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多芳胺是良好的电子给体,富勒烯C60作为电子受体的光诱导分子内和分子间电荷转移现象[1,2]引起人们普遍关注,尤其是设计合成长寿命电荷分离态的富勒烯C60-多芳胺基类衍生物研究[3,4]是热点课题之一.由于聚吡咯/聚芳胺的氧化还原电位较低[5],我们设想包含吡咯/芳胺给体的富勒烯C60衍生物能延长电荷分离态的寿命.本文用1,3-偶极环加成反应[6]对富勒烯C60与多芳胺化合物的选择性加成反应进行了研究,在不同条件下得到了单加成产物和三加成产物,用FAB-MS,UV-vis,IR,1H NMR,13C NMR,HPLC等方法确定了其分子结构.并且利用半经验AM1量子化学方法在理论上研究了它们的优化构型(如图1)、电子结构,结果表明,富勒烯C60-多芳胺基类衍生物的前沿轨道主要由富勒烯C60部分决定,富勒烯C60母体与功能化基团三苯胺基之间存在较强的分子内电荷转移,这为富勒烯C60衍生物作为光电分子器件材料的应用提供了理论和实验依据. 相似文献
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通过直接进样方式,采用电喷雾电离质谱技术分析了8个合成的富勒烯-N-甲基吡咯烷衍生物,详细研究了其在电喷雾条件下的质谱行为。由结果可知,该类化合物在电喷雾电离过程中易得到电子而负离子化;当衍生物结构中有相对易质子化基团或有活泼氢时,则可获得质子化和去质子的正负离子谱图;衍生物在负离子模式下容易失去吡咯环产生富勒烯负离子,且在合适能量碰撞下易发生衍生化基团内部的逆环加成反应,通过失去1个中性小分子物质CH2‖N—CH3,产生新的一取代亚甲基富勒烯衍生物。基于电喷雾电离源技术联合离子阱分析器建立的质谱分析方法,不但能提供准确的分子量信息,还能通过获得高分辨同位素谱峰和丰富的二级碎片离子峰,进一步确认化合物的分子结构,是一种先进、快速的富勒烯吡咯烷衍生物定性分析方法。 相似文献
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C6 0 具有 30个等同的可参与化学反应的活泼双键 ,制备并表征富勒烯多加成产物是富勒烯化学中最前沿的课题之一 .Hirsch等[15 ]通过研究C6 0 亚甲基加成反应 ,提出了双加成物立体选择性的一般规律 .我们在C6 0 氧加成方面做了类似的研究工作[6 8].本文选取几类富勒烯环双加成衍生物即富勒烯氧化产物C6 0 O2 [6 ]( 1 )、富勒烯含氮衍生物C6 0 (NH) 2 [5 ]( 2 )、富勒烯含吡咯环衍生物C6 0 (CH2 NHCH2 ) 2 [9]( 3)和富勒醇前体C6 0 (SO4) 2 [10 ]( 4)作为模型分子进行理论研究 ,以探寻富勒烯多加成反应的一般性规律 .… 相似文献
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醛不对称加成反应的进展 总被引:3,自引:0,他引:3
综述了近年来醛不对称加成反应的进展,包括加氘还原、与有机金属化合物加成、与有机硼化合物加成、与氰化物加成、与磷酸酯加成和aldol加成等反应。 相似文献
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用从头算HF/3-21G方法研究了C50的环加成衍生物C50X(X=SiH2, PH, S)所有可能的异构体的结构与稳定性, 计算结果表明, SiH2基团、PH基团与S原子在C50上环加成的优先加成位置相同, 都为C3—C4类键和C4—C4类键, 并且相应形成[5,6]-闭环和[5,5]-闭环结构的最稳定异构体; 决定C50X(X=SiH2, PH, S)各异构体稳定性的主要因素, 因加成位置以及发生加成反应的C—C键的单双键类型的不同, 可能是张力、共轭效应或者二者的共同作用. 进一步比较了C50X(X=SiH2, PH, S)与C50X(X=CH2, NH, O)的结构和稳定性等, 并总结出规律性的结论, 即加成原子的大小和加成位置C—C键的类型是影响形成开环或闭环结构的C50环加成衍生物的两种主要因素. 相似文献
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采用循环伏安法和微分脉冲伏安法对比地研究了包括五种C60的衍生物及四种C70的衍生物的电化学性质。结果表明,推电子基团的引入使得富勒烯的氧化还原电位负移,这种负移的程度与加成基团的性质,个数和富勒烯的性质有关。 相似文献
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富勒烯衍生化合物在有机光电、生物医学等领域表现出良好应用前景,相关的富勒烯衍生化方法研究引起了广泛关注,近年来发展迅速。富勒烯由于具有较强的缺电子性质,容易与亲核试剂反应。但相比于碳亲核试剂,含氧亲核试剂与富勒烯的反应发展缓慢,长期被忽略。我们结合本课题组最近开展的工作,对OH~-与MeO~-含氧亲核试剂参与的富勒烯衍生化反应的最新进展进行了总结,并对反应机理进行了较为详尽的阐述,为进一步扩展富勒烯衍生化方法提供参考。 相似文献
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富勒烯材料的催化作用研究进展 总被引:2,自引:0,他引:2
介绍了富勒烯材料(富勒烯和富勒烯衍生物)的催化作用研究进展,特别是催化有机反应方面,包括催化氢转移和硅氢化反应、烷烃裂解反应、氢氘互换反应、耦合和烷基转移反应等.这种新材料还可以催化产生单线态氧(1O2)的化学反应、催化非金属固氮反应、催化石墨合成金刚石的反应,同时还可催化高能燃料的燃烧过程,具有广泛的应用前景. 相似文献
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[reaction: see text] A variant of the Huisgen 1,3-dipolar cycloaddition reaction provides a new and convenient functionalization of fullerenes. This method complements the widely used Prato and Bingel-Hirsch reactions. The derived, highly functionalized cyclopentenone and cyclopentenamine fullerene compounds upon hydrolysis are suitable for further functionalization and may serve well in the synthesis of new C60 derivatives possessing uncommon and interesting properties. 相似文献
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Radical reaction of [60]fullerene with phosphonates or phosphine oxide mediated by manganese(III) acetate dihydrate in chlorobenzene under three different conditions afforded three different types of phosphorylated fullerenes: singly bonded fullerene dimers 2, hydrophosphorylated fullerenes 3, and acetoxylated fullerene derivatives 4. In addition, interconversions among the three types of phosphorylated fullerene derivatives have also been investigated. A possible reaction mechanism was proposed to explain experimental results. 相似文献
