Metal ions and solvents ratio co-regulate four new magnetic coordination polymers based upon an unsymmetric tricarboxylate acid ligand.

Four new coordination polymers (CPs), [Co3(L)2(bib)3(EtOH)2]·2H2O (1), [Mn3(L)2(bib)2(H2O)4]·4H2O (2), [Ni(HL)(bib)(H2O)3] (3) and [Ni3(bib)4(H2O)10]·2(L)·12(H2O) (4), were synthesized under solvothermal conditions with an unsymmetrical tricarboxylic acid ligand [biphenyl-3,3',5-tricarboxylic acid (H3L)] in the presence of the 1,4-bis(1H-imidazol-4-yl)benzene (bib) ligand. In compound 1, tricarboxylate acid ligands (H3L) link Co centers to generate two-dimensional (2D) layers which are further connected by bib ligands to exhibit a three-dimensional (3D) framework with a (4,4,5)-connected (4(2)·6(3)·8)2(4(2)·6(7)·8)2(6(4)·8·10) topology. The three-dimensional (3D) framework of 2 is defined as a (3,3,4)-connected topology with the point symbol of (6·8(2))2(6(2)·8)2(8·10(4)·12). Compound 3 contains a one-dimensional (1D) left-hand helix chain along the a direction and further extends into a 2D supramolecular network and a 3D supramolecular framework via hydrogen bonds. Compound 4 displays a one-dimensional (1D) molecular ladder, which is further combined with each other through π···π stacking to extend into 2D supramolecular sheets. The supramolecular networks of 3 and 4 resulted from the different solvent ratios [V(H2O)-V(EtOH)] in the reaction. All the CPs are characterized by single-crystal X-ray diffraction analyses, powder X-ray diffraction (PXRD), elemental analyses, IR spectroscopy, and TGA analyses. Moreover, the weak ferromagnetic properties of 2 and 3 and antiferromagnetic properties of 1 and 4 have also been investigated.

Solvents and auxiliary ligands co-regulate three antiferromagnetic Co(II) MOFs based on a semi-rigid carboxylate ligand.

By reacting an asymmetry semi-rigid Y-shaped/L-shaped linker H3cpta (H3cpta = 3-(4'-carboxyphenoxy)phthalic acid) and Co(CH3COO)2·6H2O under different N-donor ligands in different solvents, three new Co-based coordination polymers, [Co3(cpta)2(bpe)3(H2O)4] (1) [Co(µ2-H2O)(µ3-OH)(Hcpta)(bpe)(H2O)·3(DMF)3(H2O)] (2) and [Co3(cpta)2(bpa)4] (3) have been obtained. They exhibit trinodal topological nets/layer, based on Co(2+) ions and Y-shaped/L-shaped carboxylate linkers. 1 and 3 present 3D frameworks with the point symbol {4·10(2)}2{10(5)·12}{4·8(5)}2 for 1 and {4·8(2)}2{8(5)·9}{4·6(7)·9(2)}2 for 3. While, 2 exhibits a 2D layer with the point symbol {4·6·8}{4·6(2)·8(3)}{6(2)·8}. The magnetic studies indicate that all of the three complexes show antiferromagnetic exchanges transmitted through µ3-carboxylate/µ4-carboxylate bridges, µ2-H2O molecules and µ3-OH ions between Co(2+) ions, respectively. And the result of this research shows that the solvent and the secondary ligands could co-regulate coordination polymer with interesting properties, providing a constructive guidance when synthesizing versatile topologies with the same organic spacer but a different architecture.

Solvent or temperature induced diverse coordination polymers of silver(I) sulfate and bipyrazole systems: syntheses, crystal structures, luminescence, and sorption properties.

