Significant Effect of Flexibility of Bridging Alkyl Chains on?the?Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with Fourfold Rotaxane Linkage
Significant Effect of Flexibility of Bridging Alkyl Chains on?the?Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with Fourfold Rotaxane Linkage
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桥接烷基链的柔韧性对四重轮烷键共轭的堆叠卟啉和酞菁的邻近性的显着影响
DOI：
10.1002/chem.202200819
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Tanaka Kentaro
中科院分区：
文献类型：
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作者：
Yamada Yasuyuki;Iida Hayato;Shibano Shinya;Mihara Nozomi;Kato Tatsuhisa;Tanaka Kentaro
空间距离是控制共轭化合物中分子单元之间功能相互作用的一个重要因素，因此，桥联单元受到了密切的研究。在这里，我们考察了桥联烷基链的柔韧性对以四重轮烷键连接的堆积的卟啉和酞菁的接近程度的影响。我们发现，紧密堆积两个π体系需要桥联一定长度以上的烷基链，较短的桥阻碍堆积，因为它们的灵活性较低。卟啉与酞菁之间的堆积距离估计为4·03 ä，这是一种由短距离相互作用产生的独特的物理性质。较长的烷基链最大限度地减少了四重轮烷内部的空间限制，并允许卟啉和酞菁单元之间的有效通信。这是由于侧链的灵活性造成的。
Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10) chains was estimated to be 4.03 Å and showed a unique physical character arising from short‐distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains.