Dominguez Zaira, Dang Hung, Strouse M Jane, Garcia-Garibay Miguel A
Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA.
J Am Chem Soc. 2002 Mar 20;124(11):2398-9. doi: 10.1021/ja0119447.
We describe our efforts toward the preparation of materials built with molecules possessing topologies analogous to those of macroscopic compasses and gyroscopes. Samples of 1,4-bis(3,3,3-triphenylpropynyl)benzene (3) were prepared by a simple two-step procedure from triphenylmethyl chloride (1) and 1,4-diiodobenzene. The structure of compound 3 is such that the central phenylene can play the role of a gyroscope wheel while the two tritylpropynyl groups can act as an axle and shielding framework. Crystals of a benzene clathrate were characterized by single crystal X-ray diffraction and variable-temperature solid state NMR while their thermal stability was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The rotational dynamics of the phenylene group in the benzene clathrate and in desolvated samples were characterized in terms of a two-fold flipping process. Solid state rotational barriers of ca. 12.8 and 14.6 kcal/mol were estimated for the benzene clathrate and desolvated samples, respectively.
我们描述了我们为制备由具有与宏观指南针和陀螺仪类似拓扑结构的分子构建的材料所做的努力。通过由三苯甲基氯（1）和1,4 - 二碘苯经简单的两步程序制备了1,4 - 双（3,3,3 - 三苯基丙炔基）苯（3）的样品。化合物3的结构使得中心亚苯基可起到陀螺仪轮的作用，而两个三苯甲基丙炔基可充当轴和屏蔽框架。苯包合物的晶体通过单晶X射线衍射和变温固态核磁共振进行表征，同时通过差示扫描量热法（DSC）和热重分析（TGA）确定其热稳定性。根据双重翻转过程对苯包合物和去溶剂化样品中亚苯基基团的旋转动力学进行了表征。分别估计苯包合物和去溶剂化样品的固态旋转势垒约为12.8和14.6千卡/摩尔。
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