To investigate the role of solvents on the self-assembly of coordination frameworks, the reactions between MnCl2·4H2O and thiophenedicarboxylate (thb) ligand in different solvents at 120 °C produced four new Mn–thb complexes. These Mn–thb frameworks all use a rod-and-spacer assembly mode, but their rod-packing architectures are totally different because of the structure-directing effect of solvents. The topologies of 1, 2, 3 and 4 are novel (3,5)-connected net, hex, irl and sra, respectively. The results reveal that solvents with different conformations play a significant role in promoting the diversity of structures. In addition, the magnetic properties of 1, 2 and 3 have also been studied.
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