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A two-dimensional (2D) coordination polymer, [Co(4-dpds)(bdc)(H2O)2]&middot, 4-dpds (1) (4-dpds = 4,4&prime, dipyridyldusulfide and bdc2&minus, = dianion of benzenedicarboxylic acid), has been synthesized and structurally determined by single-crystal X-ray diffractometer. In 1, the bdc2&minus, and 4-dpds both act as bridging ligands connecting the Co(II) ions to form a 2D wrinkled-like layered coordination polymer. Two wrinkled-like layered coordination polymers are mutually penetrated to generate a doubly interpenetrated framework, and then extended to its 3D architecture via the supramolecular forces between doubly interpenetrated 2D frameworks and free 4-dpds ligands by intermolecular O&ndash, H&sdot, &sdot, N hydrogen bonding interaction. Crystal packing arrangements were characterized by fingerprint plots, which were derived from the Hirshfeld Surfaces analysis, and showed that intermolecular hydrogen bonding interactions are the most important interactions on the construction of the crystal 1.

A three-dimensional (3D) porous supramolecular architecture, {[Zn(bdc)(dpds)]·0.62(MeOH)·2H2O}n (1) (bdc2− = dianion of benzenedicarboxylic acid and dpds = 4,4′-dipyridyldisulfide), has been synthesized and structurally characterized. Single-crystal X-ray diffraction analysis reveals that each [Zn2(dpds)2]4+ macrocycle is connected by bdc2− ligands to form a two-dimensional (2D) layered metal–organic framework (MOF). Adjacent layers are further assembled via two interlayer π–π interactions in sandwich-type πpyridyl–πbenzene–πpyridyl and πpyridyl–πpyridyl fashions to afford a 3D porous supramolecular architecture. Controlled heating of the as-synthesized crystal 1 at ~120 °C causes de-solvated species of {[Zn(bdc)(dpds)]}n (1a). The structural determination of the de-solvated compound shows the same structural characterization as that of 1 with the only difference of the nonexistence of solvated MeOH and water molecules. The de-solvated 1a generates the re-hydrated crystal of {[Zn(bdc)(dpds)]·1.1(H2O)}n (1b) upon exposure to water vapor. The water ab-/de-sorption phenomenon by cyclic TG measurement suggests the complete reversibility upon re-/de-hydration between 1a and 1b, associated with reversible temperature-dependent emission properties. Such a reversible switching process of 1 at RT to 120 °C can proceed for at least 20 cycles, implying good thermoluminescence reversibility of 1 during the heating–cooling processes. After removal of the solvent molecules, compound 1a exhibits permanent porosity verified by the N2 sorption isotherm with a Langmuir surface area of 530.0 m2 g−1 and a Brunauer–Emmett–Teller (BET) surface area of 429.4 m2 g−1 and also exhibits significant gas storage capacities of 1.09 wt% for H2 at 77 K and 17 wt% for CO2 at 195 K. Moreover, 1a also displays interesting reversible water, methanol and ethanol vapor ad-/de-sorption behavior correlated with the polarity of the pore surface in 1a to the corresponding adsorbate molecules.