碳笼烯(C60)在高分子领域中的研究进展

综述了碳笼烯（Ｃ６０）在高分子领域中的研究进展,包括碳笼烯的高分子化、与聚合物形成电荷转移复合物以及作为催化聚合反应的催化剂。     

H2C（P（Ph）2AuX）2和HC（P（Ph）2AuX）3（X=I,CI）型配合物的…

根据配合物Ｈ２Ｃ（Ｐ（Ｐｈ）２ＡｕＸ）２（Ｘ＝Ｉ，Ｃｌ）和ＨＣ（Ｐ（Ｐｈ）２ＡｕＸ）３（Ｘ＝Ｉ，Ｃｌ）的晶体结构对它们进行了从头算研究，在ＭＰ２近似水平下得到绕Ｃ－Ｐ旋转所产生构象的势能曲线，从而揭示Ａｕ（Ｉ）－Ａｕ（Ｉ）相互作用，计算结果表明，在所研究的四个配合物中均存在Ａｕ（Ｉ）－Ａｕ（Ｉ）相互作用，该作用较弱，约为１０．０～１６．５ｋＪ／ｍｏｌ，与Ｓｃｈｍｉｂａｕｒ的实验估计值和Ｐｙｙｋｋｏ     

REACTIONS OF C_(60) WITH R_3SnH: A NEW SYNTHETIC TO C_(60)(RH)n AND THE PROPERTY OF C_(60) TO CATALYZE RADICAL REACTIONS

ＲＥＡＣＴＩＯＮＳＯＦＣ_（６０）ＷＩＴＨＲ_３ＳｎＨ：ＡＮＥＷＳＹＮＴＨＥＴＩＣＴＯＣ_（６０）（ＲＨ）ｎＡＮＤＴＨＥＰＲＯＰＥＲＴＹＯＦＣ_（６０）ＴＯＣＡＴＡＬＹＺＥＲＡＤＩＣＡＬＲＥＡＣＴＩＯＮＳ￥ＹｉＭｉｎＳＨＥ；ＹａＰｉｎｇＴＵ；ＸｉｎｇＨｕ...     

C_（60）分子间相互作用势及其晶体压缩系数的计算

根据Ｃ（６０）晶体升华焓的实验值求得了Ｃ（６０）分子间相互作用势的解析表达式。用该表达式计算了Ｃ（６０）分别为面心立方和六方晶格时晶体的结合能，讨论了不同晶格的稳定性问题，解释了Ｃ（６０）晶体一般是面心立方的原因。本文还根据Ｃ（６０）分子间相互作用势计算了Ｃ（６０）晶体的压缩系数，并与文献的实验值进行了比较，所得结果与实验值相符合。     

两种C60双氰衍生物的结构,光谱和二阶非线性光学性质？…

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βｊｋ和βμ,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。     

INVESTIGATION ON THE INTERACTION OF THE HALOGEN ATOMS WITH THE C_（60） CAGE IN THE HALOGEN－ENCLOSED COMPLEXES （HALOGEN＠C_（60））

ＩＮＶＥＳＴＩＧＡＴＩＯＮＯＮＴＨＥＩＮＴＥＲＡＣＴＩＯＮＯＦＴＨＥＨＡＬＯＧＥＮＡＴＯＭＳＷＩＴＨＴＨＥＣ_（６０）ＣＡＧＥＩＮＴＨＥＨＡＬＯＧＥＮ－ＥＮＣＬＯＳＥＤＣＯＭＰＬＥＸＥＳ（ＨＡＬＯＧＥＮ＠Ｃ_（６０））￥ＣｈｕａｎＢａｏＺＨＵａｎｄＪｉ...     

C60在卟啉衍生物Langmuir单层膜中的分散状态

研究了Ｃ６０在四苯基卟啉衍生物５，１０，１５，２０－四－对（癸酸α氧基）苯基卟啉（ＴＤＰＰ）及５，１０，１５，２０－四－对（乙酸α氧基）苯基卟啉（ＴＡＰＰ）单层膜中的分散状态。空气／Ｃｄ＾２＋水溶液界面上混合单层膜的π－Ａ等温线、混合膜与花生酸（ＡＡ）形成的交替多层膜的低角Ｘ射线衍射实验及混合单层ＬＢ膜的ＵＶ－Ｖｉｓ光谱表明，在ＴＤＰＰ／Ｃ６０（１：１）的混合单层膜中，Ｃ６０以单分子或（和）聚集体     

碳笼烯-60对Ziegler-Nata催化剂催化苯乙烯聚合的影响

碳笼烯 ６０对Ｚｉｅｇｌｅｒ Ｎａｔａ催化剂催化苯乙烯聚合的影响洪瀚周锡煌李福绵（北京大学化学学院北京１００８７１）关键词碳笼烯 ６０（Ｃ６０），Ｚｉｅｇｌｅｒ Ｎａｔａ催化剂，配位聚合，等规聚苯乙烯Ｃ６０独特的球笼形空间结构和电子结构决定了其有许...     