Three new coordination polymers, [Ag4(H2bpz)4(SO4)2]·H2O (1), [Ag2(H2bpz)2(SO4)]·3H2O (2), and [Ag3(H2bpz)4](SO4)2/3(OH)5/3·4H2O (3) have been solvothermally synthesized with Ag2SO4 and flexible ligand 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2bpz) in different solvents and temperatures. Complex 1 is a 2-fold interpenetrated three-dimensional (3D) framework with an uncommon (3,5)-connected hms topology. Complex 2 is a structural isomer of 1 and shows a three-connected 2D ths net consisting of interesting 3-fold and 2-fold heterochiral helical chains. Complex 3 discloses a grid layer structure, containing heterochiral helical chains and an unusual meso-helix. More interestingly, three sets of layers in 3 stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating cationic framework with 1D + 3D porous systems. In 1-3, H2bpz exhibit exobidentate bridging fashions with wide-ranged interpyrazole tilting angles and changeable coordination configurations, such as cis and trans fashions in 1 and 3 and uniform trans fashion in 2. These lead to the isomeric [Ag(H2bpz)]n arrays of wavelike and helical chains in 1 and 2, respectively. Complexes 1-3 display solid-state photoluminescence stemming from the ligand-centered fluorescent emissions of H2bpz. Because of the highly polar framework, 3 shows excellent adsorption selectivity for CO2 over N2.

Three new solvent-directed 3D lead(II)-MOFs displaying the unique properties of luminescence and selective CO2 sorption.

Three new solvent-directed three-dimensional (3D) lead(II) coordination polymers, [Pb2(L)2]n (1), [Pb3(L)3]n (2) and [Pb(L)]·H2O (3) [H3L = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid], have been synthesized solvothermally. As influenced by different solvent systems, compounds 1 and 3 exhibit varying architectures from a multi-nodal 3,3,4,4-connected to a uninodal 3-connected net, while 2 with helices represents a binodal 3,4-connected topological net. Moreover, 3 possesses a micropore which is decorated with pyridyl systems and uncoordinated carboxylate oxygen atoms. In addition, the small-sized and highly polar pores enable 3 to attract CO2 strongly, leading to a high sorption heat for CO2 and significant selectivity for CO2 over H2 and N2 at 293 K. The luminescent behaviors and emissive lifetimes of 1-3 are also discussed.

An unprecedented acylamide-functionalized 2D → 3D microporous metal-organic polycatenation framework exhibiting highly selective CO2 capture.

An acylamide-functionalized 3D microporous metal-organic framework built on Zn2 clusters with mixed H3bcta and dipy ligands, which shows unprecedented 2D → 3D polycatenation based on dipy-pillared honeycomb bilayers, and exhibits highly selective CO2 capture.

A 3D porous metal-organic framework containing nanotubes based on multiple helices.

Combining Co2 clusters with mixed H2bpdc and H2bpz ligands creates an unprecedented 3-fold interpenetrated 5-connected porous framework, which possesses the fascinating double-walled nanotubes structure assembled from nonuple and triple helices, and exhibits gas sorption properties.

New two-dimensional Mn(II) metal-organic framework featured spin canting.

A two-dimensional (2D) complex {[Mn(1.5)(L)(bpe)(1.5)]·(bpe)(0.5)}n (1) (H3L = 3-(2-carboxy-phenoxy)phthalic acid, bpe = 1,2-bis(4-pyridyl)ethene), consisting of manganese(II) chains and bridging bpe ligands, has been synthesized and characterized. The magnetic behavior of 1 can be simulated as a -J1J1J2- alternating chain. Magnetic studies show that this complex magnetic behavior belongs to spin canting and exhibits an unusually high T(c) around 40 K. A theoretical study based on DFT-BS calculations provides some insight into the underlying mechanism of the novel magnetic properties.

A polar tetrazolyl-carboxyl microporous Zn(II)-MOF: sorption and luminescent properties.

A Zn(II)-MOF [Zn(2)(tzba)(DMF)]·0.5DMF (1) (H(2)tzba = 4-(1H-tetrazol-5-yl) benzoic acid, DMF = N,N'-dimethylformamide) has been solvothermally synthesized and characterized. 1 is a three-dimensional (3D) microporous framework possessing an unusual multi-nodal (3,3,6)- or (4,4,4,4)-connected topological net. The small-sized pores, open metal sites, phenyl π systems and tetrazolyl groups of tzba(2-) decorating the pore with high polarity enable 1 to attract strongly for CO(2), which leads to high sorption heat for CO(2) and significant selectivities for CO(2) over H(2) and N(2). In addition, 1 and desolvated 1' display strong and weak blue luminescence in solid state, respectively, being mainly related to the framework vibration due to the residing and releasing of DMF molecules in the channel.

Four 3D "brick-wall"-like metal-organic frameworks with a flexible ligand of (S,S,R,R)-1,2,3,4-cyclopentanetetracarboxylic acid: crystal structures, luminescent and magnetic properties.

