Wang Junting, Ju Yang-Yang, Low Kam-Hung, Tan Yuan-Zhi, Liu Junzhi
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Angew Chem Int Ed Engl. 2021 May 17;60(21):11814-11818. doi: 10.1002/anie.202102637. Epub 2021 Apr 12.
Here, we report a facile method to synthesize a series of macrocycles with different conformations. The planar macrocycle dimer (1), twisted macrocycle trimer (2) and "figure-eight" tetramer (3) are clearly elucidated by X-ray single-crystal analysis, in which the electron-rich phenanthrene units offer the possibility of supramolecular assembly. As expected, in the solid state, 1 and 3 assemble into a columnar stack and an interlocking dimer, respectively, via π-π interactions between the phenanthrene units. Compared to the rigid conformation of dimer 1, the structure of tetramer 3 is more flexible due to its enlarged ring size. 3 can deform from a figure-eight into a boat-shaped geometry to host a planar electron-deficient guest using its electron-rich phenanthrene units. When assembled with spherical electron-deficient C , interestingly, 3 further undergoes a conformational transformation from a figure-eight to a belt shape in order to host C . These supramolecular assembly behaviors of 3 demonstrate that it is an adaptable macrocyclic host for both planar molecules and fullerenes.
在此，我们报道了一种简便的方法来合成一系列具有不同构象的大环化合物。通过X射线单晶分析清晰地阐明了平面大环二聚体（1）、扭曲大环三聚体（2）和“8字形”四聚体（3），其中富电子的菲单元提供了超分子组装的可能性。正如预期的那样，在固态下，1和3分别通过菲单元之间的π-π相互作用组装成柱状堆积和互锁二聚体。与二聚体1的刚性构象相比，四聚体3的结构由于其增大的环尺寸而更加灵活。3可以从8字形变形为船形几何结构，利用其富电子的菲单元容纳平面缺电子客体。有趣的是，当与球形缺电子C组装时，3进一步经历从8字形到带状的构象转变以容纳C。3的这些超分子组装行为表明它是一种适用于平面分子和富勒烯的大环主体。
