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The bifunctional pyridine-2,3-dicarboxylic acid (H2pdc) ligand has one N atom and four O atoms, which could bind more than one AgI centre with diverse binding modes. A novel infinite one-dimensional AgI coordination polymer, namely catena-poly[[silver(I)-(μ2-pyridine-2,3-dicarboxylato-κ2 N: O3)-silver(I)-tris(μ2-5-methyl-1,3,4-thiodiazol-2-amine-κ2 N: N′)] monohydrate ethanol monosolvate], {[Ag2(C7H3NO4)(C3H5N3S)3]·H2O·C2H5OH} n, has been synthesized using H2pdc and 5-methyl-1,3,4-thiadiazol-2-amine (tda), and characterized by single-crystal X-ray diffraction. One AgI atom is located in a four-coordinated AgN4 tetrahedral geometry and the other AgI atom is in a tetrahedral AgN3O geometry. A dinuclear AgI cluster formed by three tda ligands with a paddelwheel configuration is bridged by the dianionic pdc2− ligand into a one-dimensional coordination polymer. Interchain N-H...O hydrogen bonds extend the one-dimensional chains into an undulating two-dimensional sheet. The sheets are further packed into a three-dimensional supramolecular framework by interchain N-H...O hydrogen bonds. [ABSTRACT FROM AUTHOR]

The design and synthesis of functional coordination polymers is motivated not only by their structural beauty but also by their potential applications. ZnII and CdII coordination polymers are promising candidates for producing photoactive materials because these d10 metal ions not only possess a variety of coordination numbers and geometries, but also exhibit luminescence properties when bound to functional ligands. It is difficult to predict the final structure of such polymers because the assembly process is influenced by many subtle factors. Bis(imidazol-1-yl)-substituted alkane/benzene molecules are good bridging ligands because their flexibility allows them to bend and rotate when they coordinate to metal centres. Two new ZnII and CdII coordination polymers based on mixed ligands, namely, poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ2 N3: N3′]bis(μ3-2,2-dimethylbutanoato-κ3 O1: O4: O4′)dizinc(II)], [Zn2(C6H8O4)2(C14H14N4)] n, and poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ2 N3: N3′]bis(μ3-2,2-dimethylbutanoato-κ5 O1, O1′: O4, O4′: O4)dicadmium(II)], [Cd2(C6H8O4)2(C14H14N4)] n, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Both complexes crystallize in the monoclinic space group C2/ c with similar unit-cell parameters and feature two-dimensional structures formed by the interconnection of S-shaped Zn(Cd)-2,2-dimethylsuccinate chains with 1,4-bis(imidazol-1-ylmethyl)benzene bridges. However, the CdII and ZnII centres have different coordination numbers and the 2,2-dimethylsuccinate ligands display different coordination modes. Both complexes exhibit a blue photoluminescence in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4′-bipyridine ligands, namely poly[[aqua(μ2-4,4′-bipyridine-κ2 N: N′)bis(μ3-2,2-dimethylbutanedioato)-κ4 O1, O1′: O4: O4′;κ5 O1: O1, O4: O4, O4′-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O} n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear ZnII subunits into one-dimensional chains along the c axis. 4,4′-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials. [ABSTRACT FROM AUTHOR]

Six novel coordination polymers with fascinating 2D/3D architectures based on 4'-(4-(1H-imidazol-1-yl)phenyl)-4,2':6',4''-terpyridine, different polycarboxylates, and metal ions have been prepared under solvothermal conditions, and the photoluminescent behaviors for the complexes 1-6 have been investigated. [Display omitted] • Six novel coordination polymers have been prepared under solvothermal conditions. • Three complexes with 2D and the other three showing 3D network have been found. • The luminescent properties for complexes 1 – 6 have been investigated. Six novel coordination polymers (CPs) based on a rigid tridentate ligand, 4′-(4-(imidazol-1-yl)phenyl)-4,2′:6′,4′'-terpyridine (imphtpy), namely {[Zn 2 (imphtpy) 2 (p -bdc) 2 ]·(H 2 O)} n (1), [Zn(imphtpy)(m -bdc)] n (2), {[Zn(imphtpy)(qda) 1.5 ]·(H 2 O)} n (3), [Cd 2 (imphtpy) 2 (m -bdc) 2 ] n (4), [Cd(imphtpy)(abtc) 0.5 ] n (5) and [Cd(imphtpy)(qda)] n (6), (p -H 2 bdc = 1,4-benzenedicarboxylic acid, m -H 2 bdc = 1,3-benzenedicarboxylic acid, H 2 qda = hydroquinone-o,o'-diacetic acid and H 4 abtc = 3,3′,5,5′-azobenzenetetracarboxylic acid), have been solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis and single-crystal X-ray diffraction. Complex 1 displays a pseudo four-fold interpenetration of dia network in a [2 + 2] mode. Complex 2 exhibits a 2D → 2D polycatenane of two-fold interpenetrated network with the sql topology. Complex 3 shows a interdigitated 2D layer with the sql topology, which is further extended into a 3D supramolecular framework through π-π interactions and hydrogen bonds. Complex 4 features a two-fold interpenetrated (4,4)-connected 3D + 3D → 3D framework with the bbf topology. Complex 5 reveals a 2D network constructed by binuclear Cd 2 (CO 2) 4 secondary building unit (SBU) with the sql topology which is further packed into a 3D supramolecular framework through π-π interactions. Complex 6 is a 3D network constructed by binuclear Cd 2 (CO 2) 2 O 2 SBU with the uninodal 6-c pcu topology. These results indicate that the versatile coordination networks of imphtpy and various polycarboxylate ligands play crucial roles in modulating the structural topologies of coordination networks. In addtion, photoluminescence properties have been explored for complexes 1 – 6 in the solid state at room temperature, which are derived from metal perturbed intraligand charge transfer (ICT) or ligand-to-ligand charge transfer. [ABSTRACT FROM AUTHOR]