To investigate the conformation of cyclopentanetetracarboxylic acid, four new "brick-wall"-like metal-organic frameworks have been synthesized from hydrothermal reactions with different metal salts, (S,S,R,R)-1,2,3,4-cyclopentanetetracarboxylic acid (H(4)cptc) and auxiliary N-donor ligands, namely, Cu(2)(S,S,R,R-cptc)(bpe)(H(2)O)(2)·2H(2)O (1), Co(2)(S,S,R,R-cptc)(bpe)(0.5)(H(2)O)(2)·2H(2)O (2), Cd(4)(S,S,R,R-cptc)(2)(bpa)(2)(H(2)O)(5)·2H(2)O (3) and Co(2)(S,S,R,R-cptc)(bpy)(0.5)(H(2)O)(2)·2(H(2)O) (4) (bpe = 4-(2-(pyridine-4-yl)vinyl)pyridine, bpa = 4-(2-(pyridine-4-yl)ethyl)pyridine, bpy = 4-(pyridine-4-yl)pyridine). The complexes were further characterized by single-crystal X-ray diffraction, power X-ray diffraction, FT-IR spectra, fluorescent measurements and variable-temperature magnetic susceptibility measurements. The results of the structural investigations show that 1 is a charming (3,3,4)-trinodal architecture, 3 is an interesting trinodal (3,4,5)-connected architecture, and 2 and 4 are isostructural, which are both (4,5)-connected networks. In addition, the magnetic measurements indicate that 2 and 4 show weak antiferromagnetic interactions, and the fluorescent measurement shows the strong solid-state fluorescent emission at room temperature for 3.

Dynamic porous coordination polymer based on 2D stacked layers exhibiting high sorption selectivity for CO2.

A new dynamic porous coordination polymer (PCP) [Ni(dcpy)(bipy)(0.5)(H(2)O)]·1.5H(2)O (1) was synthesized by assembly of 3-(2',5'-dicarboxylphenyl)pyridine (dcpy), 4,4'-bipyridine (bipy) and NiSO(4)via solvothermal, hydrothermal and microwave methods, displaying a wavelike 2D stacked layer framework. Gas adsorption studies for 1 shows a high selective adsorption of CO(2) over other gases (N(2), CH(4) and CO). The adsorption capacity for N(2) can be moderately altered by different activation temperatures demonstrating the framework flexibility of 1.

Epidemiologic characteristics of typhoid and paratyphoid fever on related drug resistance and molecular types regarding Salmonella typhi and S.paratyphi, in Jiangsu province / 中华流行病学杂志

Objective To explore the distribution of prevalence rates of typhoid and paratyphoid,with drug resistance and molecular types ofSalmonella(S.) typhi and S.paratyphi in Jiangsu province.Methods Data,collected by the national infectious disease reporting system in Jiangsu province from 2007 to 2011,was analyzed.K-B method was used to test the sensibility to 9 kinds of antibiotics among 210 stains of S.typhi and S.paratyphi.81 strains of S.typhi were classified by pulse-field gel electrophoresis (PFGE).Results The annual average incidence of typhoid and paratyphoid was 0.47 per 100 000 in the last five years,showing a decreasing trend.Highest incidence (1.70 per 100 000)was seen in the ＜ 1 year age group,with S.typhi and S.paratyphi A accounted for 66.19％ and 23.81％ among the 210 stains.The rate of drug resistance to nalidixic acid appeared to be the highest as 66.19％.The drug resistant rates to 6 kinds of antibiotics were on average,lower than 10.00％.The multi-drug resistant rate of S.typhi and S.paratyphi was 30.00％.In the last 3 years,37 types from 81 S.typhi strains had been classified into 4 clusters by PFGE.The predominant type was JPPX01.JS0027,accounted for 11.11％.JPPX01.JS0001 type had a specific regional distribution,but JPPX01.JS0014,JPPX01.JS0018 and JPPX01.JS0024 strains were widely spread.Results from the clustering analysis showed that cases in the 3 events tended to have a clustering nature.Conclusion The morbidity of typhoid and paratyphoid was in a relatively low level in Jiangsu province.Although S.typhi and S.paratyphi were sensitive to most of the commonly used antibiotics,the resistance rates to some kinds of antibiotics were increasing.The distribution of typhoid was sporadic in Jiangsu and without the dominant strain,it was unlikely that typhoid could become epidemic in the future,in Jiangsu.

