Search

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]

This work presents a series of coordination polymers with a dipyridyl-type building block bis[3,5-dimethyl-4-(4′-pyridyl)pyrazol-1-yl]methane (pypz) and different anionic co-ligands. The elongated and flexible backbone of the pypz ligand facilitates the formation of diverse entangled coordination networks, which are well regulated by the auxiliary anionic components. Generally, the anions of nitrate, chloride, and pseudohalide (such as dicyanamide, thiocyanate, and azide) display a monodentate binding mode in this system and serve as terminal pendants of the metal–pypz coordination layers. As a result, 2D → 3D polythreading architectures are mostly observed, except in the case of small chloride anion that leads to twofold parallel interpenetration of the layers. On the other hand, the aromatic dicarboxylates such as terephthalate and biphenyl-4,4′-dicarboxylate behave as rod-like linkers for the construction of diversiform 2D or 3D interpenetrated coordination networks with the aid of pypz. Besides, these crystalline materials may also be significantly affected by other assembled elements such as metal ion, solvent, and metal-to-ligand ratio. [ABSTRACT FROM AUTHOR]

A series of nine CoII, CuII, and CdII mixed-ligand coordination complexes with a 3,3′-dipyridyl connector 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) have been achieved, by changing the incorporated benzenedicarboxylic co-ligands from isophthalic acid (H2ip) to its 5-substituted derivatives 5-nitroisophthalic acid (–NO2, H2nip) and trimesic acid (–COOH, H3tma). All compounds have been structurally determined by the X-ray diffraction technique. It is indicated that most of them are coordination polymers, with the ligands of benzenecarboxylic acids being doubly deprotonated to compensate the charge and bridge the metal ions, except for a monomeric ion-pair product [Co(3-bpt)2(H2O)4]·(H2tma)2·(H2O)2 (1c). These polymers display a variety of coordination frameworks, such as 1-D double-strand chain, 2-D layer with (4,4) topology, 2-D double layer, 2-D layer with (6,3) topology and 1-D molecular ladder etc. The results evidently reveal the profound substituent effect of the R-isophthalate building blocks on engineering such coordination arrays, in virtue of the versatility of 3-bpt with diversiform configurations and binding fashions. Nevertheless, the choice of metal ion is also significant in the structural assembly, and the low-dimensional coordination networks are further extended to diverse 3-D supramolecular crystalline lattices via noncovalent interactions especially hydrogen bonding. Solid-state properties such as thermal stability and fluorescence have also been investigated. [ABSTRACT FROM AUTHOR]

A series of nine mixed-ligand metal-organic frameworks (MOFs) have been prepared by the combination of a bent dipyridyl linker 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (bpt) and three benzenedicarboxylate isomers (pa = phthalate, ip = isophthalate, and tp = terephthalate), respectively, with different metal ions such as CoII, NiII, CuII, ZnII, and CoII. The framework structures of these neutral polymeric complexes have been determined by the X-ray single- crystal diffraction technique. Structural analysis reveals that the benzenedicarboxylate isomers display versatile coordination modes to manage the metal ions to form 1-D chain or ribbon arrays, which are further extended via the exo-bidentate bpt connectors to give rise to a variety of coordination networks, such as a simple (4,4) layer, 2-D double layer with decorated (4,4) topology, 2-D layer with decorated (3,6) topology, 2-D bilayer with 8².10 topology (2-fold interpenetration), 3-D polythreaded architecture (1-D + 2-D), and 2-fold interpenetrating porous lattice of (4,4) layers. The accessorial secondary interactions such as hydrogen bonding and/or aromatic stacking are also helpful for the extension and stabilization of the final supramolecular aggregates. This work evidently indicates that the isomeric effect of the anionic benzenedicarboxylate is significant in the construction of these network structures, which are also well regulated by the metal centers. The ZnII and CdII MOFs exhibit strong solid-state luminescence emissions at room temperature, which originate differently from intraligand transition or ligand-to-metal charge transfer. Thermal stability of these crystalline materials has been explored by thermogravimetric analysis of mass loss. The 3-D host frameworks of MOFs 8 and 9 show similar porous cavities, and their desorption/ adsorption behaviors of guest solvents have also been investigated. [ABSTRACT FROM AUTHOR]

