聚并苯掺杂C60作锂离子电池负极材料的理论与性能研究

在AM1半经验方法水平上,对不同数目的Li⁺位于C₆₀笼内和笼外时形成的复合物进行几何优化,PAS负极材料由于掺杂C₆₀而吸附更多的Li⁺,并且Li⁺容易嵌入到C₆₀中,从理论上解释了聚并苯(PAS)导电性能改善的原因,并对PAS中掺杂C₆₀的最佳比例进行了预测.     

螺二芴富勒烯吡咯烷衍生物的合成及电化学和光限幅性能

设计合成了3种新颖的螺二芴键联富勒烯(C₆₀/C₇₀)吡咯烷衍生物, 其结构通过IR, ¹H NMR, ¹³C NMR和MALDI-TOF进行确证, 其电化学性质用循环伏安法进行研究. 结果表明, C₇₀衍生物6的还原电位较C₆₀衍生物7分别向负电势移动0.1, 0.12和0.01 V. 同时, 使用纳秒和飞秒激光分别研究了化合物6, 7和8的光限幅性能, 其光限幅阈值分别为15.3, 23.3和13.7 J/cm², 表明材料具有优异的光限幅性能.     

新奇二茂铁甲基氮C60衍生物的合成、结构

尽管目前人们对富勒烯[C₆₀]的过渡金属有机物研究较多^[1],但通过氮卡宾方式连接的C₆₀二茂铁衍生物尚未见报道。鉴于对C₆₀反应的浓厚兴趣及二茂铁的广泛应用价值^[2]我们 利用C₆₀的缺电子性^[3]将其与二茂铁甲基氮卡宾进行[1+2]环加成反应,分离并表征了一种具有齿轮式结构的新奇C₆₀二茂铁衍生物(CpFeC₅H₄CH₂N)5C₆₀(l)。     

富勒烯C60硫桥键联四硫富瓦烯衍生物的理论研究

利用半经验AM1法研究了富勒烯C₆₀硫桥键联四硫富瓦烯衍生物和富勒烯C₆₀键联四硫富瓦烯衍生物的几何构型,电子结构.计算结果显示,富勒烯C₆₀硫桥键联四硫富瓦烯衍生物的四硫富瓦烯(TTF)平面与C₆₀发生作用,使其弯曲的程度比富勒烯C₆₀键联四硫富瓦烯衍生物的大,从而形成一种独特的四硫富瓦烯(TTF)平面半包裹C₆₀的空间构型的D-A体系.这很可能是由于C-S单键的灵活性造成的.而且它们的HOMO轨道主要分布在四硫富瓦烯(TTF)部分,而LUMO轨道则主要分布在C₆₀上.预测了富勒烯C₆₀硫桥键联四硫富瓦烯衍生物很有可能在激发态下产生更长寿命的电荷分离态.     

C60与甲基醚CH3OCnH2n+1的气相离子分子反应研究

自宏观量合成和分离C₆₀以来,人们不断地合成各种功能化的C₆₀衍生物.在对C₆₀化学性质的认识过程中,气相离子化学一直起着十分重要的作用。     

气相中C60与多氯代乙烷的反应

在质谱仪离子源化学电离条件下.C₆₀分别与1,2-二氯乙烷、1,1,2-三氯乙烷、1,1,1-三氯乙烷及1,1,2,2-四氯乙烷的主要碎片离子反应,生成多种C₆₀的加合离子.显示了气相中C₆₀的化学活泼性.     

C60/SBA-15介孔复合材料的合成及其荧光性质的研究

通过对介孔SBA-15孔壁氨基化(SBA-15-NH₂),然后与C₆₀反应形成化学键,成功地将C₆₀组装进入SBA-15孔道中,合成了C₆₀/SBA-15介孔复合材料.通过X射线衍射(XRD)、红外光谱(FTIR)、紫外-可见光谱(UV-V is)和差热-热重分析(TG-DTA)等方法对其进行了表征.同时,对复合材料的荧光性质进行了研究.结果发现,SBA-15-NH₂在575 nm处出现发射峰,C₆₀/SBA-15介孔复合材料在554 nm处出现发射峰,峰位蓝移21 nm.     