A rod packing microporous metal-organic framework: unprecedented ukv topology, high sorption selectivity and affinity for CO2.

An unprecedented ukv topological framework, based on a rod-like cadium-carboxylate chain, exhibits high CO(2) sorption heat and sorption selectivities of CO(2) over N(2) and CH(4).

Synthesis, structural diversity and fluorescent characterisation of a series of d10 metal-organic frameworks (MOFs): reaction conditions, secondary ligand and metal effects.

Along with our recent investigation on the flexible ligand of H(2)ADA (1,3-adamantanediacetic acid), a series of Zn(II) and Cd(II) metal-organic frameworks, namely, [Zn(3)(ADA)(3)(H(2)O)(2)](n)·5nH(2)O (1), [Zn(ADA)(4,4'-bipy)(0.5)](n) (2), [Zn(2)(ADA)(2)(bpa)](n) (3), [Zn(2)(ADA)(2)(bpa)](n) (4), [Zn(2)(ADA)(2)(bpp)](n) (5), [Cd(HADA)(2)((4,4'-bipy)](n) (6), [Cd(3)(ADA)(3)(bpa)(2)(CH(3)OH)(H(2)O)](n) (7), and [Cd(2)(ADA)(2)(bpp)(2)](n)·7nH(2)O (8) have been synthesized and structurally characterized (where 4,4'-bipy = 4,4'-dipyridine, bpa = 1,2-bis(4-pyridyl)ethane and bpp = 1,3-bis(4-pyridyl)propane). Due to various coordination modes and conformations of the flexible dicarboxylate ligand and the different pyridyl-containing coligands, these complexes exhibit structural and dimensional diversity. Complex 1 exhibits a three-dimensional (3D) framework containing one-dimensional (1D) Zn(II)-O-C-O-Zn(II) clusters. Complex 2 exhibits a 2D structure constructed by 1D double chains based on [Zn(2)ADA(2)] units and a 4,4'-bipy pillar. Complexes 3 and 4 possess isomorphic 2D layer structures, resulting from the different coordination modes of carboxylate group of ADA ligands. Complex 5 features a 2D 4(4) layer in which ADA ligands and Zn(II) atoms construct a 1D looped chain and the chains are further connected by bpp ligands. Complex 6 is composed of 1D zig-zag chains that are entangled through hydrogen-bonding interactions to generate a 2D network. Complex 7 is a rare (3,5)-connected network. Complex 8 possesses a 3D microporous framework with lots of water molecules encapsulated in the channels. The structural diversity of the complexes perhaps mainly results from using diverse secondary ligands and different metal centre ions, and means the assistant ligand and metal centre play important roles in the design and synthesis of target metal-organic frameworks. This finding revealed that ADA could be used as an effective bridging ligand to construct MOFs and change coordination modes and conformational geometries in these complexes. The thermogravimetric analyses, X-ray powder diffraction and solid-state luminescent properties of the complexes have also been investigated.

Distinct structures of coordination polymers incorporating flexible triazole-based ligand: topological diversities, crystal structures and property studies.

Six new coordination polymers, namely {[Zn(btec)(0.5)(btmb)]·2H(2)O}(n) (1), {[Co(btec)(0.5)(btmb)(H(2)O)]·3H(2)O}(n) (2), {[Cu(btec)(0.5)(btmb)]·H(2)O}(n) (3), {[Cu(4)(btc)(4)(btmb)(4)]·H(2)O}(n) (4), {[Co(3)(bta)(2)(btmb)(2)]·2H(2)O}(n) (5), [Co(Hbta)(btmb)](n) (6) (H(4)btec = 1,2,4,5-benzenetetracarboxylate, H(3)btc = 1,3,5-benzenetricarboxylate, H(3)bta = 1,2,4-benzenetricarboxylate and btmb = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl), have been successfully synthesized under hydrothermal conditions. All these complexes were structurally determined by single-crystal X-ray diffraction, elemental analysis, IR, TGA and XRD. Crystal structural analysis reveals that 1 is the first example of an unusual 3D framework with (8(6)) topology containing a 2D molecular fabric structure. Complex 2 exhibits a 3D NbO network with (6(4)·8(2)) topology. In 3, Cu(II) ions are coordinated by anti-conformational btmb ligands to form left- and right-handed double helices, which are further bridged by the 4-connected btec(4-) anions to give a 3D porous network. Complex 4 presents a rare 3D gra network structure with (6(3))(6(9)·8) topology. 5 and 6 were obtained through controllable pH values of solution, 5 features a scarce binodal (3,8)-connected tfz-d framework with the trinuclear Co(II) clusters acting as nodes, whereas 6 has an extended 2D 4(4) grid-like layer and the adjacent 2D layers are interconnected by strong hydrogen bonding interactions into a 3D supramolecular framework. The structural diversities indicate that distinct organic acid ligands, the nature of metal ions and the pH value play crucial roles in modulating the formation of the resulting coordination complexes and the connectivity of the ultimate topological nets. Moreover, magnetic susceptibility measurement of 5 indicates the presence of weak ferromagnetic interactions between the Co(II) ions bridged by carboxylate groups.

