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Four novel Zn(ii) and Cd(ii) coordination polymers, {[Zn(cmb)(dpa)]·H2O}n(1), {[Zn(cmb)(bpp)]·2.5H2O}n(2), {[Zn(cmb)(bimb)]·3H2O}n(3), and {[Cd2(cmb)2(bimb)]·H2O}n(4) (H2cmb = 2-(carboxymethoxy)benzoic acid; dpa = 4,4′-dipyridylamine; bpp = 1,3-di(4-bipy)propane; bimb = 1,4-bis(imidazol)butane), have been synthesized and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1exhibits a diamond (dia) framework of four-fold interpenetration (class IIIa). 2features a rare 1D → 3D polycatenated architecture, which is built from the interlocking of two sets of 1D supramolecular loops running in different directions (almost perpendicular). The 3D crystalline lattice of 3is constructed through the parallel packing of corrugated 2D 44(sql) nets. Complex 4shows a 2D network with the (3,4)-connected (43)2(4 × 104× 12)(42× 104) topology, which consists of 1D [Cd(cmb)]narrays and helical pillars. The results clearly indicate the importance of linking modes of organic ligands and metal centers as well as the auxiliary ligands in the direction of the diverse structures for complexes 1–4. Thermal stabilities and luminescent properties of complexes 1–4have also been investigated. [ABSTRACT FROM AUTHOR]

A series of six Ag(i) and Zn(ii) coordination polymers, namely, [Ag2(ndc)]∞(1), {[Zn(ndc)(H2O)](H2O)}∞(2), {[Ag2(ndc)(4bpy)2][Ag(4bpy)(H2O)](ClO4)(H2O)2}∞(3), [Zn5(ndc)4(4bpy)2(μ3-OH)2]∞(4), {[Ag(ndc)(abp)][Ag(abp)](H2O)3}∞(5), and {[Zn2(ndc)2(abp)(H2O)2](H2O)2}∞(6), have been prepared by using 2,3-naphthalenedicarboxylic acid (H2ndc), an analogue of 1,2-benzenedicarboxylic acid (H2bdc), and different 4,4′-bipyridyl-like bridging co-ligands 4,4′-bipyridine (4bpy) and trans-4,4′-azobis(pyridine) (abp). The initial complexes 1and 2display the unusual two-dimensional (2-D) five-connected (48.62) and the 2-D three-connected (4.82) coordination networks, respectively. When two comparable rod-like linkers 4bpy and abp (with different N,N′-donor separations of the molecular backbones of ca.7 and 9 Å) are further introduced, two one-dimensional (1-D) complexes 3and 5, a three-dimensional (3-D) coordination framework 4with (43)(43.63)(43.65.82)(44.64.82)(410.65) topology and a 2-D 63layered coordination polymer 6are constructed. A structural comparison of these complexes with those based on the structurally related bdcligand suggests that the extended π-conjugated system of ndcwith different electronic nature and steric bulk play an important role in constructing the supramolecular architectures for 1–6, which are also regulated by different bridging N-donor co-ligands and metal ions. Moreover, complexes 1–6show strong solid-state luminescence emissions at room temperature that mainly originate from the intraligand transitions of ndc. [ABSTRACT FROM AUTHOR]

This work presents eight coordination assemblies based on divalent metal ions (M = CoII, CuII, ZnII, and CdII), dicyanamide anion (N(CN)2−, dca), and two isomeric bent dipyridyl coligands (L), namely, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo). In the resulting crystalline materials, both bpo and dca tectons generally display the bidentate bridging fashion (except in the mononuclear species 5), extending the metal centers to afford diverse one-, two-, and three-dimensional (1-D, 2-D, and 3-D) coordination networks that are not commonly observed in M−dca−L systems. Notably, the inclined polycatenated 2-D → 3-D framework and 3-D polyknotting network with the unique 6-connected (44.611) topology are formed for the CuIIand CdIIspecies with dca and 4-bpo. For the polymeric CoIIand CuIIcomplexes, very weak antiferromagnetic or ferromagnetic interactions are observed between the metal centers due to the μ1,5-bridging mode of dca, and their magneto-structural correlations have been discussed in detail. The ZnIIand CdIIcomplexes show solid-state fluorescent emissions at room temperature. [ABSTRACT FROM AUTHOR]

