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Two novel microporous metal–organic frameworks were obtained by combination of a tetratopic linker and linear trinuclear cobalt(II) and cadmium(II) cluster subunits. The complexes exhibit unprecedented topological features and unique magnetic and photoluminescence properties.

Two novel 3D porous metal–organic frameworks, {[Zn2(bpt)(btc)]·4H2O}n (1) and {[Cd2(bpt)(btc)(H2O)]·(DMA)2}n (2) (DMA = N,N-dimethylacetamide), were prepared based on 3,5-bis(pyrazinyl)-1,2,4-trizole (Hbpt) with the auxiliary ligand 1,3,5-benzenetricarboxylic acid (H3btc). Complex 1 could be described as a (3,6)-connected binodal 3D network with rutile topology and Schlafli symbol of (4.62)2(42.610.83), where its coordination framework exhibits a high thermal stability up to 420 °C as well as excellent boiling-water resistance. Complex 2 shows a (3,6,8)-connected trinodal 3D framework with a Schlafli symbol of (4.62)2(414.612.82)(44.610.8), which has not been reported previously. Interestingly, the gas-adsorption investigation discloses that complex 1 possesses a high enthalpy of H2 adsorption (9.6 kJ mol−1). Intensive solid-state fluorescence spectra of complexes 1 and 2 have also been determined.

An example of structural evolution from inclined polycatenation to parallel polyrotaxane-like interpenetration is demonstrated by modifying the (6,3) layer. Notably synergies of co-ligand binding mode and metal coordination geometry provide the appropriate constituent motifs necessary to instill this entanglement variation.

Two three-dimensional coordination polymers were solvothermally prepared through in situ formation of a 2-sulfobenzoic acid ligand from a 2,2′-dithiobisbenzoic acid precursor involving the oxidative cleavage of its disulfide bond. Complex 1 shows neb-e topology, while complex 2 exhibits a scarcely reported twisting chiral dense 75.9 net.