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Vitaly V. Kresin Vladimir Z. Kresin 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):381-384
We apply the quantum transition theory of chemical reactions to ionic molecule formation in collisions between alkali-metal clusters and two types of reactive species: halogens and fullerenes. We show that the probability of a sticking collision is strongly dependent upon the nuclear dynamics. It turns out that although both halogens and fullerenes have a high electron affinity and appear promising for a harpooning reaction, this process is inhibited in the fullerene case by unfavorable Franck-Condon factors. This conclusion is in agreement with experimental observations. We predict that a strong reactive channel should reappear if the bare fullerene is replaced by a fullerene-rare gas complex. The product translational and vibrational energy distribution for such a collision is evaluated. 相似文献
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Transition-metal-salt-mediated radical reactions of fullerenes have attracted extensive attention as a new and important method for fullerene functionalization. The application of relatively cheap and easily available ferric perchlorate (Fe(ClO 4 ) 3 ) to the synthesis of [60]fullerene (C 60 ) has demonstrated remarkable advantages and afforded a series of novel fullerene derivatives. In this review we present our recent progress in this area and summarize the reactions of C 60 with malonate esters, β-keto esters, nitriles, aldehydes/ketones, and arylboronic acids in the presence of Fe(ClO 4 ) 3 to afford the C 60-fused disubstituted lactones, C 60-fused hemiketal, C 60-fused dihydrofuran, C 60-fused oxazoles, C 60-fused 1,3-dioxolanes, and fullerenyl boronic esters. The possible reaction mechanisms for the above-mentioned reactions are also described in detail. 相似文献
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Eleni Chountoulesi Christine Mitzithra Konstantinos Kordatos Constantina Kollia Zaphirios Loizos 《合成通讯》2013,43(15):2042-2049
Refined mixed fullerenes were used as a reagent in known organic reactions instead of the pure fullerene C60 with aim to find an alternative, low-cost method for the synthesis of fullerene derivatives potentially exhibiting photoconductive properties. The isolation of C60 or C70 in clean form without admixtures requires the use of large quantities of toluene or other nonpolar solvents, polluting the environment and multiplying the production cost. 1,3-Dipolar cycloaddition of azomethine ylide to fullerite was chosen because this reaction is one of the most widely used for fullerene functionalization, producing material possibly presenting photoinducing behavior. The data showed that the use of the cheaper mixed fullerenes instead of pure C60 leads to the isolation of the same expected products with similar yields. The photoelectric properties of mixed fullerenes and their organic derivatives were also examined. A slightly semiconductive behavior was confirmed as well as a noticeable photoresponse. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献