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Through a pillar-ligand extension strategy, a rare breathing behavior in polycatenated 2D→3D nets has been achieved. Three variants exhibit interesting sorption properties that range from non-breathing to breathing behaviors, which is influenced by the angles between the pillars and the single honeycomb layers. The increase in pillar length does not lead to an increase in polycatenation multiplicity, which is controlled by the length of intralayer tripodal carboxylate. It also does not induce obviously expanded interlayer separations but occupies much more the free voids, and as a consequence, a smaller pore volume is obtained. This suggests that in 2D→3D polycatenated bilayer metal-organic frameworks, the porosity is not always enhanced by increasing the length of the interlayer pillars with the intralayer linker remaining unchanged. [ABSTRACT FROM AUTHOR]

Three metal organic coordination compounds, namely, {[Cd2(L1)4]2 ·9H2O} n ( 1), {[Zn(L1)2 ·2H2O]2 ·H2O} n ( 2), and [Cu(L2)2] n ( 3), [L1 = 3-chloro-2-(5 H-tetrazol-5-yl)pyridine; L2 = 3-chloropicolinic acid], were hydrothermally synthesized, in which L1 and L2 were synthesized by in situ reactions. X-ray diffraction analyses revealed that the 2D layer of complex 1 is built from a dinuclear CdII second building blocks, whereas complex 2 shows 0D structure, which is built based on two L1 ligands, one zinc ion, and two water molecules. 3 shows a 1D infinite rod-shaped chain. Additionally, the solid-state fluorescence properties for compound 1 and 2 are also presented. [ABSTRACT FROM AUTHOR]