Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland, Canada A1B 3X7.
J Org Chem. 2010 Mar 5;75(5):1498-516. doi: 10.1021/jo9021748.
A series of linear and star-shaped pi-conjugated oligomer hybrids (2-5) composed of an oligoyne core, ranging from 1,3-butadiyne to 1,3,5,7,9,11-dodecahexayne, and fullerenyl end-capping groups has been synthesized and studied. The molecular structures of these fullerene-oligoyne hybrids were assembled through three key reactions: Pd-catalyzed cross-coupling, Cu-catalyzed oxidative homocoupling, and an in situ alkynylation reaction on [60]fullerene. The properties of these compounds were investigated by UV-vis spectroscopy, differential scanning calorimetry (DSC), and atomic force microscopy (AFM) with the purpose of understanding the thermal reactivity arising from the oligoyne moieties as well as the morphological properties on surface. Our study shows that these fullerene-oligoyne hybrids tend to aggregate in different morphologies, including nanospheres, nanoflakes, and continuous thin films, while the morphological properties appear to be subject to the influence of molecular factors such as oligomer chain length, solubilizing alkylphenyl groups, and the thermal reactivity of the oligoyne unit. The correlation between molecular property and interfacial aggregation behavior evinced by these fullerene-oligoyne hybrids suggests a viable approach to exert bottom-up control over the structures and properties of fullerene based nanomaterials.
一系列由齐聚物核心（从 1,3-丁二炔到 1,3,5,7,9,11-十二炔）和富勒烯端基组成的线性和星形π共轭寡聚物杂化物（2-5）已被合成并研究。这些富勒烯-齐聚物杂化物的分子结构是通过三个关键反应组装的：Pd 催化的交叉偶联、Cu 催化的氧化偶联和[60]富勒烯上的原位炔基化反应。通过紫外可见光谱、差示扫描量热法（DSC）和原子力显微镜（AFM）研究了这些化合物的性质，目的是了解来自齐聚物部分的热反应性以及表面的形态特性。我们的研究表明，这些富勒烯-齐聚物杂化物倾向于以不同的形态聚集，包括纳米球、纳米薄片和连续的薄膜，而形态特性似乎受到分子因素的影响，如寡聚物链长、溶解的烷基苯基基团和齐聚物单元的热反应性。这些富勒烯-齐聚物杂化物的分子性质与界面聚集行为之间的相关性表明，通过自下而上的方法来控制富勒烯基纳米材料的结构和性质是可行的。
