【作者】 江岸；

【导师】 吴庆银； 刘子阳；

【作者基本信息】 浙江大学 ， 有机化学， 2010， 博士

【摘要】 本论文通过电弧放电法合成配合二氯苯超声提取,并进一步利用HPLC分离得到了一系列异构体纯的含Sm金属富勒烯,其中包括分子式为Sm@C_2n（n=40-42,44-47）的单金属富勒烯和分子式为Sm₂@C_2n（2n=88,92,104）的双金属富勒烯。对分离得到的金属富勒烯进行了LDI-TOF-MS和UV-Vis-NIR表征。利用扩散方法培养出Sm₂@C₁₀₄（Ⅰ）与Ni（OEP）的共晶,通过单晶X-射线衍射确定了Sm₂@C₁₀₄（Ⅰ）的结构。对Sm₂@C₁₀₄（Ⅰ）的分子轨道能级进行了理论计算。研究了部分Sm金属富勒烯的反应活性。分离得到的单金属富勒烯中有8种新的Sm金属富勒烯,即Sm@C₈₂（Ⅰ）、Sm@C₈₈、Sm@C₉₀（Ⅰ-Ⅳ）、Sm@C₉₂、Sm@C₉₄。其中Sm@C₉₀（Ⅲ）的UV-Vis-NIR吸收光谱与文献报道的含Ca、Eu、Yb的+2价金属富勒烯都不相同,可能是一种不同的碳笼。另外七种Sm单金属富勒烯的UV-Vis-NIR吸收光谱分别与某种已经报道的Ca、Eu、Yb单金属富勒烯相似。对比分离得到的Sm₂C₈₈、Sm₂C₉₂和Sm₂C₁₀₄（Ⅰ-Ⅲ）与文献报道的双金属富勒烯、碳化物型金属富勒烯、TNT型金属富勒烯的UV-Vis-NIR吸收光谱,发现Sm₂C₈₈、Sm₂C₉₂和Sm₂C₁₀₄（Ⅱ）的吸收与文献报道的M₂C₉₀（Ⅱ）（M=Dy,Er）、M₂C₉₄（Ⅰ）（M=Dy,Er,Gd）、Gd₂C₁₀₆相似,其结构应为双金属富勒烯而非碳化物型金属富勒烯,碳笼内的Sm以+2价存在。Sm₂@C₁₀₄（Ⅰ）·2Ni（OEP）单晶X-射线晶体学研究结果显示,碳笼为符合IPR规则的D_3d（822）-C₁₀₄。该碳笼为扁平形,两个Sm原子分别处在碳笼的两端,靠近C₃轴,相距5.8322（7）（?）。D_3d（822）-C₁₀₄可以由I_h-C₈₀沿垂直于C₃轴的方向分开后插入24个碳原子得到,具有纳米胶囊特征。通过B3LYP密度泛函计算研究了D_3d（822）-C₁₀₄及其负4价离子的电子结构,发现D_3d（822）-C₁₀₄的HOMO和LUMO能级的差值比较小,不利于空心富勒烯生成,但其负四价离子的HOMO和LUMO能级差值显著增大,有利于生成金属富勒烯Sm₂@D_3d（822）-C₁₀₄。研究了Sm@C₈₄、Sm@C₈₈、Sm@C₉₀（Ⅳ）和Sm@C₉₄四种金属富勒烯与三苯基膦、丁炔二酸二甲脂的反应,通过HPLC分离得到四种金属富勒烯衍生的主产物,并进行了LDI-TOF-MS和UV-Vis-NIR表征。四个主产物都是单加成产物,其中Sm@C₈₄和Sm@C₈₈的主产物的UV-Vis-NIR吸收与原始的金属富勒烯不同,具有环丙烷结构;Sm@C₉₀（Ⅳ）和Sm@C₉₄的主产物的UV-Vis-NIR吸收与原始的金属富勒烯类似,具有开环桥式结构。更多还原

