Structures and Supramolecular Properties of Inclusion Complexes of Anthracene‐Triptycene Nanocages with Fullerene Guests and Their Dynamic Motion as Molecular Gyroscopes
Structures and Supramolecular Properties of Inclusion Complexes of Anthracene‐Triptycene Nanocages with Fullerene Guests and Their Dynamic Motion as Molecular Gyroscopes
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富勒烯客体蒽-三蝶烯纳米笼包合物的结构和超分子性质及其作为分子陀螺的动态运动
DOI：
10.1002/chem.202203462
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Toyota Shinji
中科院分区：
文献类型：
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作者：
Mitani Takuji;Tsurumaki Eiji;Toyota Shinji
合成了三种由二芳基和三茂铁单元组成的大环笼状化合物的衍生物。经核磁共振氢谱和荧光光谱证实，这些纳米笼与C60和其他富勒烯客体形成了主客体络合物。甲苯基和2，4，6-三氧基苯衍生物与C60的结合常数为2.2×104L −1，大于五氟苯衍生物的结合常数。X-射线衍射分析得到了该络合作用的直接实验证据：客体C60分子通过多点CH-⋅⋅⋅π相互作用被包合在空腔中。变温X射线分析表明，C60分子的动力学无序表现为单轴运动，如陀螺运动。通过密度泛函理论计算，讨论了笼型定子在晶体中通过CH-⋅⋅⋅π相互作用锚定的球形C60转子的独特动力学行为，以及取代基对缔合性质的影响。
Three derivatives of macrocyclic cage compounds consisting of diarylanthracene and triptycene units were synthesized. These nanocages formed host‐guest complexes with C60and other fullerene guests as confirmed by1H NMR and fluorescence spectroscopy. The association constant of the mesityl and 2,4,6‐tributoxyphenyl derivatives with C60was determined to be 2.2 × 104L mol−1, which was larger than that of the pentafluorophenyl derivative. Direct experimental evidence of the complexation was obtained by X‐ray diffraction analysis: the guest C60molecule was included in the cavity via multipoint CH⋅⋅⋅π interactions. Dynamic disorders of the included C60molecule in variable‐temperature X‐ray analysis indicated uniaxial motion, such as gyroscopic motion. The unique dynamic behavior of the spherical C60rotor anchored by the cage stator via CH⋅⋅⋅π interactions in the crystal, as well as substituent effects on the association properties, are discussed with the aid of DFT calculations.