The formation, crystal structures, and properties of a series of three-dimensional (3-D) CuII coordination polymers, {[Cu(L)2(H2O)2](PF6)2(H2O)1.25}n (1), {[CuL(N3)2](H2O)1.5}n (2), and {[CuL(H2O)(SO4)](H2O)2}n (3), with an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L) are reported. Complex 1 crystallizes in the tetragonal /41/a space group (a = b = 13.462(2) Å, c = 46.47(1) Å, Z = 8), complex 2 in the orthorhombic Pna21 space group (a = 6.379(2) Å, b = 10.060(3) Å, c = 27.232(9) A, Z = 4), and complex 3 in the orthorhombic P212121 space group (a = 5.510(2) Å, b = 10.576(4) ,Å, c = 28.34(1) Å, Z = 4). Different polymeric frameworks are obtained by only varying the counterions. These include the 2-fold interpenetrated diamondoid structure of 1, the acentric α-Po network of 2, and the chiral open framework of 3 with (6³).(69.8) topology. The interesting anion-exchange, porous, and magnetic properties of these coordination supramolecules have been investigated in detail. [ABSTRACT FROM AUTHOR]

Examines the crystal structure with three-dimensional coordination of polymer with angular dipyridyl ligand. Discussion on the magnetic properties and anion effects; Degree of interpenetration of diamondoid networks; Integration of diffraction profiles.

Investigates the varying coordination modes and magnetic properties of copper(II) complexes with diazamesocyclic ligands by altering additional donor pendants on 1,5-diazacyclooctane. Syntheses of ligands; Description of the crystal structures; Binuclear, trinuclear and polymeric complexes; Electronic spectra.

The reaction of copper(II) nitrate, oxamide, and an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) under hydrothermal conditions affords a 3D pillared-layer coordination framework {[Cu2(4-bpo)(ox)2](H2O)4}n (1) (ox = oxalate), featuring the unique zeolite-type NiP2 network and interesting properties. [ABSTRACT FROM AUTHOR]

A series of mixed-ligand coordination complexes have been prepared using diffusion method, by reacting the CoII, NiII, ZnII, AgI, CdII, CuII, or PbIInitrate with tetrabromoterephthalic acid (H2tbta) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo). These complexes show various 0D, 1D, 2D, and 3D coordination motifs with different geometries of the metal centers, indicating a metal-directed assembly. The synthetic condition will also affect the resulting crystalline products for ZnIIspecies. Crystal structure analysis reveals that secondary interactions such as hydrogen bonding and aromatic stacking will further extend the coordination arrays to diverse supramolecular architectures. All complexes have been characterized by IR, elemental analysis, and powder X-ray diffraction techniques. In addition, the polymeric coordination systems with d10metal centers show solid-state fluorescent emissions at room temperature, which thus may be applied as potential hybrid luminescent materials. [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]

