Supramolecular Isomerism of Metal−Organic Frameworks Derived from a Bicarboxylate Linker with Two Distinct Binding Motifs

Two novel metal−organic frameworks (MOFs), Cu(3,4′-bpdc)(H2O)·DMF·2H2O (1) and Cu(3,4′-bpdc)(H2O)·2DMF·4.5H2O (2), have been solvothermally synthesized by the reaction of a unsymmetrically substituted carboxylate ligand 3,4′-biphenyldicarboxylic acid (3,4′-bpdc) and Cu(NO3)2·2.5H2O. X-ray crystal structural analyses reveal that both MOFs possess the binuclear paddle-wheel units [Cu2(O2CR)4], which are linked by the biphenyl connectors, to give two different three-dimensional (3-D) frameworks. The structural diversities are due to the different coordinated arrangements of the two distinct carboxylate groups. In 1, the noncentral symmetrical A−A−B−B arrangement leads to an uncommon twisted Cu-paddlewheel unit, which favors a tetrahedral configuration to generate a 3-fold interpenetrating 3-D framework with a diamond topology. In 2, the paddle-wheel unit constructed by the central symmetrical A−B−A−B arrangement of the ligand acts as a square-planar 4-connected node to give a 2-fold interpenetrating 3-D fram...