Light-driven monodirectional molecular rotor
Light-driven monodirectional molecular rotor
复制标题
光驱动单向分子转子
作者：
N. Koumura;R. Zijlstra;R. Delden;Nobuyuki Harada;B. Feringa
图5二氯化羰基促进2的单向旋转的光谱证据。部分氢核磁共振谱（监测相对于（CH3）4Si=0 p.p.m.的桥头堡质子）表明事件的顺序是时间的函数。光谱中峰旁的数字为图3中的结构。a， CDCl3中2；b、t0;Cl2C=O和Et3N的加入。2通过异氰酸酯3迅速转化为分子内聚氨酯5；异氰酸酯3和4转化为5的速度太快，在光谱中看不到。c，在环境温度（~22℃）下1.6小时后，~30%的5已经“越过驼峰”（图2d至图2f）旋转到6。d, e, f，随着时间的推移，5到6的旋转继续进行，5到6的单向转化在6小时内完成了约80%。氨基旋流剂7与Cl2C=O/Et3N反应直接制备的材料相同，氨基旋流剂6被分离出来。对照实验确定6不转化为5；也就是说，5→6的转换是单向的。利用ReactIR技术对2、7和9与Cl2C=O/NEt3（在9的情况下也是10）的相关反应进行红外光谱监测，证实了3-6的结构分配；该设备可以现场实时记录反应混合物的红外光谱，从而测定发生时官能团的变化。用氯化碳= O/氯化氮处理7可迅速生成6，但6不能明显转化为5)。最后，6被裂解为7，从而完成化学驱动的2到7的旋转。对照实验表明，在没有cl2c =O/Et 3n的情况下，纯2（在几天内）缓慢地转化为2,7和8的约1:0.8:1的平衡混合物（第三个低能转子：见图4）。在图5中，我们展示了实验数据，这些数据表明图3中的事件按照所示进行。1. 等。肌动蛋白-肌球蛋白复合物的结构及其对肌肉收缩的影响。脊椎动物平滑肌肌球蛋白运动域的结构及其与基本轻链的复合体：动力中风前状态的可视化。基于[2]轮烷衍生三联体的光诱导分子穿梭。
Figure 5 Spectroscopic evidence that carbonyl dichloride fuels the unidirectional rotation of 2. Partial 1 H NMR spectra (monitoring the bridgehead proton relative to (CH3)4Si=0 p.p.m.) indicate the sequence of events as a function of time. Numbers next to peaks in the spectra refer to structures in Fig. 3. a, 2 in CDCl3; b, t0; addition of Cl2C=O and Et3N. 2 is rapidly converted to intramolecular urethane 5 via isocyanate 3; the isocyanates 3 and 4 convert to 5 too rapidly to be seen in the spectra. c, After 1.6 h at ambient temperature (~22 °C), ~30% of 5 has rotated " over the hump " (Fig. 2d to Fig. 2f) to 6. d, e, f, Over further time, rotation of 5 to 6 continues, with unidirectional conversion of 5 to 6 being >80% complete in ~6 h. Urethane 6 was isolated and shown to be identical to material prepared directly from amine rotamer 7 by reaction with Cl2C=O/Et3N. Control experiments established that 6 does not convert to 5; that is, that the conversion of 5 → 6 is unidirectional. The assignment of structures to 3-6 is corroborated by infrared spectroscopic monitoring of the relevant reactions of 2, 7 and 9 with Cl2C=O/NEt3 (and also 10 in the case of 9), performed using ReactIR technology; this equipment makes it possible to record in situ, and in real time, the infrared spectra of reaction mixtures and to thereby assay functional group changes as they occur. treatment of 7 with Cl 2 C = O/Et 3 N leads rapidly to 6, but 6 does not detectably convert to 5). Finally, 6 is cleaved to give 7, thereby completing the chemically driven rotation of 2 to 7. Control experiments demonstrate that in the absence of Cl 2 C=O/Et 3 N, pure 2 slowly converts (over several days) to an approximately 1:0.8:1 equilibrium mixture of 2, 7 and 8 (the third low-energy rotamer: see Fig. 4). In Fig. 5 we show the experimental data which establish that the events in Fig. 3 proceed as indicated. 1. Rayment, I. et al. Structure of the actin-myosin complex and its implications for muscle contraction. structure of a vertebrate smooth muscle myosin motor domain and its complex with the essential light chain: visualization of the pre-power stroke state. A light-induced molecular shuttle based on a [2]rotaxane-derived triad.
影响因子：
15
作者：
Harada, N;Koumura, N;Feringa, BL
通讯作者：
Feringa, BL
N.Koumura：“独特手性烯烃的光化学和绝对立体化学，反式和顺式-1,1,2,2,3,3,4,4-八氢-3,3-二甲基-4，
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