• Six coordination polymers have been prepared under solvothermal conditions with a newly designed and synthesized ligand 4′-(4-(benzimidazol-1-yl)phenyl)−4,2′:6′,4′'-terpyridine (bimphtpy). • Various structures with 2D+2D→3D polycatenation (1 and 5), undulated 2D (2) or two-fold 2D→2D interpenetrated network (3) and uninterpenetrated 3D network (4 and 6) have been found. • The photoluminescence behaviors of complexes 1–6 have been investigated. • The activated complex 3 shows moderate CO 2 adsorption of 15.9 cm3 (STP)/g (0.7 mmol/g, 3.08 wt%). Six Zn(II)/Cd(II) coordination polymers (CPs), namely, {[Zn 2 (bimphtpy)(p -bdc) 1.5 (OH)]·(H 2 O) 0.5 } n (1), [Zn 2 (bimphtpy) 2 (tdc) 2 ] n (2), {[Zn(bimphtpy)(cpoa)]·4H 2 O} n (3), [Cd 2 (bimphtpy)(p -bdc) 2 (H 2 O)] n (4), {[Cd 2 (bimphtpy)(m -bdc) 2 (H 2 O) 2 ]·(H 2 O) 0.75 } n (5), and {[Cd(bimphtpy)(qda)]·H 2 O} n (6), constructed from N-heterocyclic ligand 4'-(4-(benzimidazol-1-yl)phenyl)-4,2':6',4''-terpyridine (bimphtpy) and five dicarboxylic acids, (p -H 2 bdc = 1,4-benzenedicarboxylic acid, H 2 tdc = 2,5-thiophenedicarboxylic acid, H 2 cpoa =4-carboxyphenoxyacetatic acid, m -H 2 bdc = 1,3-benzenedicarboxylic acid, H 2 qda = hydroquinone-o,o'-diacetic acid), have been solvothermally synthesized and structurally characterized mainly by single-crystal X-ray diffraction along with elemental analysis, IR spectroscopy, PXRD and TG analysis. Complex 1 exhibits a 2D + 2D → 3D polycatenated framework with bilayers showing the uninodal 5-c (4,4)Ia topology if Zn 2 (CO 2)(OH) SBU (secondary building unit) are considered. Complex 2 reveals a 2D → 2D polycatenane of two-fold interpenetrated network with rods threading loops showing 63- hcb topology. Complex 3 presents a highly undulated 2D 44- sql sheet with thickness of about 18.5 Å. Complex 4 displays a single 3D network constructed by binuclear Cd 2 (CO 2) 4 O 2 SBU showing the uninodal 6-c pcu topology. Complex 5 features a 2D + 2D → 3D polycatenated framework showing an unidentified topology with point symbol of {42·6·72·9}{42·6}{6·72}{64·8·10}. Complex 6 shows a single 3D network constructed by binuclear Cd 2 O 4 C 2 SBU with 8-c cds topology. Moreover, the fluorescent properties of complexes 1–6 in the solid state at room temperature as well as the adsorption properties of complex 3 are also investigated, suggesting their potential applications as luminescence materials and gas adsorption selectivity materials. Six novel coordination polymers with fascinating 2D/3D architectures based on a newly designed and synthesized N-heterocyclic ligand 4′-(4-(benzimidazol-1-yl)phenyl)-4,2′:6′,4′'-terpyridine (bimphtpy), along with different dicarboxylates, and Zn(II)/Cd(II) ions have been prepared under solvothermal conditions, and the photoluminescence behaviors of complexes 1–6 and the gas adsorption property of complex 3 have been investigated. [Display omitted] [ABSTRACT FROM AUTHOR]