Kubota Ryou, Tashiro Shohei, Shionoya Mitsuhiko
Department of Chemistry , Graduate School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku , Tokyo 113-0033 , Japan . Email:
Chem Sci. 2016 Mar 1;7(3):2217-2221. doi: 10.1039/c5sc04570c. Epub 2016 Jan 11.
Porous molecular solids composed of discrete macrocycles/cages have great potential for catalysis, separation and sensing techniques. Dynamic structural transformation of the host building blocks, especially a helicity inversion responsive to chemical triggers, is central to upgrading the spatial functions. Here we have achieved the syntheses of homochiral porous molecular solids composed of helical metal macrocycles through supramolecular chirality induction to both enantiomorphic forms with the aid of two different enantiopure sugar-derived lactones in the crystallization process. Moreover, we found that the helicity of the macrocyclic skeletons can be inverted in the crystalline state only by changing the type of solvent. This finding would lead to dynamic control of space chirality in connection with optical resolution, chiral amplification and asymmetric reactions.
由离散大环/笼状结构组成的多孔分子固体在催化、分离和传感技术方面具有巨大潜力。主体结构单元的动态结构转变,尤其是对化学触发因素响应的螺旋性反转,对于提升空间功能至关重要。在此,我们通过在结晶过程中借助两种不同的对映体纯糖衍生内酯对两种对映形态进行超分子手性诱导,实现了由螺旋金属大环组成的同手性多孔分子固体的合成。此外,我们发现仅通过改变溶剂类型就能在晶体状态下反转大环骨架的螺旋性。这一发现将导致与光学拆分、手性放大和不对称反应相关的空间手性的动态控制。