Six new metal-organic coordination networks based on linking unit 2,5-bis(4-pyridyl)-l,3,4-thiadiazole (L¹) or 2,5bis(3-pyridyl)-l,3,4-oxadiazole (L³) and inorganic CuΙΙ CdΙΙ, and CoΙΙ salts have been prepared and structurally characterized by single-crystal X-ray analysis. Using L¹ to react with three different CuΙΙsalts, Cu(OAc)2·H2O, Cu(NO3)2·3H2O, and CuSO4·5H20, respectively, two different one-dimensional (l-D) coordination polymers, {[Cu2L¹(μOAc)4](CHCI3)2}n (1) [triclinic, space group P1macr;, a = 7.416(3) Å, b = 8.207(3) Å, c = 14.137(5) Å, α = 100.333(7)°, β = 105.013(6)°, γ = 94.547(6)°, Z = 1] and {[CuL¹(NO3)2](CHCI3)0.5}n (2)[monoclinic, space group C2/c, a = 28.070(8) Å, b = 9.289(3) Å, c= 15.235(4) Å, β = 113.537(5)°, Z = 8], and a chiral 3-D open framework, {[CuL¹(H2O)(SO4)](H20)2}n (3)[orthorhombic, space group P212121, a = 5.509(2), Å b = 10.545(4) Å, c = 29.399(11) Å, Z = 4], were obtained. Reaction of L¹ and Cd(ClO4)2·6H2O or Co(ClO4)2·6H2O, in the presence of NH4SCN, yielded another 3-D open framework, {[CdL¹(NCS)2](CH3OH) 1,5}n (4) [monoclinic, space group C2/c, a = 28.408(10) Å, b = 9.997(5) Å, c = 7.358(4) Å, β = 99.013(8)°, Z= 4], or a 2-D network, {[Co(L¹)2 (NCS) 2](H2O)2.5}n (5) [orthorhombic, space group Pnna, a = 22.210(5) Å, b = 12.899(3) Å, c = 20.232(4) Å, Z = 4]. When L¹ was replaced by L³ to react with Co(CIO4)2·6H20 and NH4SCN, another 2-D coordination polymer, [Co(L³)2(NCS)2]n (6) [monoclinic, space group P21/c, a = 8.120(3) Å, b = 9.829(4) Å, c = 17.453(6) Å, β = 103.307(6)°, Z = 2], was constructed. These results indicate that the nature of the ligands, metal centers, or counteranions plays the critical role in construction of these novel coordination polymers. The interesting porous natures of two 3-D open frameworks 3 and 4 were investigated by TGA and XPRD techniques, and the magnetic properties of the CuΙΙ and CoΙΙ complexes were studied by variable-temperature magnetic susceptibility and magnetization measurements. [ABSTRACT FROM AUTHOR]

Examines the features of metal complexes with a flexible bis(sulfinyl). Propensity to form multidimensional coordination polymers with transition metals and rare earth elements; Preference for O-binding in hard acid metal complexes; Ability of the ligands to form diverse extended networks.

Examines the crystallography and photophysical and electrochemical properties of dinuclear or chain polymeric silver(I) complexes with polypyridyl bridging ligands by cyclic voltammetry and emission and electronic absorption spectra. Bond lengths and angles; Thermal ellipsoid at 30% probability.

Controlled assembly of ZnII with a versatile ligand 5-(4-pyridyl)-1H-1,2,4-triazole-3-thiol (Hptt) in conventional or solvothermal condition affords two distinct coordination frameworks, in which the former shows a unique 3-D pseudo-polyrotaxane architecture with 1-D water tapes penetrating the 2-D Zn–ptt layers, whereas the later is generated from in situ S–S coupling of Hptt and has a very rare 2-fold interpenetrating LiGe (lig) topology. [ABSTRACT FROM AUTHOR]

The mol­ecular structure of the neutral mononuclear complex [Fe(NCS)2(3-bpo)2(H2O)2], in which 3-bpo denotes 2,5-di-3-pyrid­yl-1,3,4-oxadiazole (C12H8N4O), is centrosymmetric, with FeII located on an inversion center. This complex is octa­hedral, and the FeII atom is trans coordinated by two monodentate NSC− ligands, two monodentate 3-bpo ligands and two water mol­ecules. Each complex is linked to four others, forming a (011) sheet, by O—H⋯N hydrogen bonding. Weak C—H⋯S inter­actions link each (011) sheet to the two adjacent sheets, hence forming a three-dimensional array. There is also some slipped π stacking within each sheet. [ABSTRACT FROM AUTHOR]

In the centrosymmetric dinuclear title complex, [Cu2(CH3O)2(C4H8N3O2)2], the two CuII ions are linked by a pair of methoxide bridges, with a non-bonding Cu⋯Cu distance of 3.048 (1) Å. Each CuII center adopts a CuO2N2 square-planar geometry, coordinated by the bidentate bis­(methoxy­carbimido)aminate and two methoxide ligands. [ABSTRACT FROM AUTHOR]

The article presents information on the structure of the organic compound, di-2-pyridyl ketone azine. It has been long associated with the spectrometric determination of microamounts of metal ions. In the crystal structure of di-2-pyridyl ketone azine each molecule is disposed about a twofold axis perpendicular to the central N-N single bond. Recent studies of the coordination chemistry of this potential multidentate ligand suggests that di-2-pyridyl ketone azine forms a discrete tetranuclear complex with AgNO3.