To systematically explore the influence of the pyridyl N-donor spatial positions of benzotriazol-1-yl-based pyridyl tectons on structural assemblies of coordination polymers, three closely related ligands, 1-(2-pyridylmethyl)-1H-benzotriazole (2-pbt), 1-(4-pyridylmethyl)-1H-benzotriazole (4-pbt), and 1-(3-pyridylmethyl)-1H-benzotriazole (3-pbt), were designed and prepared. Their reactions with CuI under hydrothermal conditions afforded three new copper(i)-iodide coordination polymers, namely, [CuI(2-pbt)]∞(1), [Cu2I2(4-pbt)]∞(2), and [Cu3I3(3-pbt)]∞(3). Single-crystal X-ray diffraction analysis shows that 1has a two-dimensional (2D) (4,4) sheet structure containing rhomboid [Cu2I2] dimeric units, which are further extended to form a three-dimensional (3D) framework by interlayer C–Hπ supramolecular interactions. Complexes 2and 3, with one-dimensional (1D) looped-chain [Cu2I2]nand 1D staircase double-chain [Cu3I3]ncopper(i)-iodide arrays, show an unusual 3D six-connected self-penetrating robnet with the Schläfli symbol of (48.66.8) and a 3D four-connected homochiral diamond net, respectively. The results reveal that the different spatial positions of pyridyl N-donors in this series of ligands play an important role in constructing coordination polymers 1–3. Moreover, the photoluminescent properties and thermal stability of 1–3in the solid state have also been investigated. [ABSTRACT FROM AUTHOR]

Six Cd(II) coordination polymers with a flexible fulconazole ligand, {[Cd(HFlu)2(H2O)2](ClO4)2}n(1), {[Cd(HFlu)3(NO3)]2(NO3)2·H2O}n(2), {[Cd(HFlu)2(SCN)](ClO4)}n(3), {[Cd(HFlu)2(SCN)](NO3)}n(4), {[Cd(HFlu)2Cl](SCN)}n(5) and {[Cd(HFlu)2(SCN)2]·2H2O}n(6) [HFlu = 2-(2′,4′-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol] have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1presents a 1-D chain-like structure with anti–gauche(A-G) conformation of HFlu. Complex 2shows a 1-D ladder-like structure with both A-G and anti–anti(A-A) conformations of HFlu, and complexes 3, 4and 5show the 2-D grid structures bridged by A-G and A-A HFlu. However, in the 2-D grid network of 6, only A-A conformation of HFlu is observed. The conformational change of the HFlu ligand is induced step-by-step by the addition of the SCN−inorganic anion. The thermal stability and fluorescence of these complexes have also been studied. [ABSTRACT FROM AUTHOR]

A new coordination polymer, {[Mn(mip)(dps)](dpts)0.5}2n(1) (mip = 5-methylisophthalate) has been solvothermally synthesized by in situgeneration of 4,4′-dipyridylsulfide (dps) and 4,4′-dipyridyltrisulfide (dpts) ligands from a 4,4′-dipyridyldisulfide (dpds) precursor. The coordination framework of 1shows a new (3,5)-connected 3-D net topology with a Schläfli symbol of (42.65.83)(42.6), in which weak antiferromagnetic interactions are observed between the MnIIions. [ABSTRACT FROM AUTHOR]

