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The formation and analysis of ten microporous triazolyl isophthalate based MOFs, including nine isomorphous and one isostructural compound is presented. The compounds 1 M – 3 M with the general formula [ M ( R 1 - R 2 - trz - ia ) ] ∞ 3 ·x H 2 O (M 2+ = Co 2+ , Cu 2+ , Zn 2+ , Cd 2+ ; R 1 = H, Me; R 2 = 2py, 2pym, prz (2py = 2-pyridinyle; 2pym = 2-pyrimidinyle; prz = pyrazinyle)) crystallize with rtl topology. They are available as single crystals and also easily accessible in a multi-gram scale via refluxing the metal salts and the protonated ligands in a solvent. Their isomorphous structures facilitate the synthesis of heteronuclear MOFs; in case of 2 M , Co 2+ ions could be gradually substituted by Cu 2+ ions. The Co 2+ :Cu 2+ ratios were determined by ICP-OES spectroscopy, the distribution of Co 2+ and Cu 2+ in the crystalline samples are investigated by SEM-EDX analysis leading to the conclusions that Cu 2+ is more favorably incorporated into the framework compared to Co 2+ and, moreover, that the distribution of the two metal ions between the crystals and within the crystals is inhomogeneous if the crystals were grown slowly. The various compositions of the heteronuclear materials lead to different colors and the sorption properties for CO 2 and N 2 are dependent on the integrated metal ions.
An isomorphous series of 10 microporous copper-based metal–organic frameworks (MOFs) with the general formulas ∞3[{Cu3(μ3-OH)(X)}4{Cu2(H2O)2}3(H-R-trz-ia)12] (R = H, CH3, Ph; X2– = SO42–, SeO42–, 2 NO32– (1–8)) and ∞3[{Cu3(μ3-OH)(X)}8{Cu2(H2O)2}6(H-3py-trz-ia)24Cu6]X3 (R = 3py; X2– = SO42–, SeO42– (9, 10)) is presented together with the closely related compounds ∞3[Cu6(μ4-O)(μ3-OH)2(H-Metrz-ia)4][Cu(H2O)6](NO3)2·10H2O (11) and ∞3[Cu2(H-3py-trz-ia)2(H2O)3] (12Cu), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.