基于全-6-脱氧-6-(4-甲酰苯基)-β-环糊精的一维自组装通道结构构筑的有机框架结构

Hydrogen-bonded Organic Frameworks with Straight 1D Channels Based on the Self-assembly of 6-Perdeoxy-6-Per(4-Formyl-Phenyl)-β-Cyclodextrin

合成了全-6-脱氧-6-(4-甲酰苯基)-β-环糊精(1),利用X射线晶体学研究了其在固相中的自组装行为.结果显示,苯甲酰基沿着β-环糊精的侧壁伸展,分子呈冠状,两个分子形成了头-对-头的二聚体,并沿c轴形成了一维通道超结构。相邻的一维通道结构通过氢键相连形成了具有孔隙的有机框架结构。在这个有机框架结构中,芳香环通过C-H…O氢键在环糊精的小口端形成了疏水层,羟基通过氢键相互作用在大口端形成了亲水层。

A novel 6-perdeoxy-6-per(4-formyl-phenyl)-β-cyclodextrin(1)was synthesized and its self-assembly behavior in the solid state was determined by X-ray crystallography.The crystal structure shows a‘crown’shape that the substituent groups stretch along the side wall of theβ-cyclodextrin.The original skeleton of cyclodextrin moiety with an approximate 7-fold axis is not changed with substituting aromatic groups for hydroxyl groups.The 6-per-modifiedβ-cyclodextrins are aligned on the c-axis and form the one-dimensional channel superstructure with a head-to-head dimer as the repeating motif.Furthermore,the 1 Dchannels stack into hexagon periodically and extend to an organic frameworks.In this organic frameworks,the aromatic rings are interacted by C-H…O hydrogen bonds which results in the hydrophobic layers at the primary side,and the hydroxyl groups are interacted by hydrogen bonds,which form the hydrophilic layers at the secondary side.These preliminary studies reveal that the 6-per-substituted-β-cyclodextrins can self-assemble into organic frameworks in the solid state,which opens new avenues toward cyclodextrins chemsitry.