Seven Zn(II) and Cd(II) coordination polymers, formulated as {[Zn2(5-Br-ip)2(bpy)(H2O)]·2H2O}n(1), {[Zn(5-Br-ip)(bpa)(H2O)]}n(2), {[Cd(5-Br-ip)(bpp)(H2O)]}n(3), {[Zn(5-Br-ip)(bpe)]}n(4), {[Zn2(4-Br-ip)2(bpy)]·H2O}n(5), {[Zn(4-Br-ip)(bpa)(H2O)]}n(6), and {[Cd(4-Br-ip)(bpp)]}n(7), were prepared by hydrothermal reactions based on 4-bromo- or 5-bromoisophthalic acid (4-Br-H2ip or 5-Br-H2ip) and different dipyridyl-type coligands 4,4′-bipyridyl (bpy), 1,2-bi(4-pyridyl)ethane (bpa), 1,3-di(4-pyridyl)propane (bpp), and 1,2-di(4-pyridyl)ethene (bpe). All complexes 1−7were characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. Complex 1is a 2D (6,3) coordination network and further assembled into a 3D framework via π−π stacking interactions. Complex 2shows a 1D coordination array and further forms a 2D supramolecular network via H-bonding interactions. Complex 3has a 2-fold interpenetrating 3D diamond framework. Complex 4is a 3-fold interpenetrating 3D network with CdSO4topology, constructed from alternately left- and right-handed helical arrays. Complex 5has a 3D (3,4)-connected network with (4·82)(4·82·103) topology. Complex 6features a 1D coordination chain and further forms a 2D helical supramolecular pattern by H-bonding. Complex 7exhibits a (3,5)-connected 2D layer with the Schläfli symbol of (42·6) (42·67·8). The results reveal that the diverse coordination networks of 1−7can be adjusted by the different dispositions of the -Br substituent of isophthalate building blocks, as well as the metal ions and the dipyridyl coligands. Moreover, the luminescent properties of the complexes have been investigated. [ABSTRACT FROM AUTHOR]

A new pillared-layer coordination polymer, [Co3(pybz)2(pico)2]n (1; pybz = 4-(pyridin-4-yl)benzoate, pico = 3-hydro- xypicolinate), contains rare 2D [Co3(pico)2]n2n+ layers formed by linear cobalt(ll) tnmers through the unusual μ4∙KN, O:KO'-μ2:KO"-μ2 bridging mode of pico ligands, which are further cross-pillared by exotridentate bridging pybz ligands to form a three-dimensional structure with an unusual uninodal 8-connected body-centered-cubic topology. The bulk magnetic behavior of 1 exhibits ferrimagnetic long-range ordering below 2.6 K, which mainly arises from the cooperative magnetic effect of the intra- and intertrimer arrangements in the 20 magnetic system based on the nature of the exchange modes of μ2-hydroxyl, μ2-carboxylate oxygen, and 1,1 ,3-μ3-carboxylate bridges. [ABSTRACT FROM AUTHOR]

Five novel zinc(II) and cadmium(II) metal−organic coordination polymers with a tricarboxyl tecton and N-donor ancillary ligands, {[Zn(Hnbta)(2,2′-bipy)]·H2O}n(1), {[Cd3(nbta)2(2,2′-bipy)2(H2O)2]}n(2), {[Cd3(nbta)2(bpa)2]}n(3), {[Zn2(nbta)(OH)(bpa)1.5]·2H2O}n(4), and {[Zn3(nbta)2(bpp)2(H2O)2]}n(5) (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, bpa = 1,2-bi(4- pyridyl)ethane, and bpp = 1,3-bi(4-pyridyl)propane), have been prepared and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1has a two-dimensional (2D) bilayer supramolecular network constructed from one-dimensional (1D) zigzag coordination chains via π···π interactions, whereas 2exhibits a three-dimensional (3D) supramolecular network assembled from 1D coordination arrays through π···π interactions and weak C−H···O interactions. Complex 3features a (4,5)-connected self-penetrating 3D coordination net with a (43·65·82)(43·62·8)(44·64·82)(45·65) topology. The 3D framework of 4can be described as a trinodal (4,5)-connected (3·4·53·6)(3·52·62·84·9)(3·4·5·83) topology, which consists of 2D [Zn(nbta)] helical arrays and bpa pillars. Complex 5has a 3D trinodal 4-connected (4·64·8)(44·62)(43·63) topology. Moreover, thermal stabilities and luminescent properties of complexes 1−5have also been investigated. [ABSTRACT FROM AUTHOR]