在平面构型[PdnClm]^2-阴离子驱动下三种瓜环基超分子框架化合物的构筑

Three Cucurbit[n]uril-Based Supramolecular Frameworks Assembled by Planar Configuration[PdnClm]^2-Anions

采用无机阴离子诱导方法,以具有平面构型的[PdnClm]^2-阴离子为结构导向试剂,成功制备了3种具有框架结构特征的瓜环基超分子化合物:{Na2(H2O)6TMeQ[6]}[Pd2Cl6]·3H2O(1)、(H3O)2{CyH5Q[5]}[Pd2Cl6]·3H2O(2)及(H3O)2{Q[5]}[PdCl4]·23H2O(3)。X射线单晶衍射的结果表明:在1中,Na+离子与TMeQ[6]端口羰基氧直接配位形成一维结构的超分子链,在[Pd2Cl6]2-阴离子与TMeQ[6]的外壁作用下,进一步构筑形成三维的框架结构;在2中,在[Pd2Cl6]2-阴离子与CyH5Q[5]的外壁作用下,CyH5Q[5]以一维链有序排列,且4条CyH5Q[5]分子链可堆砌成一孔道,孔道中填充了[Pd2Cl6]2-阴离子,最终形成三维框架结构;在3中,8个[PdCl4]2-阴离子与4个Q[5]分子通过瓜环外壁相互作用,形成二维层状框架结构,层与层之间再通过非共价键作用力,最终形成三维层状框架结构。在这3种瓜环基超分子框架化合物中,[PdnClm]^2-阴离子促进了瓜环分子有序化排列,形成了具有框架结构特征的自组装体。这种主要驱动力来源于瓜环的外壁作用,即瓜环“正电性外壁”与[PdnClm]^2-阴离子间的离子偶极作用。

Three novel cucurbit[n]uril-based(Q[n]-based)supramolecular frameworks(QSFs)have been successfully prepared by using the planar configuration[PdnClm]^2-anion as the structure-directing agent,namely{Na2(H2O)6TMeQ[6]}[Pd2Cl6]·3H2O(1),(H3O)2{CyH5Q[5]}[Pd2Cl6]·3H2O(2)and(H3O)2{Q[5]}[PdCl4]·23H2O(3),respectively.Structural analysis reveals that using the[PdnClm]^2-anion as the structure-directing agent in different Q[n]systems that can promote the orderly arrangement of Q[n]s,and contribute to the formation of QSFs with different frame structures.For 1,the carbonyl groups of TMeQ[6]bind directly to the Na􀃬ions to form 1D coordination chains,which can be further built into 3D supramolecular architecture by outer surface interactions between TMeQ[6]and the[Pd2Cl6]2-anions.For 2,under the guidance of[Pd2Cl6]2-anions,CyH5Q[5]molecules can be orderly arranged to con-struct a 3D structure with pores which are filled with[Pd2Cl6]2-anions,while it can be found in 3 that Q[5]molecules can also be orderly arranged by[PdCl4]2-anionsto form a 3D frameworks with a 1D channel.The driving force to result in the formation of such frameworks is attributed to the outer surface interaction of Q[n]s,which is ion-dipole between the electrostatic potential positive outer surface of Q[n]s and the[PdnClm]^2-anions.CCDC:1956589,1;1956591,2;1956590,3.