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

本研究的目的是通过给体-受体相互作用制备含富勒烯的索烃和轮烷并阐明它们的性质。我制备了[60]具有缺电子萘四甲酸二酰亚胺部分的富勒烯单加合物1a-c作为索烃和轮烷的共同起始原料，并成功地将1a-c与富电子的二萘并冠醚2结合制备了轮烷3和索烃4。78 ℃成功地合成了具有D-A-D-A堆积结构的新型中性[2]索烃4，而1与过量[60]富勒烯发生分子间Bingel反应，合成了[2]轮烷3。通过柱色谱（硅胶）和GPC分离索烃4和轮烷3，并通过1H NMR、MALDI-TOF质谱和UV-Vis光谱表征。[2]Catenane 4（n = 2），其中包括一个[60]富勒烯双加合物部分，被成功地通过HPLC分离成三个区域异构体，它们被确定为反式-2，反式-3，e通过紫外可见光谱。反应温度的降低对[2]索烃和[2]轮烷的生成是至关重要的。轮烷3的UV-Vis光谱在400-500 nm区域显示了一个新的归属于CT-带的带。在轮烷3的荧光光谱中，二萘并冠醚部分的发射被显著淬灭，这主要是由于能量和/或电子转移到萘四羧酸二酰亚胺和/或富勒烯部分。为了提高索烃和轮烷的产率，现在研究使用带有更多缺电子的二萘嵌苯二酰亚胺部分的[60]富勒烯单加合物。

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.