两种C60双氰衍生物的结构、光谱和二阶非线性光学性质的理论研究

用INDO/2和INDO/SCI方法计算了C₆₀(C≡N)₂和C₆₀C(C≡N)₂基态电子结构和电子光谱,所得结果与实验值基本一致.在此基础上,用ZINDO-SOS方法计算了两个分子的二阶非线性光学系数β_ijk和β_μ,并对其结果进行了分析和讨论.结果表明,乙氰基与C₆₀相连的两种碳笼衍生物都有大的非线性光学系数,C₆₀C(C≡N)₂是有希望的非线性光学材料.     

共轭聚合物/C60复合体系及其在光伏打电池中的应用

共轭聚合物/C₆₀复合体系在有机太阳能电池中的应用引起了化学工作者的广泛兴趣.本文介绍了共轭聚合物/C₆₀复合体系的光诱导电子转移,以及近年来该体系在光伏打电池中的研究进展.     

中间体C60(CH3)-和产物C60(CH3)2的结构及产物

用INDO系列方法对C₆₀^2-与CH₃反应的中间体C₆₀(CH₃)^-进行理论研究,得到具有Cs对称性的构型。结果表明,CH₃加成到C₁₅上,将使与其相邻的双键碳(C₃₀)的电荷密度和自旋密度达极大值,故加成反应部位在C₃₀处;另外,C₁₅的对位C₁₂(或C₂₇)也较其它部位易于反应,且有两个反应场所,因而产物C₆₀(CH₃)₂可能为六元环上的1,2-加成和1,4-加成两种异构体的混合物。同时对两种加成产物的结构和电子光谱进行了理论研究,指认其电子跃迁,并讨论了其光谱红移的原因。     

侧链上带有C60基团的聚苯乙烯的光电导性能

近几年来,可溶性高分子C60衍生物的合成已取得明显的进展.Weis等[1]报道了以C60封端的聚苯乙烯大分子衍生物,Hawker等[2]合成出聚苯乙烯C60的共聚物.这些单取代的C60衍生物很好地保持了C60原有的性质,加工性能和机械性能均较好.唐本忠等[3]用紫外光照射聚碳酸酯和C60溶液或在AIBN存在的条件下加热以上溶液,得到可溶的聚碳酸酯C60衍生物,该法产率很高(可达99%),且简单易行.Patil等[5]也用类似的方法通过自由基聚合将C60接枝到聚烯烃的高分子链上.我们已报道了将C60接枝到聚烯烃上所得到的共聚物的性能[5,6],但C60高分子衍生物的用途尚不清楚.     

含C60聚苯乙烯微球的制备及光电导性能研究

目前,多功能、高性能聚合物微球的合成及应用已成为研究热点.制备聚合物微球的方法有乳液聚合法、分散聚合法、无皂乳液聚合法、超微乳液聚合法和悬浮聚合法等.制备微米级微球通常采用乳液聚合法和分散聚合法.     

C60接枝聚(N-乙烯基咔唑)的合成、表征及光电导性能

自从Ｃ６０被发现和被制备出来以后,其特殊的结构和独特的物理和化学性质受到各研究领域学者的广泛青睐．聚（Ｎ－乙烯基咔唑）（ＰＶＫ）体系经 Ｃ６０掺杂后光电导性能有很大幅度提高．但掺杂体系不稳定,因而限制了对该类材料的应用．为了克服这种缺点,我们尝试用各种简单的方法把Ｃ６０化学键合到高分子链中,制备具有光电导性能的Ｃ６０高分子衍生物． 最近,唐本忠［１］和 Ｐａｔｉｌ［２］等分别用常规的自由基聚合方法,将Ｃ６０接枝到聚合物分子主链上,我们已研究了不含导电高分子的Ｃ６０共聚物的光电导性能［３］,本文采用…     

Gas-phase synthesis and the structural and electronic properties of C60S studied by mass spectrometry and molecular orbital calculation

C₆₀S⁺ was synthesized through the gas-phase ion-molecule reaction of C₆₀ with the plasmas of carbon disulfide under self-chemical-ionization (self-CI) conditions in the ion source of a mass spectrometer. Semi-empirical PM3-UHF and density functional B3LYP levels of theory with 6-31G(d) basis set calculations were performed on all the possible structures and electronic properties of the product. The results showed that the most stable structure among the possible isomers was the 6/6 closed derivative. The reaction energies of C₆₀+S⁺→C₆₀S⁺ and C₆₀+S→C₆₀S were also calculated to suggest the possibility of C₆₀S synthesis in condensed phase.     