碳六十内嵌复合物中钠及氯与碳六十之间的相互作用

本文用量化学及分子力学方法计算了（Ｎａ＠Ｃ６０）及（Ｃｌ＠Ｃ６０）中Ｎａ及Ｃｌ与Ｃ６０之间的相互作用，总的相互作用是吸引。在静电相互作用、色散相互作用及电子云重排斥相互作用三项中前一项占９０％以上，有着决定性的影响，色散相互作用约占５％。对电子云重叠排斥作用来说，由于Ｃｌ＾－的半径比Ｎａ＾＋的大很多，所以在（Ｃｌ＠Ｃ６０）中这种作用要比在（Ｎａ＠Ｃ６０）中大很多。     

聚(丙烯酰胺-丙烯酸)/聚(丙烯酰胺-二甲基二烯丙基氯化铵)聚电解质复合溶液动态光散射研究

通过动态光散射、粘度和透光率测定，研究了聚（丙烯酰胺 丙烯酸）［Ｐ（ＡＭ ＡＡ）］／聚（丙烯酰胺 二甲基二烯丙基氯化铵）［Ｐ（ＡＭ ＤＭＤＡＡＣ）］聚电解质复合溶液的结构和性能．结果表明，Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）复合比、溶液浓度和氯化钠用量影响溶液中复合物的构象和流体力学半径．Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）分子链间适度的库仑相互作用，可形成均相Ｐ（ＡＭ ＡＡ）／Ｐ（ＡＭ ＤＭＤＡＡＣ）聚电解质复合溶液，复合物具有较伸展的构象和较大的流体力学半径，因而溶液粘度较高．Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）分子链间过强的库仑相互作用或小分子电解质的屏蔽作用，可使复合物构象卷曲，结构紧缩，流体力学半径减小，甚至产生相分离，导致溶液粘度降低．     

He+C60↔(He@C60)的反应势垒研究

The reaction barriers of (He+C60(He＠60)) have been calculated by the quantum-chemical method EHMO/ASED in the following four paths: (1) penetrate through the pentagon on the C60 cage; (2) penetrate through the hexagon on the C60 cage,(3) penetrate through the short bond; (4) penetrate through the long bond. Corresponding to each path, there are two choices: (a) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a planar extension and a concerned window is formed; (b) while He penetrate C60 cage, the distances of the C’s which are the most adjacent to He are changed with a spherical extension and a concerned window is formed. The results are given in Figs. 1-2 and Tables 1-2. It is shown that the reaction through path(4) with choice (a) has the least reaction barrier, being optimum. At that case, a window of 9-membered ring is formed. Because the window extension of C6H6 is more free than that of C60, the barrier of He penetrating through C6H6 will be lower than that of He penetrating through C60.     

Molecular mechanics on bonding and non-bonding interactions in (atom@C60)

The interactions between the embedded atom X (X = Li, Na, K, Rb, Cs; F, Cl, Br, I) andC60 cage in the endohedral-form complexes (X@C₆₀) are calculated and discussed according to molecular mechanics from the point of view of the bonding and non-bonding. It is found from the computational results that for atoms with radii larger than Li’s, their locations with the minimum interaction in (X@C₆₀) are at the cage center, while atom Li has an off-center location with the minimum interaction deviation of ~0.05 nm, and the cage-environment in C₆₀ can be regarded as syhero-symmetry in the region with radiusr of ~0.2 nm. It is shown that the interaction between X and C₆₀ cage is of non-bonding characteristic, and this non-bonding interaction is not purely electrostatic. The repulsion and dispersion in non-bonding interactions should not be neglected, which make important contribution to the location with minimum interaction of X, at center or off center. Some rules about the variations of interactions with atomic radii have been obtained. Project supportt:d by the National Natural Science Foundation of China.     

C60微电极伏安法研究

The microdisk electrode voltammetric behaviors of C_(60) are reported in this communication. This was accomplished by use of a mixed solvent system as Acetonotrile:Xylene=1:4 and a supporting electrolyte as 0.1 mol·L~(-1) Bu_4NPF_6. Au, Pt and Hg (Pt) were used as working electrode. In this new conditions, the successive six step reduction of C60 were obtained at below 15 ℃. It was found that the former five steps are all the single electron reversible reduction, but behaviors of the sixth steps are like EC' processes. Several electrochemical data were determined.     

C60离子束撞击固体表面的坍塌沉积(I)共焦显微拉曼光谱研究

Raman spectroscopy was applied to characterize the species deposited from the mass-selected C60 ion beam which was accelerated to 900 eV. The substrates for the deposition were (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold crystal. The species do not exhibit the Raman scattering features of buckminsterfullerene, but displays peaks at 1585 and 1332 cm-1 instead. The former peak is the chararteristic Ranan peak of hexagonal graphite, and the latter can be attributed to the amorphous carbon in sp3 hybridization. The result reveals that C60 was collapsed to form a new phase when it collides on the solid surface.     

C60离子束撞击固体表面的坍塌与沉积(II)扫描隧道显微研究

Mass-selected C60 beam produced by laser ablation was accelerated and bombarded the (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold single crystal. The samples were characterized by STM. The STM images showed that, the deposited species collapsed and formed planar structure on the solid surface, but the collapsed species were not dissociated and well oriented on the surface. Both positive and negative C60 ions were observed in the desorption mass spectra, confirming that the species collapsed on the solid surface are still the C60 clusters.     