Trinuclear-based copper(I) pyrazolate polymers: effect of trimer π-acid···halide/pseudohalide interactions on the supramolecular structure and phosphorescence.

Under different situations, solvothermal reactions of 3,5-diethyl-4-(4-pyridyl)-pyrazole (HL) with CuX or CuX(2) (X = Cl, Br, I, and SCN) afforded five copper(I) coordination polymers, {CuX[CuL](3)·solvent}(n) (X = Cl, 1; Br, 2; I, 3; X = SCN and solvent = MeCN, 4) and {Cu(2)I(2)[CuL](3)}(n) (5). X-ray diffraction analyses show that all the complexes have trinuclear [CuL](3) (referred as Cu(3)) secondary building units featuring planar nine-membered Cu(3)N(6) metallocycles with three peripheral pyridyl groups as connectors, which are further linked by CuX or Cu(2)X(2) motifs to generate single- or double-strand chains. Interestingly, the Cu(I) atoms within the Cu(3) units in 1-5 behave as coordinatively unsaturated π-acid centers to contact soft halide/pseudohalide X atoms of CuX and Cu(2)X(2) motifs, which lead to novel sandwich substructures of [(Cu(3))(Cu(2)X(2))(Cu(3))] (X = Br, I, and SCN) in 2-4. In addition, both the π-acid [Cu(3)]···X contacts and intertrimer Cu···Cu interactions contribute to the one-dimensional (1D) double-strand and 2D/3D supramolecular structures of 1-5. All of these complexes exhibit high thermostability and bright solid-state phosphorescence upon exposure to UV radiation at room temperature. The emissions arise from the mixtures of metal-centered charge transfer, metal to ligand charge transfer, and halide-to-ligand charge transfer excited states, and can be tuned by intermolecular π-acid [Cu(3)]···halide/pseudohalide contacts.

An unusual 3D entangled Co(II) coordination polymer directed by ferromagnetic molecular building block.

A fascinating 3D entangled metal-organic framework, namely, {[Co(2)(bcp)(2)]·3H(2)O}(n) (1), was obtained through the solvothermal generation of flexible and long dicarboxylate (bcp) and metal salt. The crystal structure contains a 1D metal chain with bcp ligands wrapped around it in a wavy line and features an unusual entangled topological net. Furthermore, the magnetic behavior of 1 was also studied and indicated the existence of ferromagnetic interaction and long-range ordering character.

Syntheses and crystal structures of a series of coordination polymers constructed from C2-symmetric ligand 1,3-adamantanedicarboxylic acid.

