C80-Mono中加成基團(tuán)為單鍵加成模式,這和文獻(xiàn)中的報道的基于單一稀土金屬的氮化物原子簇富勒烯(NCF)通常所得到的環(huán)丙烷型的Bingel-Hirsch衍生物完全不同。另外,對比研究表明TiY2N@Ih-C80的Bingel-Hirsch反應(yīng)活性明顯高于Y3N@Ih-C80,而YiY2N@C80-Mono的區(qū)域選擇性也比類似的MMNCF TiSc2N@C80更高。UV-vis-NIR光譜研究表明單鍵加成模式對TiY2N@Ih-C80電了結(jié)構(gòu)產(chǎn)生很大的改變。根據(jù)理論計算,我們提出了TiY2N@C80-Mono單鍵加成產(chǎn)物的形成機(jī)理。通過用Ti原子取代Y3N@Ih-C80中一個Y原子,不僅提高了Bingel-Hirsch反應(yīng)活性,而且衍生物由環(huán)丙烷結(jié)構(gòu)變成了單鍵加成產(chǎn)物,這表明通過一個內(nèi)嵌金屬原子的取代可以操縱NCF的反應(yīng)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.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TQ127.11
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本文編號：1861729