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]

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]

Eight ZnIIand CdIIcoordination complexes, {[Zn3(nbta)2(bpy)2(H2O)2](H2O)2}n(1), [Zn4(nbta)2(bpe)2(OH)2]n(2), {[Cd3(nbta)2(bpy)5(H2O)2](H2O)6}n(3), {[Cd3(nbta)2(bpe)2(H2O)2](H2O)2}n(4), [Zn2(Hbta)2(bpy)2(H2O)2](H2O) (5), [Zn(bta)(Hbpe)]n(6), [Cd5(bta)2(Hbta)2(bpy)3(H2O)2]n(7), and {[Cd4(bta)2(bpe)2(H2O)4(OH)2](H2O)2}n(8), were prepared via hydrothermal reactions based on H3nbta or H3bta (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid and H3bta = 1,2,3-benzenetricarboxylic acid) and the dipyridyl-type coligand 4,4′-bipyridyl (bpy) or 1,2-di(4-pyridyl)ethene (bpe). All complexes were characterized by elemental analysis, IR spectra, and X-ray powder diffraction techniques. Complexes 1−4all display unusual three-dimensional (3-D) self-penetrating coordination networks. From the topology point of view, complexes 1and 2display the 4-connected frameworks with the Schläfli symbols of (4.104.12)2(43.62.8)2(44.62) and (4.62.72.8)2(42.62.7.8), respectively. Complex 3features an unprecedented 3-nodal network with (3,5,6)-connectivity and the Schläfli symbol of (52.64.72.86.10)(52.65.72.8)2(52.6)2, also exhibiting an intriguing polyrotaxane entangled motif. Complex 4shows a new 4-connected (42.63.8)4(64.8.10) topology. Different from 1−4, complexes 5−8based on H3bta all present the non-self-penetrating structural type. Complex 5possesses binuclear units which are further extended to a two-dimensional (2-D) supramolecular network via extensive H-bonding interactions, showing alternate left- and right-handed helical chains. Complex 6has a 2-D layered motif generated via H-bonding interactions between the one-dimensional (1-D) coordination chains. Complex 7shows a 3-D coordination framework, which is constructed from the 2-D metal-carboxylate layers pillared by the rod-like bipy spacers. Complex 8presents a 2-D net with the [Cd4(μ3-OH)2]6+clusters as the linking nodes. These results reveal that the existence of the electron-withdrawing -NO2group in such a tricarboxyl building block plays a critical role in structural direction of the self-penetrating coordination frameworks. [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]

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]

A series of CdII, CoII, NiII, and PbIImixed-ligand coordination complexes 1−8based on 5-sulfoisophthalic acid (H3sip) and the bent dipyridyl ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) or its 4-pyridyl N-donor analogue (4-bpo) have been synthesized and fully characterized by IR spectra, microanalyses, and single crystal and powder X-ray diffraction techniques. The significant pH effect on assembly of the CdIIcomplexes 1−4has been demonstrated, which leads to the formation of distinct crystalline products, whereas the CoII, NiII, and PbIIsystems 5−8are independent to pH condition of the synthetic reaction. Complexes 1−8display various coordination motifs with different existing forms, conformations, and coordination modes of the organic ligands. Further, extended supramolecular networks are constructed via secondary interactions such as hydrogen-bonding and aromatic stacking. Solid-state properties of thermal stability and fluorescence for these crystalline materials are also presented. [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]

The title complex, [CdCl(NCS)(C10H8N2)] n, represents an unusual CdII coordination polymer constructed by two types of anionic bridges and 2,2′-bipyridyl (bipy) terminal ligands. These two types of bridges are arranged around inversion centers. The distorted octahedral coordination of the CdII center is provided by two chloride ions, one N- and one S-donor atom from two thiocyanate ions, and a pair of N atoms from the chelating bipy ligand. Interestingly, adjacent CdII ions are interconnected alternately by paired chloride [Cd...Cd = 3.916 (1) Å] and thiocyanate bridges [Cd...Cd = 5.936 (1) Å] to generate an infinite one-dimensional coordination chain. Furthermore, weak interchain C—H...S interactions between the bipy components and thiocyanate ions lead to the formation of a layered supramolecular structure. [ABSTRACT FROM AUTHOR]