【Abstract】 Arc discharging synthesis, o-dichlorobenzene extraction aided withultrasonication, and multi-step HPLC isolation were implied to Sm endohedralfullerenes. Complete Sm containing metallofullerene series Sm@C_2n （n = 40-42, 44-47） and Sm₂@C_2n （2n = 88, 92, 104） were obtained, and each individual product hasbeen characterized by LDI-TOF-MS and UV-Vis-NIR spectroscopy. Sm₂@C₁₀₄（Ⅰ）was successfully grown cocrystalizing with Ni（OEP）, and X-ray diffraction studieswere performed on Sm₂@C₁₀₄（Ⅰ）·Ni（OEP） single crystal. Density functional theorycalculations have been carried out on the neutral and tetraanion forms of the D_3d（822）-C₁₀₄ iosmer. Reactivities of some Sm endohedral fullerenes were also studied.There are 8 new mono-metallofullerenes among the endohedral fullerenessynthesized, which are Sm@C₈₂（Ⅰ）, Sm@C₈₈, Sm@C₉₀（Ⅰ-Ⅳ）, Sm@C₉₂, Sm@C₉₄. It isinteresting that the UV-Vis-NIR spectrum of Sm@C₉₀（Ⅲ） are different from those ofall the divalent mono- metallofullerenes encapsulated Ca, Eu, Yb reported, indicatingits unique carbon cage. UV-Vis-NIR spectra of other new metallofullerenes resembleto M@C_2n （M = Ca, Eu, Yb） respectively.Di-metallofullerenes Sm₂@C₈₈, Sm₂@C₉₂ and Sm₂@C₁₀₄（Ⅰ-Ⅲ） were obtained。All UV-Vis-NIR spectra of Sm₂C_2n were also made careful comparison withcorresponding dimetallofullerenes, carbide and TNT metallofullerenes reported.Those of Sm₂C_2n （2n=88, 92, 104） resemble the relevant ones of M₂C_2n+2 （M=Er, Dy,Gd）. The comparability indicate that these Sm₂C_2n are Sm₂@C_2n but not Sm₂C₂@C_2n,and Sm is divalent.Crystallographical studies of Sm₂C₁₀₄（Ⅰ）·2Ni（OEP） single crystal revealed thatSm₂@C₁₀₄（Ⅰ） utilized a D_3d（822）-C₁₀₄ isomer. In this flat carbon cage, the two primarysamarium atoms are located near the threefold axis of the cage and are separated by5.8322（7） （?）. D_3d（822）-C₁₀₄ will be produced by cutting perpendicular to the C₃ axesof I_h-C₈₀ the molecule, addition of 24 carbon atoms. Sm₂@C₁₀₄（Ⅰ） is a nanocaosule.DFT B3LYP level calculation was successively adopted to find out HOMO-LUMO band gaps of D_3d（822）-C₁₀₄ and D_3d（822）-C₁₀₄^4-. Band gap of D_3d（822）-C₁₀₄ istoo small to form the neutral fullerene, but band gap D_3d（822）-C₁₀₄^4- is big enough toform Sm₂@D_3d（822）-C₁₀₄ Reactivity of Sm@C₈₄, Sm@C₈₈, Sm@C₉₀（Ⅳ）, Sm@C₉₄ were studied throughreaction of endohedral fullerenes with dimethyl acetylenedicarboxylate andtriphenylphosphine. Four major products have been separated by HPLC andcharacterized by LDI-TOF-MS and UV-Vis-NIR spectra. The major products aremonoadducts. Difference between derivative of Sm@C₈₄ and Sm@C₈₈ with motherendohedral fullerenes suggest that these adducts possess a "closed" cyclopropylstructure, whereas similarity between derivative of Sm@C₉₀（Ⅳ） and Sm@C₉₄ withmother metallofullerenes indicate these adducts have ring-opened type structure.更多还原