Synthesis of a bistable [3]rotaxane and its pH-controlled intramolecular charge-transfer behavior

Synthesis of a bistable [3]rotaxane and its pH-controlled intramolecular charge-transfer behavior
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双稳态[3]轮烷的合成及其pH控制的分子内电荷转移行为

DOI:
10.1016/j.cclet.2013.04.007
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发表时间:
2013-07
影响因子:
9.1
通讯作者:
Liu, Yu
Liu, Yu
中科院分区:
化学1区
文献类型:
--
作者:
Wang, Hui;Zhang, Zhi-Jun;Zhang, Heng-Yi;Liu, Yu

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合成了一个含有两个萘并-21-冠-7(N21 C7)环和一个哑铃状结构的轮烷1。哑铃形分子4含有一个紫精核,两个仲烷基铵位点和两个苯基终止子。在用线状铵客体3将N21 C7环穿线之后,进行铜(I)催化的Huisgen炔-叠氮化物1,3-偶极环加成(CuAAC“点击”反应)以将假轮烷与紫精单元2连接并生成1。通过对[3]轮烷进行碱、酸循环处理,使两个N21 C7环沿着轴作往复运动。同时,该化合物的缺电子紫精单元和富电子萘酚基团之间的距离可以沿着精确调节,并具有明显的分子内电荷转移(CT)行为。
A [3]rotaxane 1 involving two naphtho-21-crown-7 (N21C7) rings and a dumbbell-shaped component 4 was synthesized. The dumbbell-shape molecule 4 contains one viologen nucleus, two secondary alkyl ammonium sites and two phenyl stoppers. After threading the N21C7 ring with the thread-like ammonium guest 3, the copper(I)-catalyzed Huisgen alkyne-azide 1,3-dipolar cycloaddition (CuAAC “click” reaction), was performed to connect the pseudorotaxanes with viologen unit 2 and generate 1. Through treating the [3]rotaxane by the base and acid circularly, the two N21C7 rings can make shuttling motion along the axle. Meanwhile the distance between the electron-deficient viologen unit and the electron-rich naphthol group can be adjusted precisely along with a remarkable intramolecular charge-transfer (CT) behavior.
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