This article systematically investigates the influence of the properties of inhomogeneous N-auxiliary ligands and pH value on the helical structures of complexes based on C(2)-symmetric ligand 1,3-adamantanedicarboxylic acid (H(2)ADC). Five kinds of neutral ligands (phen=1,10-phenanthroline, bipy=4,4'-bipyridine, bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane) were selected, and a series of new Zn(II)/Co(II) dicarboxylates have been synthesized by slow diffusion, namely, [Zn(phen)(ADC)(H(2)O)](2).CH(3)OH (1), {[Zn(ADC)(bpe)].H(2)O}(n) (2), {[Zn(ADC)(bipy)].2H(2)O}(n) (3), {[Zn(ADC)(bpa)](2).5H(2)O}(n) (4), {[Zn(ADC)(bpp)](2).CH(3)OH}(n) (5), {[Zn(ADC)(bpp)]}(n) (6), {[Co(ADC)(bpp)(CH(3)OH)(H(2)O)].CH(3)OH2 H(2)O}(n) (7), and {[Co(ADC)(bpp)]}(n) (8). Single-crystal X-ray structural analysis shows that complex 1 forms a 0D dinuclear with closed-loop unit. The complex 2 is a 2D layer framework. Compounds 3 and 4 are isomorphous with a small discrepancy and present one-dimensional chainlike structures. It is interesting that the 2D organic-inorganic hybrid frameworks containing meso-helical chains have been observed. Compound 5 is a 2D interpenetrated network with (4,4) topology, in which homochiral left-handed helical chains are arranged in an ABAB sequence parallel to the plane defined by (a,c), and right-handed helical chains running along the a axis are also observed in the solid state, resulting in a meso-helical structure. Compounds 6, 7, and 8 crystallize in a chiral space group P212121. Highly dimensional 6 and 8 are essentially isostructural and present a threefold interpenetrated 3D diamondoid network containing three helical chains, whereas 7 exhibits a 2D grid layer with a left-handed helical chain. Furthermore, thermal stability, X-ray powder diffraction, and the luminescent properties of 1-6 are also discussed.

DMF/H2O volume ratio controls the syntheses and transformations of a series of cobalt complexes constructed using a rigid angular multitopic ligand.

Through middle-temperature solvothermal reactions of CoCl(2).6H(2)O with the rigid-angled ligand 3-(2'-pyridyl)-5-(4''-pyridyl)-1,2,4-triazole (Hdpt24), we obtained the three cobalt complexes {[Co(dpt24)(2))](3).4DMF.1.5H(2)O}(n) (1), {[Co(dpt24)(2))](2).H(2)O}(n) (2), and Co(dpt24)(2)(Hdpt24).H(2)O] (4) at N,N-dimethylformamide (DMF)/H(2)O volume ratios of 9:1, 1:1, and 0:1, respectively. Interestingly, 1 underwent transformations into 2, {[Co(dpt24)(2)].0.5DMF}(n) (3), and 4 when treated with DMF/H(2)O at volume ratios of 1:1, 1:9, and 0:1, respectively. Moreover, 3 and 4 converted back to 1 in 9:1 DMF/H(2)O and to 2 in 1:1 DMF/H(2)O; 3 transformed into 4 in H(2)O and vice versa in 1:9 DMF/H(2)O. Structurally, 1 is a three-dimensional (3D) 2-fold interpenetrating distorted NbO-type complex, 2 possesses a two-dimensional layer metal-organic framework, 3 is a 3D 2-fold interpenetrating typical NbO-type complex, and 4 is a wheel-shaped mononuclear neutral complex. This approach, using a mixed solvent's component ratio to direct the syntheses and conversions of four cobalt complexes, provides unprecedented control for crystal engineering.

New types of di-, tetra-, hexa- and octanuclear Ag(I) complexes containing 1,3-adamantanedicarboxylic acid.

This article represents a systematical investigation on the structures of silver(I) dicarboxylate incorporating secondary ligands, revealing that the secondary interactions could play an important role in interlinking low-dimensional entities to high-dimensional supramolecular frameworks. A new 2D silver(I) crystalline dicarboxylate, {[Ag(6)(ADC)(3)(H(2)O)(1.5)](2).5.18H(2)O}(n) (1) (H(2)ADC = 1,3-adamantanedicarboxylic acid), has been obtained by slow diffusion of corresponding precursors. To investigate the influence of the properties of pyridylic neutral ligands on the complex structures based on compound 1, five kinds of neutral ligands (bipy = 4,4'-bipyridine; bpa = 1,2-bis(4-pyridyl)ethane; bpe = 1,2-bis(4-pyridyl)ethene; bpp = 1,3-bis(4-pyridyl)propane; bpdap = N,N'-bis(3-pyridyl)-2,6-diaminopyridine) were selected, and a series of new silver(I) dicarboxylate have been synthesized: {[Ag(bpa)(HADC)]}(n) (2), {[Ag(bpp)(HADC)].CH(3)OH}(n) (3), {[Ag(4)(bpe)(3)(ADC)(2)].2H(2)O}(n) (4), {[Ag(bipy)(HADC)].H(2)O}(n) (5), {[Ag(2)(bipy)(2)(ADC)].6H(2)O}(n) (6), and [Ag(8)(bpdap)(4)(ADC)(4)].2C(2)H(5)OH.6H(2)O (7). Single-crystal X-ray structural analysis shows that complexes 1 and 4 are formed by hexanuclear and tetranuclear Ag(I) clusters with weak Ag-Ag interactions. Complexes 2 and 3 are dinuclear structures, 5 and 6 exhibit an infinite 1D chain structure, whereas 7 is a discrete octanuclear Ag(I) unit. The structures of 1-7 span from dinuclear, tetranuclear, hexanuclear, to octanuclear Ag(I) complexes, which indicates that secondary ligands do play important roles in the formation of such coordination architectures. Thermal stability, X-ray powder diffraction and luminescent properties of the compounds are also discussed.

