Chamberlain Thomas W, Pfeiffer Rudolf, Peterlik Herwig, Kuzmany Hans, Zerbetto Francesco, Melle-Franco Manuel, Staddon Luke, Champness Neil R, Briggs G Andrew D, Khlobystov Andrei N
School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, UK.
Small. 2008 Dec;4(12):2262-70. doi: 10.1002/smll.200800552.
Mechanisms for controlling the assembly of molecular arrays in carbon nanotubes via alteration of the size and geometry of the functional groups attached to the molecules inserted into the nanotubes are studied. As model compounds, a series of structurally related fullerenes functionalized with polyaryl groups (C(60)X, where X is a polyaryl group) of various lengths are synthesized to explore this effect. These molecules are inserted into single-walled carbon nanotubes (SWNTs) under mild conditions to prevent their decomposition and to form C(60)X@SNWT structures. The molecular chains thus formed are studied by high-resolution transmission electron microscopy, X-ray diffraction, and Raman spectroscopy, revealing that the functional groups increase the interfullerene separation proportionally with the size of X. However, the functional groups themselves appear to adopt various orientations with respect to each other and exhibit intermolecular pi-pi interactions within the cavities of the carbon nanotubes. All these effects create a distribution of observed interfullerene separations in nanotubes, which are examined by theoretical simulations and interpreted in terms of molecular geometries and intermolecular interactions.
研究了通过改变插入碳纳米管的分子上连接的官能团的大小和几何形状来控制碳纳米管中分子阵列组装的机制。作为模型化合物，合成了一系列用不同长度的多芳基（C(60)X，其中X是多芳基）官能化的结构相关的富勒烯，以探索这种效应。在温和条件下将这些分子插入单壁碳纳米管（SWNTs）中，以防止它们分解并形成C(60)X@SNWT结构。通过高分辨率透射电子显微镜、X射线衍射和拉曼光谱对由此形成的分子链进行了研究，结果表明官能团使富勒烯间的间距与X的大小成比例增加。然而，官能团本身似乎相互采取各种取向，并在碳纳米管的腔内表现出分子间的π-π相互作用。所有这些效应导致在纳米管中观察到的富勒烯间间距的分布，通过理论模拟对其进行了研究，并根据分子几何形状和分子间相互作用进行了解释。