Preparation and Characterization of Fullerene C_(60) and Phthalocyanine Co-grafted Poly(epoxy propyl carbazole)

Fullerenes and its derivatives have attracted great interest from the viewpoints of both fundamental science and potential application. Fullerene-doping polymeric photoconductors have been extensively investigated due to their potential technological application. The enhancement of the photoconductivity of the poly (N-vinylcarbazole) (PVK) films by dopong with fullerenes (a mixture of C60 and C70) was for the first time reported by Wang1. He proposed that enhanced photoconductivity was attr…     

Semiempirical molecular dynamics studies of C60/C70 fullerene oxides: C60O, C60O2 and C70O

The spectral analysis indicates that all isomers of C₆₀O, C₇₀O and C₆₀O₂ have an epoxide-like structure (an oxygen atom bridging across a C–C bond). According to the geometrical structure analysis, there are two isomers of fullerene monoxide C₆₀O (the 5,6 bond and the 6,6 bond), eight isomers of fullerene monoxide C₇₀O and eight isomers of fullerene dioxide C₆₀O₂. In order to simulate the real reaction conditions at 300 K, the calculation of the different isomers of C₆₀O, C₆₀O₂ and C₇₀O fullerene oxides was carried out using the semiempirical molecular dynamics method with two different approaches: (a) consideration of the geometries and thermodynamic stabilities, and (b) consideration of the ozonolysis mechanism. According to the semiempirical molecular dynamic calculation analysis, the probable product of this ozonolysis reaction is C₆₀O with oxygen bridging over the 6–6 bond (C_2v). The most probable product in this reaction contains oxygen bridging across in the upper part of C₇₀ (6–6 bond in C₇₀O-2 or C₇₀O-4) an epoxide-like structure. C₆₀O₂-1, C₆₀O₂-3 and C₆₀O₂-5 are the most probable products for the fullerene dioxides. All of these reaction products are consistent with the experimental results. It is confirmed that the calculation results with the semiempirical molecular dynamics method are close to the experimental work. The semiempirical molecular dynamics method can offer both the reaction temperature effect by molecular dynamics and electronic structure, dipole moment by quantum chemistry calculation.     

Electron Spin Resonance Spectra of Some Free Radical in Pure C60 and Mixture of C60/C70

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Copolymerization of benzoquinone with norbornene

For the first time, the conjugated dicarbonyl compound benzoquinone has been copolymerized with the strained cyclo-olefin norbornene using catalytic amounts of the Friedel-Crafts metathesis catalytic system WOCl₄+AlCl₃. All analyses reveal that the products consist of conjugated blocks originating from benzoquinone connected with spacers originating from norbornene. The products are soluble in benzene, toluene, chlorobenzene, etc. but possess properties of the conjugated polymers. They have been synthesized via a very simple one-pot procedure.     

富勒烯(C60/70)-丙烯酸的自由基共聚

富勒烯及其衍生物在超导、光电、磁学等领域展现出奇特性能[1],富勒烯的化学修饰成为化学工作者们关注的热点之一,而其中合成含富勒烯的新型聚合物是一个非常重要的方面.     

Design,Synthesis and Properties of Novel C60-Crown Dyads by 1,3-Dipolar Cycloaddition

Based on the 1,3-dipolar cycloaddition of azomethine ylide generated in situ from aldehyde and sarcosine attached to C60,two novel benzo-15-crown-5/C60 dyads with a different linking chain in each were designed and synthesized in yields of 30％ and 38％,respectively.It was found that their UV-Vis absorption spectra could be regulated hypsochromically by metal ions complexed.The long and soft linking chain was favorable for cooperate interaction of crown ether unit and C60 unit.