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Four novel 3D metal–organic frameworks, [Ba (H2O)4 (L1)2]·4H2O (1), [Ba(H2O)4(L2)2]·8H2O (2) [Ba(H2O)7](L3)2·2H2O (3) and [Ba(H2O)7(L4)2]·3H2O (4) were obtained by self-assembly of barium(II) with four isoflavonesulfonate ligands [L1 = 7,4′-dihydroxyisoflavone-3′-sulfonate, L2 = 4′- hydroxy-7-methoxyisoflavone-3′-sulfonate, L3 = 5-hydroxy-7,4′-dimethoxyisoflavone-3′-sulfonate, L4 = 5,7-dihydroxy-6,4′-dimethoxyisoflavone-3′-sulfonate]. To survey the influences of different substituents in isoflavonesulfonate ligands on their self-assembly manners, the crystal structures of 1–4 have been determined by single-crystal X-ray diffraction. The results show that they have an intriguing variety of coordination modes and stacking manners with the changes of substituents in isoflavonesulfonate ligands. The sulfo-groups of isoflavonesulfonate ligands play important roles, they not only can coordinate with Ba2+ directly, but also provide an important bridge in a structural link between the hydrophilic region and the hydrophobic region in the crystal structure of 1–4.
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