Novel Metallosupramolecular Networks Constructed from Cu II , Ni II , and Cd II with Mixed Ligands: Crystal Structures, Fluorescence, and Magnetism

Reactions of mixed ligands succinic acid (H2suc) and bent dipyridines, such as 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and its 4-N-donor analog (4-bpo), with inorganic CuII, NiII, and CdII salts yield three new metal-organic coordination frameworks {[Cu(suc)(3-bpo)(H2O)2]·(H2O)1.75}n (1), {[Ni(suc)(4-bpo)(H2O)2]·(H2O)5}n (3), and {[Cd2(suc)2(3-bpo)2(H2O)2]·(H2O)6.75}n (4), in which the metal centers are linked by bridging ligands 3-bpo/4-bpo and suc2– along two directions to form 2D infinite networks. The corrugated 2D nets of 1 and 4, obtained under hydrothermal conditions, align in an interdigitated manner with the presence of significant aromatic-stacking interactions to result in similar 3D architectures. The 2D sheets in 3 are extended by interlayer hydrogen bonds to afford a 3D structure. However, when succinic acid is replaced by fumaric acid (H2fum) in the reaction with 3-bpo and CuII salt, a metallacyclophane [Cu(Hfum)2(3-bpo)(H2O)]2·(3-bpo)2·(H2O)6 (2) is generated. The binuclear coordinated motifs are hydrogen-bonded to the lattice water chains to furnish a unique 3D channel-like framework, in which the guest 3-bpo molecules are accommodated. The thermal stabilities of these new materials were investigated by thermogravimetric analysis (TGA) of mass loss. The magnetic coupling in complexes 1–3 is antiferromagnetic and very small, which is as expected considering the long organic bridges between the paramagnetic centers. The solid-state luminescence properties of 4 reveal an intense fluorescence emission at 378 nm. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)