Nine new coordination polymers [Mn(L)(OX)] (1), [Zn(L)(MBDC)] (2), [Zn(L)(BPDA)] (3), [Co3(L)2(BTA)2]·2H2O (4), [Co2(L)2(BTCA)]·2H2O (5), [Ni(L)(e,a-cis-1,2-CHDC)]·2H2O (6), [Co(L)(e,a-cis-1,4-CHDC)] (7), [Co(L)(e,e-trans-1,4-CHDC)]·2H2O (8) and [Co(L)(e,e,e-cis-1,3,5-HCHTC)]·0.45H2O (9) were obtained by reactions of varied metal salts with 1,4-di(1H-imidazol-4-yl)benzene (L) in the presence of corresponding auxiliary ligands of oxalic acid (H2OX), 5-methyl-1,3-benzenedicarboxylic acid (H2MBDC), 4,4′-biphenyldicarboxylic acid (H2BPDA), benzene-1,3,5-triacetic acid (H3BTA), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), cis-1,2-cyclohexanedicarboxylic acid (cis-1,2-H2CHDC), cis-/trans-1,4-cyclohexanedicarboxylic acid (cis-/trans-1,4-H2CHDC) and cis-1,3,5-cyclohexane tricarboxylic acid (cis-1,3,5-H3CHTC), respectively. Complex 1 has a one-dimensional (1D) chain structure and 2 has a two-dimensional (2D) network with 63-hcb topology. Complex 3 is a complicated uninodal 4-connected three-dimensional (3D) net with Point (Schlafli) symbol (4·6·83·10)(4·63·82)(63·103)(64·82) while 4 is a (3,8)-connected tfz-d 3D net with Point (Schlafli) symbol (43)2(46·618·84) based on the trinuclear Co(II) secondary building units (SBUs). Complex 5 is a 3-fold interpenetrating mog net with Point (Schlafli) symbol of (4·64·8)2(42·62·82), while 6 is a 2D net with (4,4) topology based on binuclear SBUs. In contrast to the 2D network of 7 with e,a-cis-1,4-CHDC2−, 8 with e,e-trans-1,4-CHDC2− is a 5-fold interpenetrating 66-dia 3D net. Complex 9 has a 1D ladder-like chain structure with a stable conformation from the e,e,e-cis-1,3,5-HCHTC2− ligand. Complexes 2 and 3 exhibit intense light blue emission in the solid state at room temperature and the results of magnetic measurements showed that there are antiferromagnetic interactions in 1.

Construction of coordination frameworks based on 4-imidazolyl tecton 1,4-di(1H-imidazol-4-yl)benzene and varied carboxylic acids

Eight new coordination polymers [Mn(H2btc)2(4,4′-bpy)2]n (1), {[Cd(Hbtc)(phen)(H2O)]·H2O}n (2), [Pb(Hbtc)(phen)]n (3), {[Cd3(btc)2(H2O)5]·4H2O}n (4), {[Cd3(btc)2(phen)2(H2O)]·H2O}n (5), [Mn3(btc)2(2,2′-bpy)2]n (6), {[Ni3(btc)2(4,4′-bpy)2.5(μ2-H2O)(H2O)3]·3H2O}n (7), and {[Co2(btc)(μ3-OH)(μ2-H2O) (8), were assembled from different metal(II) chlorides and biphenyl-2,4,4′-tricarboxylic acid (H3btc) as a main building block, and various aromatic N-donors (phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine) as supporting ligands. By adjusting the reaction pH, H3btc undergoes a partial deprotonation to give the H2btc− form in 1, and the Hbtc2− moiety in 2 and 3, and the fully deprotonated btc3− form in 4–8. All the products were fully characterized by single crystal X-ray diffraction analysis. Compounds 1 and 2 possess the double helical chain and wheel chain 1D coordination networks, respectively, which are further extended into the 3D supramolecular architectures via hydrogen bonds. The 2D and 3D metal–organic networks of 6 and 3 were topologically classified, revealing the trinodal 3,6,6-connected and uninodal 4-connected nets with the 3,6,6L3 and sra topologies, respectively. Compounds 4, 5, 7, and 8 feature the very complex 3D metal–organic framework structures, generating either pentanodal 3,4,5,6,6- (4), 3,3,4,5,5- (5), and 4,4,4,5,6-connected (7), or tetranodal 3,5,6,6-connected (8) underlying nets with the hitherto undocumented topologies. The obtained data revealed that different coordination modes of the H2btc−/Hbtc2−/btc3− ligands and the resulting crystal architectures depend on a variety of factors, such as the solution pH and the nature of metal ions and N-donor auxiliary ligands. Magnetic susceptibility measurements indicate that 1 and 8 show a dominating ferromagnetic coupling, while 6 and 7 exhibit an antiferromagnetic coupling between the metal centers. Furthermore, thermal stability of 1–8 and luminescent properties of 2–5 were also studied and discussed.

