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    茆敏, 刘月, 杨舜, 曲大辉. 一种光酸响应型[2] 轮烷分子梭的合成与表征[J]. 华东理工大学学报(自然科学版), 2020, 46(5): 665-671. DOI: 10.14135/j.cnki.1006-3080.20191128001
    引用本文: 茆敏, 刘月, 杨舜, 曲大辉. 一种光酸响应型[2] 轮烷分子梭的合成与表征[J]. 华东理工大学学报(自然科学版), 2020, 46(5): 665-671. DOI: 10.14135/j.cnki.1006-3080.20191128001
    MAO Min, LIU Yue, YANG Shun, QU Dahui. Synthesis and Characterization of A Photoacid-Responsive [2]Rotaxane Molecular Shuttle[J]. Journal of East China University of Science and Technology, 2020, 46(5): 665-671. DOI: 10.14135/j.cnki.1006-3080.20191128001
    Citation: MAO Min, LIU Yue, YANG Shun, QU Dahui. Synthesis and Characterization of A Photoacid-Responsive [2]Rotaxane Molecular Shuttle[J]. Journal of East China University of Science and Technology, 2020, 46(5): 665-671. DOI: 10.14135/j.cnki.1006-3080.20191128001

    一种光酸响应型2 轮烷分子梭的合成与表征

    Synthesis and Characterization of A Photoacid-Responsive 2Rotaxane Molecular Shuttle

    • 摘要: 光诱导质子转移是一种可应用于酸碱响应主客体系统的新型调控策略。基于光诱导质子转移机制,设计和合成了光酸(部花青,MEH)响应型2 轮烷R分子梭,并采用核磁共振氢谱、碳谱和高分辨质谱对其结构进行表征。通过紫外-可见吸收光谱和变温核磁共振氢谱等手段,对比研究光照和置于暗处前后体系中吸收光谱和核磁共振氢谱的变化。结果表明:在MEH存在下于419 nm处光照时,分子梭中联吡啶鎓(CBPQT4+)大环在杆状组分一侧的萘环上络合,轮烷分子梭R处于“静止”状态;当体系置于暗处12 h时,CBPQT4+大环在杆状组分的两个萘环之间运动,分子梭R处于“运动”状态。该工作将为分子水平上的信息传递提供一种策略。

       

      Abstract: Stimulus-responsive molecular shuttles have unique shuttle movement capabilities in mechanically interlocked nanosystems, but how to choose appropriate and efficient control methods in a complex host-guest system has always been a difficult problem to be solved. Photochemical stimulation is considered to be the most promising and most valuable mode for regulating molecular machines, because light control is not only accurate in time and space, but also has the advantages of simplicity, cleanness and no pollution. Light-induced proton transfer is a novel regulation strategy that can be applied in the host-guest system of acid-base response. Based on the photo-induced proton transfer mechanism, a 2rotaxane R molecular shuttle with photoacid (merocyanine, MEH) controlled response was successfully designed and synthesized, and its structure was confirmed by 1H-NMR, 13C-NMR and mass spectrometry. Before and after exposing to light, the UV absorption and 1H-NMR spectra of the system were compared by means of UV-Vis and variable-temperature 1H-NMR spectroscopy. The results showed that in the presence of photoacid (MEH) at 419 nm, the cyclobis (paraquat-p-phenylene) (CBPQT4+ ) macrocycle was located on one side of the naphthalene, and the 2rotaxane R molecular shuttle was in a "stationary" state; while in the dark for 12 h, the CBPQT4+ macrocycle shuttled between the two naphthalene components, and the 2rotaxane R molecular shuttle was in a "moving" state. This work offers a strategy for conformational transmission in molecular level.

       

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