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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]

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]

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]

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]

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]

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]

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]