卤化富勒烯研究进展

自从C60被发现并能被大量制备以来,富勒烯化学已成为有机化学学科发展最快的领域之一.富勒烯通过多加成反应形成具有独特结构和性能的富勒烯卤化物和全氟烷基化物,为设计合成新型富勒烯基功能材料开辟了新方向.本文综述了近几年来在卤化富勒烯和全氟烷基化富勒烯的合成方法、结构及性能方面取得的最新进展,重点介绍了氟化富勒烯及其衍生化反应,并展望了该领域今后的发展趋势.     

卤化富勒烯研究进展

自从C60被发现并能被大量制备以来,富勒烯化学已成为有机化学学科发展最快的领域之一。富勒烯通过多加成反应形成具有独特结构和性能的富勒烯卤化物和全氟烷基化物,为设计合成新型富勒烯基功能材料开辟了新方向。本文综述了近几年来在卤化富勒烯和全氟烷基化富勒烯的合成方法、结构及性能方面取得的最新进展,重点介绍了氟化富勒烯及其衍生化反应,并展望了该领域今后的发展趋势。     

富勒烯的全氟烷基化

全氟烷基富勒烯具有较高的稳定性和溶解性,已成为富勒烯研究领域中逐步兴起的一类重要衍生物,有望用于合成具有特殊性能的新型富勒烯基功能材料,进而为富勒烯的衍生化和功能化研究指出了一个新方向.本文综述了近年来全氟烷基富勒烯的合成、结构及性能研究等方面取得的最新进展,重点介绍了富勒烯的三氟甲基化研究,并展望了该领域的发展趋势.     

富勒烯合成化学研究进展

富勒烯是一类由12个五元环和若干六元环组成的笼状分子, 自20世纪80年代中期被发现以来就以其独特的结构和新奇的性质而成为科学界研究的热点, 25年来, 无论在基础研究还是在实际应用领域都有了长足的进步, 人们在发展富勒烯合成新方法和寻找富勒烯新结构方面做了大量的工作。本文对富勒烯的各种宏量合成方法进行了回顾, 并概述了迄今已发表的60余种富勒烯新结构,包括各种富勒烯空笼、内嵌富勒烯、富勒烯笼外修饰衍生物及氮杂富勒烯等结构。     

含铥金属富勒烯的生成及其特殊的溶解行为

金属富勒烯的合成及结构研究是当前富勒烯化学研究的重要内容[1]．一些稀土金属元素，如Sc[2]、Y[3]及大部分斓系元素（La、Ce、Nd、Sin、Eu、Gd、Tb、Ho）[4]形成的金属富勒烯已被合成出来．但仍有一些稀土富勒烯的合成尚未见报道，使人们难以对金属富勒烯的形成机制及物化性能作出全面的判断．本文采用原位活化、交换电极回放电弧放电及两步提取法首次得到含锡金属富勒烯．通过空白对比实验确定了Tin＠C。怕9生成．对甲苯及毗院提取液的质谱研究表明含镀金属富勒烯具有区别于其它金属富勒烯的特殊的溶解性能，显示出其可能具有独特的…     

氟化富勒烯的研究进展

介绍了近几年来氟化富勒烯的合成、分离和一般性能.     

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.     

笼内金属富勒烯研究进展

回顾了十年来关于笼内金属富勒烯的研究工作，详细介绍了笼内金属富勒烯的各种合成方法、提取手段以及分离方法，阐明了笼内金属富勒烯的电子结构并给出了各类方法对其结构、性质研究取得的成果，最后指出了笼内金属富勒烯的研究前景与应用潜力。     

富勒烯/环糊精复合物及其在生物医药领域的应用

富勒烯有着独特的球形结构,这一结构赋予了其优异的光电及生物性能,在生物医药领域备受关注。环糊精具有良好的水溶性和生物相容性,锥筒状结构赋予了其特异性包合作用,在主客体化学中有着非常重要的地位。富勒烯/环糊精的复合物,结合了富勒烯和环糊精的优势,在DNA切割,光动力学疗法,药物载体等领域发挥了重要作用。本文从富勒烯与环糊精体系的构筑出发,综述了富勒烯/环糊精非共价包合物及共价偶联物在生物医药领域应用的研究进展,且对富勒烯/环糊精复合物的应用进行了展望,为构建新型富勒烯/环糊精复合物提供参考。     

η^2—C60[RhCI（CO）（PPh3）2]配合物的合成与表征

从1985年Smalley等^[1]发现C60等富勒烯至1996年富勒烯的发现者获诺贝尔化学奖期间,在化学、材料、物理等领域形成了富勒烯的研究热潮^[2-5]。现在科学工作者正以较大的注意力投向富勒烯的化学修饰,研究富勒烯各类衍生物的结构与性能之间内在联系规律,以期望在开发应用方面取得突破性进展,为此也十分重视对具有特殊组成与结构的富勒烯衍生物的研究。本文首次合成出η^2-C60[RhCI(CO)(PPh3)2]配合物,并对其结构进行了表征。     

富勒烯的化学研究进展

本文评述了富勒烯化学研究的新进展, 从[ 60 ]、[ 70 ]富勒烯的化学修饰、富勒烯金属包合物、掺杂富勒烯、碳纳米管以及富勒烯的化学合成等几个方面着重介绍了国际上富勒烯研究的热点, 对进一步研究的方向进行了讨论。     

