Synthesis and Properties of Fullerene-Containing Catenanes and Rotaxanes and Their Application into Molecular Machines

本研究旨在利用给体-受体相互作用的方法合成富勒烯类单环戊二烯和轮烷类化合物，并对它们的性质进行了研究。本论文合成了[60]富勒烯类单加合物1a-c，它们都具有缺电子的萘四甲酸二亚胺结构，作为合成单环戊二烯和轮烷类化合物的共同原料，并成功地将1a-c与富含电子的二氮杂环芳醚反应合成了轮烷类化合物3和4。在-78℃时，单加成物1的分子内Bingel反应成功地得到了具有D-A-D-A堆积结构的中性[2]烯4而1与过量的[60]富勒烯发生分子间Bingel反应得到[2]轮烷3。用硅胶柱层析和凝胶渗透色谱分离得到2个轮烷4和3，并用~1H核磁共振、MALDI-TOF和UV-Vis光谱进行了表征。[2]含[60]富勒烯双加成结构的环烯4(n=2)经高效液相色谱分离得到3个区域异构体，经UV-Vis光谱鉴定为反式-2、反式-3和反式-3。反应温度的降低是形成[2]链烷和[2]轮烷的关键。轮烷3的UV-Vis光谱在400-500 nm范围内有一个新的CT谱带。在轮烷3的荧光光谱中，二氮杂冠醚部分的发射被显著地熄灭，这主要是由于能量和/或电子转移到萘四甲酸二亚胺和/或富勒烯部分。为了提高环烷和轮烷的产率，现在考察了使用[60]富勒烯单加合物来携带更缺乏电子的环二亚胺部分。

The present study aims at the preparations of the fullerene-containing catenanes and rotaxanes by using donor-acceptor interaction and the elucidation of their properties.I have prepared [60]fullerene monoadducts 1a-c possessing an electron-deficient naphthalenetetracarboxylic diimide moiety as common starting materials for the catenanes and rotaxanes, and succeeded in the preparation of rotaxanes 3 and catenanes 4 by combining 1a-c with electron-rich dinaphthocrown ether 2.The intramolecular Bingel reactions of monoadducts 1 in the presence of 2 at -78 ℃ successfully afforded novel neutral [2]catenanes 4 with D-A-D-A stacking structure, while the intermolecular Bingel reactions of 1 with excess [60]fullerene gave [2]rotaxanes 3. Both catenanes 4 and rotaxanes 3 were isolated by column chromatography (silica gel) and GPC, and characterized by ^1H NMR, MALDI-TOF mass, and UV-Vis spectroscopies. [2]Catenane 4 (n = 2), which includes a [60]fullerene bisadduct moiety, was successfully separated by HPLC into three regioisomers, which were identified as trans-2, trans-3, and e by UV-Vis spectroscopy. The lowering of reaction temperature is critical for the formation of [2]catenanes and [2]rotaxanes.The UV-Vis spectra of rotaxanes 3 show a new band assigned to the CT-band in the region of 400-500 nm. In the fluorescence spectra of rotaxanes 3, the emission of dinaphthocrown ether moiety was significantly quenched, mainly due to the energy and/or electron transfer to the naphthalenetetracarboxylic diimide and/or fullerene moiety.In order to increase the yield of the catenanes and rotaxanes, the use of [60]fullerene monoadducts carrying a more electron-deficient perylene diimide moiety is now examined.