A series of ZnIIand CdIIcomplexes with a flexible dicarboxylate building block and various heterocyclic co-ligands, formulated as {[Zn2(pda)2(phen)2]·2H2O}n(1), {[Zn(pda)(dpe)]·H2O}n(2), [Zn(pda)(bpp)]n(3), {[Cd2(pda)2(2,2′-bipy)2]·2H2O}n(4), {[Cd(pda)(4,4′-bipy)(H2O)]·H2O}n(5) and {[Cd2(pda)2(bpp)3]·14H2O}n(6) (pda = 1,3-phenylenediacetate, phen = 1,10-phenanthroline, dpe = 1,2-di(4-pyridyl)ethylene, bpp = 1,3-bi(4-pyridyl)propane, 2,2′-bipy = 2,2′-bipyridine, and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and structurally characterized. In 1, the (H2O)8clusters interlink the cyclic coordination dimers to give a 3D network through hydrogen bonding. Both 2and 3feature 2D corrugated (4,4) layers, which are of 2-fold interpenetrating for 3. In 4, the dimeric CdIIsubunits are connected by the 1,3-pda ligands to generate a rampart-shaped 1D chain motif. As for 5, the [Cd(pda)]2rings are connected by the paired 4,4′-bipy ligands to afford a tube-shaped 1D motif. In contrast to 1–5, complex 6displays a 3D diamond network and, interestingly, the T5(0)A(0)A(2) water tapes are found to locate in the channels of this 3-D array. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands (from chelating to bridging) play a key role in governing the coordination motifs as well as the 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stability of 1–6have also been studied. [ABSTRACT FROM AUTHOR]

Five new Mn(II) metal–organic coordination polymers, [Mn(tbip)(bipy)]n(1), {[Mn(tbip)(dpe)]·1.5H2O}n(2), [Mn(tbip)(bpa)]n(3), [Mn(mip)(bpa)]n(4) and {[Mn3(mip)2(Hmip)2(bpp)2(H2O)2]·2H2O}n(5), were prepared through hydrothermal reactions of Mn(II) acetate with H2tbip (H2tbip = 5-tert-butyl isophthalic acid) or H2mip (H2mip = 5-methylisophthalic acid) in the presence of different dipyridyl co-ligands (bipy = 4,4′-bipyridine, dpe = 1,2-bi(4-pyridyl)ethene, bpa = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-di(4-pyridyl)propane). All these compounds were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. The structures of 1and 2are constructed of [Mn2(tbip)2]nlayers, which consist of alternate left- and right-handed helical chains, and further pillared by bipy or dpe ligands into a 3D porous framework. Interestingly, there are two different sizes of pores in 1and 2. From the topology point of view, both complexes 1and 2exhibit the rare rob network based on the dimeric [Mn(COO)]2subunits as the 6-connected nodes. The ribbon-like chains having 8- and 16-membered rings in 3and 4result from dimeric Mn(II) units bridged by H2tbip or H2mip ligands, which are connected by the flexible dpa into 2D open layers. Complex 5contains rare isophthalato-bridged trimanganese clusters as building units, which are further linked by mip anions to form a one-dimensional ladder-like chain with less common unidentate coordinated bpp decorated as pendants. The thermal stabilities and X-ray powder diffraction studies indicate that the microporous framework of 2can keep stable even after the loss of guest water molecules. In addition, dominant antiferromagnetic coupling was observed in compounds 1–3and 5. [ABSTRACT FROM AUTHOR]

Assembly of isophthalate derivatives with ZnIIin the presence of a flexible ligand 1,3-bis(4-pyridyl)propane yields distinct 4-connected coordination frameworks of sql(3.85)(32.83.9) and diatopologies, which reveal the delicate substituent effect of isophthalate tectons. The 3-D network in complex 2is of 4-fold interpenetration with a new topology, displaying a unique polyrotaxane and polycatenane character. [ABSTRACT FROM AUTHOR]