富勒烯硫化反应进展

富勒烯官能化研究是富勒烯化学的重要组成部分。 近年来,随着富勒烯化学研究的深入发展,许多新颖富勒烯衍生物被陆续合成出来,并在生物医学和有机太阳能电池方面显示出良好的应用潜力。 与快速发展的富勒烯化学相比,富勒烯硫化反应研究进展较慢,近年来逐步引起广泛兴趣。 在此,我们结合本课题组开展的工作,对富勒烯硫化反应的最新进展进行总结。     

Strain Release of Fused Pentagons in Fullerene Cages by Chemical Functionalization

According to the isolated pentagon rule (IPR), for stable fullerenes, the 12 pentagons should be isolated from one another by hexagons, otherwise the fused pentagons will result in an increase in the local steric strain of the fullerene cage. However, the successful isolation of more than 100 endohedral and exohedral fullerenes containing fused pentagons over the past 20 years has shown that strain release of fused pentagons in fullerene cages is feasible. Herein, we present a general overview on fused‐pentagon‐containing (i.e. non‐IPR) fullerenes through an exhaustive review of all the types of fused‐pentagon‐containing fullerenes reported to date. We clarify how the strain of fused pentagons can be released in different manners, and provide an in‐depth understanding of the role of fused pentagons in the stability, electronic properties, and chemical reactivity of fullerene cages.     

Geometrical and Electronic Rules in Fullerene‐Based Compounds

The discovery of buckminsterfullerene C₆₀ opened up a new scientific area and stimulated the development of nanoscience and nanotechnology directly. Fullerene science has since emerged to include fullerenes, endohedral fullerenes (mainly metallofullerenes), exofullerenes, and carbon nanotubes as well. Herein, we look back at the development of fullerene science from the perspective of epistemology by highlighting the proposed main rules or criteria for understanding and predicting the structures and stability of fullerene‐based compounds. We also point out that a rule or criterion may contribute significantly to the corresponding discipline and suggest that two unsolved issues in fullerene science are the addition patterns of fullerene derivatives and the structures and stability of nonclassical fullerenes.     

Hydrogen-bonding motifs in fullerene chemistry

The combination of fullerenes and hydrogen-bonding motifs is a new interdisciplinary field in which weak intermolecular forces allow modulation of one-, two-, and three-dimensional fullerene-based architectures and control of their function. This Minireview aims to extend the scope of fullerene chemistry to a truly supramolecular level from which unprecedented architectures may evolve. It is shown that electronic communication in C(60)-based hydrogen-bonded donor-acceptor ensembles is at least as strong as that found in covalently connected systems and that hydrogen-bonding fullerene chemistry is a versatile concept for the construction of functional ensembles.     

Supramolecular Interaction of Fullerenes with a Curved π‐Surface of a Monomeric Quadruply Ring‐Fused Porphyrin

Molecular binding of fullerenes, C₆₀ and C₇₀, with the Zn^II complex of a monomeric ring‐fused porphyrin derivative ( 2 ‐py) as a host molecule, which has a concave π‐conjugated surface, has been confirmed spectroscopically. The structures of associated complexes composed of fullerenes and 2 ‐py were explicitly established by X‐ray diffraction analysis. The fullerenes in the 2:1 complexes, which consist of two 2 ‐py molecules and one fullerene molecule, are fully covered by the concave surfaces of the two 2 ‐py molecules in the crystal structure. In contrast, in the crystal structure of the 1:1 complex consisting of one 2 ‐py molecule and one C₆₀ molecule, the C₆₀ molecule formed a π–π stacked pair with a C₆₀ molecule in the neighboring complex using a partial surface, which was uncovered by the 2 ‐py molecule. Additionally, the molecular size of fullerene adopted significantly affects the ¹H NMR spectral changes and the redox properties of 2 ‐py upon the molecular binding.     

Computational Studies on Non‐covalent Interactions of Carbon and Boron Fullerenes with Graphene

First‐principles DFT calculations are carried out to study the changes in structures and electronic properties of two‐dimensional single‐layer graphene in the presence of non‐covalent interactions induced by carbon and boron fullerenes (C₆₀, C₇₀, C₈₀ and B₈₀). Our study shows that larger carbon fullerene interacts more strongly than the smaller fullerene, and boron fullerene interacts more strongly than that of its carbon analogue with the same nuclearity. We find that van der Waals interactions play a major role in governing non‐covalent interactions between the adsorbed fullerenes and graphene. Moreover, a greater extent of van der Waals interactions found for the larger fullerenes, C₈₀ and B₈₀, relative to smaller C₆₀, and consequently, results in higher stabilisation. We find a small amount of electron transfer from graphene to fullerene, which gives rise to a hole‐doped material. We also find changes in the graphene electronic band structures in the presence of these surface‐decorated fullerenes. The Dirac cone picture, such as that found in pristine graphene, is significantly modified due to the re‐hybridisation of graphene carbon orbitals with fullerenes orbitals near the Fermi energy. However, all of the composites exhibit perfect conducting behaviour. The simulated absorption spectra for all of the graphene–fullerene hybrids do not exhibit a significant change in the absorption peak positions with respect to the pristine graphene absorption spectrum. Additionally, we find that the hole‐transfer integral between graphene and C₆₀ is larger than the electron‐transfer integrals and the extent of these transfer integrals can be significantly tuned by graphene edge functionalisation with carboxylic acid groups. Our understanding of the non‐covalent functionalisation of graphene with various fullerenes would promote experimentalists to explore these systems, for their possible applications in electronic and opto‐electronic devices.