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Abstract: Four 4,4′-bipyridine α,ω-dicarboxylate coordination polymers Cu(bpy)(C5H6O4) (1), Zn(bpy)(C5H6O4) (2), Zn(bpy)(C6H8O4) (3) and Mn(bpy)(C8H12O4)·H2O (4) have been synthesized and structurally characterized by single crystal X-ray diffraction methods (bpy=4,4-bipyridine, (C5H6O4)2−=glutarate anion, (C6H8O4)2−=adipate anion, (C8H12O4)2−=suberate anion). Their crystal structures are featured by dimeric metal units, which are co-bridged by 4,4′-bipyridine ligands and dicarboxylate anions such as glutarate, adipate and suberate anions to generate 2D layers with a (4,4) topology in 1, 2 and 4 as well as to form 3D frameworks in 3. Two 3D frameworks in 3 interpenetrate with each other to form a topology identical to the well-known Nb6F15 cluster compound. Over 5–300K, the paramagnetic behavior of 4 follows the Curie–Weiss law χm(T−Θ)=4.265(5)cm3mol−1 with the Weiss constant Θ=−6.3(2)K. Furthermore, the thermal behavior of 3 and 4 is also discussed. [Copyright &y& Elsevier]

Three suberato-bridged Mn(II) phen complexes {[Mn(phen)2]L2/2}2·H2L·8H2O (1), {[Mn(phen)(H2O)3]2L}L·2H2L·4H2O (2) and {[Mn(phen)2(HL)]2L}·H2L (3) have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The [Mn(phen)2]2+ moieties in 1 are interlinked by bis-monodentate suberato ligands to generate ∞1[Mn(phen)2L2/2] polymeric chains. Complex 2 features a nanoporous hydrogen bonded framework made up of suberate anions, suberic acid molecules and lattice water molecules with the bis-monodentate suberato bridged dinuclear {[Mn(phen)(H2O)3]2L}2+ complex cations residing in tunnels. The bis-monodentate suberato bridged dinuclear {[Mn(phen)2(HL)]2L} molecules in 3 are assembled into a 3D framework with suberic acid molecules situated in the tunnels. [Copyright &y& Elsevier]

Reactions of freshly-prepared Cu(OH)2 with sebacic acid (H2L) and 1,10-phenanthroline (phen) in EtOH/H2O (1:1 v/v) and CH3OH/H2O (1:1 v/v) at pH 6.4 afforded two novel sebacato-bridged Cu(II) phen complexes 2 ∞[Cu2(phen)2L4/2](H2O)6 (1) and [(phen)2Cu(μ-L)Cu(phen)2](HL)2(H2L)(H2O)4 (2), respectively. Complex 1 consists of 2D 2 ∞[Cu2(phen)2L4/2] layers and lattice H2O molecules. The Cu atoms are each square-pyramidally coordinated by two N atoms of one phen ligand and three O atoms of different sebacato ligands. Two adjacent square pyramids are edge-shared to form [Cu2N4O4] dimers, which are interlinked by sebacato ligands to 2D 2 ∞[Cu2(phen)2L4/2] layers with rhombus-like 52-membered rings. The resulting layers are assembled by interlayer π–π stacking interactions and hydrogen bonding interactions. Complex 2 comprises divalent [(phen)2Cu(μ-L)Cu(phen)2] complex cations, hydrogensebacate anions, sebacic acid molecules and lattice H2O molecules. In the divalent complex cations, the Cu atoms are each octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis-chelating sebacato ligand. The complex cations are assembled via π–π stacking interactions into positively charged 2D network. The hydrogensebacate anions, sebacic acid molecules and H2O molecules build negatively charged 2D hydrogen-bonded networks. Both positively and negatively charged 2D networks are interwoven with each other to generate a novel supramolecular architecture. [Copyright &y& Elsevier]