Supramolecular Isomerism in Cobalt(II) Coordination Polymers Built from 3,5-Bis(trifluoromethyl)benzoate and 4,4′-Bipyridine

The reaction of [Co2(H2O)(TFMBz)4(py)4] (1) (TFMBz: 3,5-bis(trifluoromethyl)benzoate; py: pyridine) with 4,4′-bipyridine (bpy) in different solvents yields four coordination polymers with unlikely structures but with the same stoichiometry. Three of them contain similar ladder chains consisting of binuclear nodes "Co2(TFMBz)4", in which two of the TFMBz ligands show bidentate bridge coordination, double linked to each adjacent node by bpy but packed in different fashions. The different packing affects the compound porosity; thus, [Co2(TFMBz)4(bpy)2]n (2), precipitated using low-polarity solvents such as supercritical CO2 (scCO2), n-butyl acetate, or heptane and also in acetonitrile, is microporous, with a surface area of 330 m2 g-1, showing the N2 adsorption/desorption isotherm at 77 K with a gate-opening effect at low relative pressures (P/P0 = 0.05). The isomer [Co2(TFMBz)4(bpy)2]n (3), synthesized in ethoxyethanol, presents a surface area of 230 m2 g-1. A third chain packing isomer, [Co2(TFMBz)4(bpy)2]n (4), is obtained in acetone and has only non-interconnected voids. Finally, precursor 1 is combined with bpy in a highly polar solvent such as water to give [Co(TFMBz)2(bpy)]n (5). In this isomer, all the carboxylate units act as bidentate bridging ligands, generating chains that are interlinked by bpy, leading to a 2D network, which after packing yields a non-porous structure. The resolution of structures 2-5 is only possible with the recently developed 3D electron diffraction method based on the collection of diffraction patterns on sub-micron-sized single crystals. The variation of magnetic susceptibility as a function of temperature is also measured. Overall, our work provides insightful information on the complex landscape of metal-organic framework solids that are formed by crystallization using different solvent media.