The hydrothermal reaction of M(NO3)2·6H2O (M = Ni and Zn) with benzene-1,3,5-tricarboxylic acid (H3btc) and 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) produced the mixed-ligand coordination polymers (MOFs) 3∞{[Ni3(µ3-btc)2(µ4-btre)2(µ-H2O)2]·∼22H2O} (1) and 3∞{[Zn3(µ4-btc)2(µ4-btre)(H2O)2]·2H2O} (3). The compounds, characterized by single-crystal X-ray diffraction, X-ray powder diffraction and thermoanalysis feature trinuclear secondary building units (SBU) within the three-dimensional frameworks. The trinuclear nickel unit in 1 exhibits an intra-trimer together with some weak inter-trimer antiferromagnetic coupling with J = −13.88(8) cm−1 from the magnetic susceptibility measurement between 1.9–300 K. The zinc coordination polymer 3 shows a strong fluorescence at 423 nm upon excitation at 323 nm (not seen in the free btre ligand). Compound 3 is thermally robust until 200 °C (ambient pressure) where loss of the water molecules starts. Careful control of the dehydration procedure (freeze-drying) for 1 and (heating to 280 °C) for 3 allowed for a solid-state reaction with single-crystal-to-single-crystal structural transformations in obtaining the largely dehydrated products 3∞{[Ni3(µ2-btc)2(µ4-btre)2(µ-H2O)2(H2O)2]·4H2O} (2) and 3∞{[Zn3(µ6-btc)2(µ4-btre)2]·∼0.67H2O} (4), respectively. In the transformation from 1 to 2 the unit cell volume is reduced to about 60%. The transition from 3 to 4 involves breakage and formation of new Zn–O bonds.
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