A Series of Metal-Organic Frameworks with 2,2'-Bipyridyl Derivatives: Synthesis vs. Structure Relationships,...

Five new metal-organic frameworks based on Mn(II) and 2,2'-bithiophen-5,5'-dicarboxylate (btdc^2-) with various chelating N-donor ligands (2,2'-bipyridyl = bpy; 5,5'-dimethyl-2,2'-bipyridyl = 5,5'-dmbpy; 4,4'-dimethyl-2,2'-bipyridyl = 4,4'-dmbpy) [Mn₃(btdc)₃(bpy)₂]·4DMF, 1; [Mn₃(btdc)₃(5,5'-dmbpy)₂]·5DMF, 2; [Mn(btdc)(4,4;-dmbpy)], 3; [Mn₂(btdc)₂(bpy)(dmf)]·0.5DMF, 4; [Mn₂(btdc)₂(5,5'-dmbpy)(dmf)]·DMF, 5 (dmf, DMF = N,N-dimethylformamide) have been synthesized, and their crystal structure has been established using single-crystal X-ray diffraction analysis (XRD). The chemical and phase purities of Compounds 1-3 have been confirmed via powder X-ray diffraction, thermogravimetric, and chemical analyses as well as IR spectroscopy. The influence of the bulkiness of the chelating N-donor ligand on the dimensionality and structure of the coordination polymer has been analyzed, and the decrease in the framework dimensionality, as well as the secondary building unit's nuclearity and connectivity, has been observed for bulkier ligands. For three-dimensional (3D) coordination polymer 1, the textural and gas adsorption properties have been studied, revealing noticeable ideal adsorbed solution theory (IAST) CO₂/N₂ and CO₂/CO selectivity factors (31.0 at 273 K and 19.1 at 298 K and 25.7 at 273 K and 17.0 at 298 K, respectively, for the equimolar composition and the total pressure of 1 bar). Moreover, significant adsorption selectivity for binary C₂-C₁ hydrocarbons mixtures (33.4 and 24.9 for C₂H₆/CH₄, 24.8 and 17.7 for C₂H₄/CH₄, 29.3 and 19.1 for C₂H₂/CH₄ at 273 K and 298 K, respectively, for the equimolar composition and the total pressure of 1 bar) has been observed, making it possible to separate on 1 natural, shale, and associated petroleum gas into valuable individual components. The ability of Compound 1 to separate benzene and cyclohexane in a vapor phase has also been analyzed based on the adsorption isotherms of individual components measured at 298 K. The preferable adsorption of C₆H₆ over C₆H₁₂ by 1 at high vapor pressures (V_B/V_CH = 1.36) can be explained by the existence of multiple van der Waals interactions between guest benzene molecules and the metal-organic host revealed by the XRD analysis of 1 immersed in pure benzene for several days (1≅). Interestingly, at low vapor pressures, an inversed behavior of 1 with preferable adsorption of C₆H₁₂ over C₆H₆ (K_CH/K_B = 6.33) was observed; this is a very rare phenomenon. Moreover, magnetic properties (the temperature-dependent molar magnetic susceptibility, χ_p(T) and effective magnetic moments, μ_eff(T), as well as the field-dependent magnetization, M(H)) have been studied for Compounds 1-3, revealing paramagnetic behavior consistent with their crystal structure.