Tuning Two-Dimensional Layer to Three-Dimensional Pillar-Layered Metal-Organic Frameworks: Polycatenation and Interpenetration Behaviors

A two-dimensional honeycomb network of {[Zn-2(bpydb)(2)(H2O)(2)](DMA)(3)(H2O)}(n) (1) was solvothermally synthesized and structurally characterized. By employing 4,4'-bipyridine (bpy) as a pillar, two additional three-dimensional (3D) metal-organic frameworks (MOFs) of {[Zn-2(bpydb)(2)(bpy)(EtO-H)(2)](DMF)(EtOH)}(n) (2) and {[Zn(bpydb)(bpy)](DMA)-(EtOH)(6)}(n) (3) (bpydbH(2) = 4,4'-(4,4'-bipyridine-2,6-diyl) dibenzoic acid, DMA = N,N- dimethylacetamide, DMF = N,N-dimethylformamide) were obtained. MOF 2 displays a 3D pillar-bilayered network generated from polycatenation of the 2D bilayers. By carefully adjusting the reaction condition, MOF 3 was harvested, showing a 2-fold interpenetrated (3,5)-connected hms net. The phase purity, thermal stability, and luminescent properties of the three MOFs were studied. In addition, N-2 and CO2 adsorption behaviors of the activated 3 were investigated.