Interplay of coordinative and supramolecular interactions in formation of a series of metal-organic complexes bearing diverse dimensionalities.

A series of new metal-organic coordination complexes, {[Ni(IP)(H(2)O)(4)].(2H(2)O)(SO(4))} (1), [M(IP)(mu(2)-SO(4))(H(2)O)(2)] (M = Zn 2 , and M = Mn 3 ), {[M(2)(IP)(2)(mu(2)-SO(4))(2)(H(2)O)(4)].2H(2)O} (M = Zn 4 , and M = Co 5 ), {[Mn(2)(IP)(mu(2)-SO(4))(H(2)O)(2)].(6.5H(2)O)(sdba)} (6), {[Mn(IP)(2)(H(2)O)(2)][Mn(pydc)(2)(H(2)O)(2)].(4H(2)O)} (7), {[Mn(IP)(fum)(H(2)O)].H(2)O} (8), {[M(3)(IP)(3)(fum)(3)].(8H(2)O)} (M = Cd 9, and M = Zn 10 ), {[Cd(2)(IP)(2)(bptc)(H(2)O)(2)].(7.3H(2)O)} (11), {[Zn(2)(IP)(2)(bptc)(H(2)O)(2)].(3H(2)O)} (12), {Cd(1,4-BDC)(IP)(H(2)O)].(0.5H(2)O)} (13), {[Mn(1,4-BDC)(IP)(H(2)O)].H(2)O} (14), {[Zn(2)(1,4-BDC)(2)(IP)].2.5H(2)O} (15) (IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, H(2)sdba = 4,4'-sulfonyldibenzoic acid, H(2)pydc = pyridine-2,6-dicarboxylic acid, H(2)fum = fumaric acid, H(4)bptc = 3,3',4,4'-benzophenonetetracarboxylic acid and 1,4-H(2)BDC = 1,4-benzendicarboxylic acid) were prepared via self-assembly of pharmaceutical agent IP with different metal sulfates in the absence/presence of the carboxylate under mild conditions. All these compounds were structurally determined by single-crystal X-ray diffraction. Compounds 2-6 crystallize with N-donor chelating ligands and sulfate anion linkers. Complexes 2-6 possess sulfate anions with mu(2)-bridging modes, the roles of sulfate anions result in 1D chains (2 and 3) and dinuclear units (4, 5and 6). For complex 7 , two different Mn units are chelated by two IP and pydc ligands, respectively. Compound 8 is a 1D chain connected by fum ligands. Polymers 9-12 exhibit 2D network structures composed of tetrametallic and hexametallic clusters. The Cd(ii)/Zn(ii) layers are interdigitated in pairs for complexes 11 and 12 by stacking forces, which exhibit unusual 2D-->3D interdigitated architectures. In 13 and 14, they show 1D undulating and linear chains due to the different coordinate modes of 1,4-BDC. IP firstly acts in a tridentate mode via the two N atoms of pyridyl rings and the third N atom of imidazole ring, and the two carboxylate groups of 1,4-BDC ligand taking three types of coordinative modes connect Zn atoms into a complicated 3D network in 15 . The structural differences among complexes 1-15 indicate the backbone of such dicarboxylate ligands, nature of metal resources and the ratio of metal to ligand play important roles in modulating the formation of the coordination polymers. Thermal stabilities of these crystalline materials, fluorescent properties of these complexes and TD-DFT calculation of spectra of IP were also investigated.