A cage-based cationic body-centered metal-organic framework was successfully synthesized using a custom-designed bifunctional triazolcarboxylate ligand. It shows interesting single-crystal-to-single-crystal transformation upon solvent exchange process and selective uptake of organic dyes.

A two-dimensional honeycomb network of {[Zn 2 (bpydb) 2 (H 2 O) 2 ](DMA) 3 (H 2 O)} 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,Ndimethylformamide) were obtained. MOF 2 displays a 3D pillarbilayered 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 CO 2 adsorption behaviors of the activated 3 were investigated.