Zeolite Ionic Crystals Assembled through Direct Incorporation of Polyoxometalate Clusters within 3D Metal−Organic Frameworks

Polyoxometalate-based metal−organic frameworks {[Gd(dpdo)4(H2O)3](PMo12O40)(H2O)2CH3CN}n (2), {[Dy(dpdo)4(H2O)3](PMo12O40)(H2O)2CH3CN}n (3), {[Gd(dpdo)4(H2O)3](H3O)(SiMo12O40)(dpdo)0.5(CH3CN)0.5 (H2O)3}n (4), {[Ho(dpdo)4(H2O)3](H3O)(SiMo12O40)(dpdo)0.5(CH3CN)0.5(H2O)3}n (5), {[Ni(dpdo)2(CH3CN) (H2O)2]2(SiMo12O40)(H2O)2}n (6),
and {[Ni(dpdo)3]4(PW12O40)3[H(H2O)27(CH3CN)12]}n (7) (where dpdo is 4,4‘-bipyridine-N,N‘-dioxide) were constructed
via self-assembly by embedding Keggin-type polyanions within the intercrystalline voids as guests or pillars.
Compounds 2 and 3 are isomorphic and exhibit three-dimensional (3D) noninterwoven 64 frameworks with distorted-honeycomb cavities occupied by the polyanions. Compounds 4 and 5 are comprised of 3D noninterwoven frameworks
formed by linking the adjacent folded sheets through hydrogen bonds and π−π stacking interactions relative to the
free isolated dpdo ligand. Compound 6 is a pillar-layered framework with the [SiMo12O40]4- anions located on the
square voids of the two-dimensional bilayer sheets formed by the dpdo ligands and nickel(II) ions. Compound 7 is
a 3D metal−organic framework formed by nickel(II) and 4,4‘-bipyridine-N,N‘-dioxide with the globular Keggin-structure [PW12O4]3-anion as the template. A large protonated water cluster H+(H2O)27 is trapped and stabilized
within the well-modulated cavity.

以多金属氧酸盐（Polyoxometalate）为基础的金属有机框架（metal−organic frameworks）{[Gd(dpdo)4(H2O)3](PMo12O40)(H2O)2CH3CN}n (2)、{[Dy(dpdo)4(H2O)3](PMo12O40)(H2O)2CH3CN}n (3)、{[Gd(dpdo)4(H2O)3](H3O)(SiMo12O40)(dpdo)0.5(CH3CN)0.5(H2O)3}n (4)、{[Ho(dpdo)4(H2O)3](H3O)(SiMo12O40)(dpdo)0.5(CH3CN)0.5(H2O)3}n (5)、{[Ni(dpdo)2(CH3CN)(H2O)2]2(SiMo12O40)(H2O)2}n (6) 以及{[Ni(dpdo)3]4(PW12O40)3[H(H2O)27(CH3CN)12]}n (7)（其中dpdo为4,4'-联吡啶-N,N'-二氧化物（4,4‘-bipyridine-N,N‘-dioxide)），通过自组装策略构建，将凯金型（Keggin-type）多阴离子作为客体或柱体嵌入晶间空隙中。
化合物2与3为同构体，均呈现三维（3D）非互穿64拓扑框架，其扭曲蜂窝状空腔由多阴离子占据。
化合物4与5由三维非互穿框架构成，该框架通过氢键与π−π堆积作用，借助游离的孤立dpdo配体连接相邻的折叠片层。
化合物6为柱层状框架，[SiMo12O40]4-阴离子位于由dpdo配体与镍(II)离子形成的二维双层片层的方形空隙中。
化合物7为由镍(II)与4,4'-联吡啶-N,N'-二氧化物构建的三维金属有机框架，以球状凯金结构[PW12O4]3-阴离子作为模板，包封并稳定了大质子化水团簇H+(H2O)27，该团簇被限域在经精准调控的空腔内。