Molecular mechanics on bonding and non-bonding interactions in (atom@C_(60))

The interactions between the embedded atom X (X=Li,Na,K,Rb,Cs; F,Cl,Br,I) and C60cage in the endohedral-form complexes (X@C60) are calculated and discussed according to molecular mechanics from the point of view of the bonding and non-bonding.It is found from the computational results that for atoms with radii larger than Li's,their locations with the minimum interaction in (X@C60) are at the cage center,while atom Li has an off-center location with the minimum interaction deviation of-0.05 nm,and the cage-environment in C60 can be regarded as sphero-symmetry in the region with radius r of ~0.2 nm.It is shown that the interaction between X and C60 cage is of non-bonding characteristic,and this non-bonding interaction is not purely electrostatic.The repulsion and dispersion in non-bonding interactions should not be neglected,which make important contribution to the location with minimum interaction of X,at center or off center.Some rules about the variations of interactions with atomic radii have been ob     

Al(2Pu)+H2(X1Σ+g)的分子反应动力学

基于多体展式方法所导出的ＡｌＨ２（Ｘ＾２Ａ１）分析势能函数,用准经典的Ｍｏｎｔｅ－Ｃａｒｌｏ轨迹法对Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｕ＝ｊ＝０）的分子反应动力学过程进行了计算。结果表明,此反应的主产物为交换反应Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｖ＝ｊ＝０）→ＡｌＨ（Ｘ＾１∑＾＋,Ｖ’,ｊ’）＋Ｈ（＾２Ｓｇ）的ＡｌＨ（Ｘ＾１∑＾＋,ｖ’,ｊ’）没有发现ＡｌＨ２（Ｘ＾２Ａ１）的络合物。而     

g-C3N4碳位掺杂电学及光学性质的分析

使用第一性原理研究了C位掺杂的g-C₃N₄的电学性质和光学性质,掺杂原子为B、P、S. g-C₃N₄有C1位和C2 位两种对称位碳原子,其中在C1 位上的掺杂易于C2 位,掺杂体系也较C2 位稳定. 相比于磷和硫在g-C₃N₄上的掺杂,硼掺杂最易于进行. 掺杂后体系的晶体结构之间差别较大,这与掺杂原子的大小以及电负性有关. 由轨道布居分布可知,掺杂后的硼、磷、硫原子价电子发生了变化,表明掺杂原子发生了杂化,与相邻原子以强的共价键相连. 掺杂原子与被取代的碳原子之间的价电子差异导致了能带的增加. 在原来的体系中,掺杂后的体系出现了一条新的能带,因此导致实际带隙下降,表明了掺杂后的体系导电性能增强. 对纯g-C₃N₄及掺杂g-C₃N₄的光学性质分析表明,g-C₃N₄的光学吸收主要在紫外光区,掺杂磷和硫后对g-C₃N₄的光吸收波长范围无改变,掺杂硼后的g-C₃N₄光吸收不再局限于紫外光区,而且延伸至可见光区和红外光区,并在红外光区有很强的吸收,表明g-C₃N₄掺杂硼后能大大地提高光催化效率. 电子能量损失光谱和光导率谱以及介电常数都佐证了上述观点.     

Reactions of chlorofullerene C60Cl6 with N-substituted piperazines

It was shown for the first time that reactions of C₆₀ halides with aliphatic amines provide a facile route for the synthesis of aminofullerenes, valuable precursors for water-soluble cationic fullerene derivatives. Particularly, chlorofullerene C₆₀Cl₆ and N-substituted piperazines were investigated in this work. It was shown that substitution of chlorine atoms in C₆₀Cl₆ by amine groups is accompanied by partial elimination of addends from the fullerene cage that yields mixtures of di-, tetra- and, hexaaminofullerenes as the final products. Separation of these mixtures by column chromatography resulted in isolation of pure 1,4-diaminofullerenes; this procedure gives much higher and more reproducible yields of these compounds than direct oxidative photoaddition of secondary amines to C₆₀. ESI mass spectrometry and NMR spectroscopy data showed that hexaaminofullerene isomers are major components in inseparable mixtures of polyaddition products. Polyaminofullerenes were found to be readily soluble in aqueous acids; these solutions are unstable because of a facile substitution of protonated amine groups with hydroxyls. Nevertheless, the use of other amine substrates in the investigated reaction can potentially allow the preparation of more stable water-soluble cationic fullerene derivatives for biological studies.     

以C60为媒介的网状金纳米粒子聚集体的构筑

通过全甲基化环糊精和卟啉之间的"Click"反应,合成了一种不对称环糊精修饰的卟啉衍生物,并对其结构进行了表征.该化合物与氯金酸作用可以形成平均粒径为5 nm的水溶性金纳米粒子,该金纳米粒子进一步与C60作用形成网状纳米聚集体,并通过紫外光谱和透射电子显微镜验证了聚集体的结构.