http://www.rsc.org/suppdata/ce/c3/c3ce41457d/c3ce41457d.pdf

Synthesis, structural versatility, luminescent and magnetic properties of a series of coordination polymers constructed from biphenyl-2,4,4′-tricarboxylate and different N-donor ligands

A 3D MOF showing unprecedented solvent-induced single-crystal-to-single-crystal transformation and excellent CO2 adsorption selectivity at room temperature

Six new mixed-ligand coordination polymers, namely, [Zn(1,3-bdc)(3-bpdb)]n (1), {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2), [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3), [Ni(1,4-bdc)(3-bpdb)(H2O)]n (4), {[Co5(1,4-ndc)4(3-bpdb)(μ3-OH)2(H2O)2(DMF)2]·2H2O·CH3OH}n (5), and {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6), where 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, 1,3-H2bdc = 1,3-benzenedicarboxylic acid, 1,4-H2bdc = 1,4-benzenedicarboxylic acid, and 1,4-H2ndc = 1,4-naphthalenedicarboxylic acid, were synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that the structures of complexes 1 and 2 were isomorphic and exhibited two-dimensional (2D) double-layered sql nets. Complex 3 had an interesting 2D → three-dimensional (3D) inclined polycatenation net based on 44-sql subunits. Complex 4 featured an uncommon 3D 2-fold cds network, while complex 5 possessed a rare uninodal self-penetrating 10-connected pentacobalt-cluster-based ile-(36.43...

Intriguing Architectures Generated from 1,4-Bis(3-or 4-pyridyl)-2,3-diaza-1,3-butadiene with Aromatic Dicarboxylates: Syntheses, Crystal Structures, and Properties

Based on an asymmetric pyridinyl triazole carboxylate ligand 1-(4-pyridinylmethyl)-1H-1,2,4-triazole-3-carboxylic acid (Hpmtc), 12 cadmium(II) polymers {Cd1.5(pmtc)2(NO3)]·H2O}n (1), {[Cd2(pmtc)2(μ2-SO4)(H2O)]}n (2), [Cd(pmtc)(SCN)]n (3), [Cd2(pmtc)2(SCN)2]n (4), {[Cd1.5(pmtc)2(N3)]·H2O}n (5),{[Cd(pmtc)2]}n (6), [Cd(pmtc)(NO2)(CH3OH)]n (7), {[Cd2(ppmtc)3(NO2)]}n (8), {[Cd2(pmtc)2(Cl)2(H2O)2]}n (9),{[Cd(pmtc)(Br)(H2O)]·CH3OH}n (10), {Cd(pmtc)(I)(H2O)]}n (11), and [Cd(pmtc)(I)]n (12) have been synthesized and structurally characterized. Employment of different anions has resulted in different architectures and topological structures, ranging from two-dimensional (2D) to three-dimensional (3D) frameworks, in which 2 and 4 present a new (42·6·103)(42·63·8)2(42·6) topology. Through calculations to the frontier molecular orbital (FMOs) of 9–11, their photoluminescence should be assigned as the n → π* transition. Moreover, the photoluminescent properties of 1–12 indicate that the coordination anions make great c...

Twelve Cadmium(II) Coordination Frameworks with Asymmetric Pyridinyl Triazole Carboxylate: Syntheses, Structures, and Fluorescence Properties

Five coordination polymers, Mn4(nbpdc)4(bip)(H2O)2 (1), Co5(nbpdc)4(bip)2(H2O)6(OH)2 (2), Cu5(nbpdc)4(bip)2(H2O)2(OH)2 (3), Zn5(nbpdc)4(bip)2(OH)2 (4), and Cd2(nbpdc)2(bip) (5), (H2nbpdc = 2,2′-dinitro-4,4′-biphenyldicarboxyl acid, bip = 1,5-bis(imidazole)pentane), have been prepared and structurally characterized. In these compounds, nbpdc and bip link different secondary building units (SBUs) to construct a variety of architectures based on different metals. Compound 1 presents a 3D hex net based on infinite rod-shaped SBUs. Compound 2 shows a 3D framework with mab topology based on Co5 clusters and exhibits an interesting self-penetration feature. Compound 3 presents a 3D framework with pcu topology constructed by Cu5 clusters. Compound 4 is a 3D framework with pcu topology based on infinite rod-shaped SBUs. Compound 5, like compound 4, also exhibits pcu topology constructed by rod-shaped SBUs, but they both possess different structures. The magnetic properties of compounds 1 and 2 have been characterized.

Design and construction of coordination polymers based on 2,2′-dinitro-4,4′-biphenyldicarboxylate and imidazole-based ligands: The effect of ligand length and metal ions

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Design and construction of coordination polymers based on 2,2′-dinitro-4,4′-biphenyldicarboxylate and imidazole-based ligands: The effect of ligand length and metal ions