摘要/Abstract

设计合成了四吡啶基取代的碗烯衍生物COPY2. 通过核磁研究表明, 在模板分子C₆₀或C₇₀存在下, 配体COPY2与金属钯分别在室温和55 ℃下通过自组装形成1∶1分子笼络合物C_60/70?COPY2-Pd. 当络合物C₆₀?COPY2-Pd与C₇₀等物质的量混合或者络合物C₇₀?COPY2-Pd与C₆₀等物质的量混合于90 ℃加热48 h后, 络合物C₆₀?COPY2-Pd与C₇₀?COPY2-Pd的比例均为4∶1. 将配体COPY2与Pd(CH₃CN)₂Cl₂加入等物质的量C₆₀和C₇₀混合物中加热平衡后, 络合物C₆₀?COPY2-Pd与C₇₀?COPY2-Pd的比例同样为4∶1. 当C₆₀和C₇₀的比例为2∶1时, 体系中只生成络合物C₆₀?COPY2-Pd; 而当C₆₀和C₇₀的比例为1∶2时, 平衡后络合物C₆₀?COPY2-Pd与C₇₀?COPY2-Pd的比例为3.3∶1. 这些结果表明, 配体COPY2在金属钯存在时对C₆₀络合能力强于C₇₀的络合能力. 加入DMAP能够实现络合物解离, 释放笼内富勒烯并回收COPY2. 因此, 配体COPY2可应用于室温下对C₆₀的富集.
关键词: 碗烯, 分子笼, 富勒烯, 自组装
A tetrapyridyl substituted corannulene derivative COPY2 was designed and synthesized. Only in the presence of template molecule C₆₀ or C₇₀, COPY2 and palladium could form 1∶1 molecular cage complex C_60/70?COPY2-Pd by self-assembly at room temperature and 55 ℃ respectively. C₆₀ and C₇₀ were used not only as a template for constructing target molecular cages, but also as a stabilizer for molecular cage. When 1.0 equiv. C₇₀ mixed with C₆₀?COPY2-Pd or 1.0 equiv. C₆₀ mixed with C₇₀?COPY2-Pd, the ratio of complex C₆₀?COPY2-Pd to C₇₀?COPY2-Pd is 4∶1 after the mixtures were heated at 90 ℃ for 48 h, which is consistent with the ratio of COPY2 and Pd(CH₃CN)₂Cl₂ mixed with C₆₀ and C₇₀ (1∶1). Only the complex C₆₀?COPY2-Pd was observed when the ratio of C₆₀ to C₇₀ is 2∶1. However, even the ratio of C₆₀ to C₇₀ is 1∶2, complex C₆₀?COPY2-Pd is still the dominant species in the mixture. These results demonstrate that complexing ability of COPY2 with C₆₀ is stronger than that of COPY2 with C₇₀. 4-Dimethylaminopyridine (DMAP) was chosen to dissociate the cage so as to release fullerene and ligand. Therefore, the ligand COPY2 could be used to the enrichment of C₆₀ at room temperature.
Key words: corannulene, molecular cage, fullerene, self-assembly


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