Zinc(II) and lead(II) coordination polymers built by 3-(4-carboxyphenylhydrazono)pentane-2,4-dione

Two coordination polymers [Zn(L)₂(4,4′-bipy)₂] _n (4,4′-bipy = 4,4′-bipyridine) (1) and [Pb(η ²-L)(µ₃-η ²-CH₃COO)(H₂O)] _n (2) have been prepared by the reaction of 3-(4-carboxyphenylhydrazono)pentane-2,4-diketone (HL) with zinc(II) or lead(II) in solution. Polymer 1 shows an infinite zigzag chain, in which Zn(II) are linked by 4,4′-bipy bridges with carboxylate of L^? monodentate to Zn(II). In 2, Pb(II) are bridged by tetradentate µ₃-η ²-CH₃COO^? to form a linear 1-D chain, and each Pb(II) is chelated by carboxylate of L^?. Their molecular structures have been characterized by elemental analysis, infrared, and single-crystal X-ray diffraction. Thermal and fluorescent properties of the two complexes have been investigated.     

One-dimensional coordination polymers of Co(II) and Cd(II)-squarate with 2-methylimidazole and 4(5)-methylimidazole ligands

Two new mixed-ligand coordination polymers, {[Co(μ_1,3-sq)(H₂O)₂(2-Meim)₂]·2(2-Meim)}_n (1) and [Cd(μ_1,3-sq)(H₂O)₂(4(5)-Meim)₂]_n (2), (sq = squarate, 2-Meim = 2-methylimidazole, 4(5)-Meim = 5-methylimidazole) have been synthesized and structurally characterized by X-ray crystallography. The spectral (IR and UV–Vis) and thermal analyses are also reported. The Co(II) and Cd(II) ions are distorted octahedrally coordinated by four oxygen atoms of two O¹–O³-bridging squarate ligands and two trans-aqua ligands, and by two nitrogen atoms of the trans-imidazole (2-Meim or 4(5)-Meim) ligands. The structures of 1 and 2 consist of one-dimensional chains of μ-1,3-squarato bridged metal(II) complex units. These chains are held together by hydrogen bonding interactions, forming three-dimensional framework.     

Two different anionic manganese(II) coordination polymers constructed through dicyanamide coordination bridges

In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, two manganese dicyanamide complexes, poly[tetramethylammonium [di‐μ₃‐dicyanamido‐κ⁶N¹:N³:N⁵‐tri‐μ₂‐dicyanamido‐κ⁶N¹:N⁵‐dimanganese(II)]], {[(CH₃)₄N][Mn₂(NCNCN)₅]}_n, (I), and catena‐poly[bis(butyltriphenylphosphonium) [[(dicyanamido‐κN¹)manganese(II)]‐di‐μ₂‐dicyanamido‐κ⁴N¹:N⁵]], {[(C₄H₉)(C₆H₅)₃P]₂[Mn(NCNCN)₄]}_n, (II), were synthesized in aqueous solution. In (I), one Mn^II cation is octahedrally coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands, while the second Mn^II cation is coordinated by four nitrile N atoms and two amide N atoms from six anionic dca ligands. Neighbouring Mn^II cations are linked together by μ‐1,5‐ and μ‐1,3,5‐bridging dca anions to form a three‐dimensional polymeric structure. The anionic framework exhibits a solvent‐accessible void of 289.8 ų, amounting to 28.0% of the total unit‐cell volume. Each of the cavities in the network is occupied by only one tetramethylammonium cation. In (II), each Mn^II cation is octahedrally coordinated by six nitrile N atoms from six dca ligands. Neighbouring Mn^II cations are linked together by double dca bridges to form a one‐dimensional polymeric chain, and C—H...N hydrogen‐bonding interactions are involved in the formation of the one‐dimensional layer structure.     

Crystal structure and fluorescence/phosphorescence of two novel Cd(II) coordination polymers

Two novel Cd(II) coordination polymers [Cd₄(C₆H₄O₂N)₈(H₂O)₄]_n (1) and [Cd₂(C₁₀H₂O₈)(H₂O)₆]_n (2) have been synthesized under hydrothermal condition and structurally characterized. Crystal data: (1), orthorhombic, Pbca, a=11.4494(19) Å, b=12.0969(6) Å, c=17.4073(8) Å, V=2410.9(4) ų, Z=8, D _calc=2.064 g·cm⁻³; (2), triclinic, P , a=5.5962(7) Å, b=7.7758(6) Å, c=9.6975(10) Å, α=111.981(5)°, β=101.649(6)°, γ=98.240(5)°, V=371.95(7) ų, Z=2, D _calc=2.603 g·cm⁻³. Complex (1) possesses three-dimensional infinite structure, while complex (2) adopts two-dimensional layers and the layers are connected by the many types of hydrogen bonds, forming three-dimensional network. Study results of the photophysical properties show that both complexes can emit strong blue fluorescence and complex (1) also emits phosphorescence (λ ^pl _max=511 nm, τ=32 ms) in the solid state at room temperature.     

Cu(II)/Cd(II) coordination polymers based on polycarboxylate and 2-(2-pyridyl)benzimidazole

Three polycarboxylate coordination polymers containing 2-(2-pyridyl)benzimidazole as co-ligand, [Cu(Bdc)(2-PyBIm)] _n (1), [Cu(HBtc)(2-PyBIm)] _n (2) and [Cd₂(HBtc)₂(2-PyBIm)₂] _n ·; nH₂O (3) (H₂Bdc?=?1,4-benzenedicarboxylic acid; H₃Btc?=?1,3,5-benzenetricarboxylic acid), have been synthesized and characterized by elemental analyses, IR spectra, TG-DSC and X-ray structural analyses. Complex 1 is a one-dimensional zigzag chain in which the Cu(II) is cis six-coordinated by two chelating carboxyl groups and a 2-PyBIm ligand. Complex 2 is a two-dimensional (4, 4) network in which H₃Btc is partially deprotonated. Complex 3 has a three-dimensional framework in which one Cd(II) is six-coordinate and the other is seven-coordinate. All 2-PyBIm groups are neutral, chelating, bidentate ligands in 1–3. These complexes are quite thermally stable. The luminescence of 3 has also been investigated.     

Structural assemblies of four Cd(II) coordination polymers based on 5-methylisophthalic acid

Four new metal-organic coordination polymers, Cd(mip)(DMF)(1), Cd(mip)(EtOH)(2), Cd₂(mip)₂(H₂O)₅·3H₂O (3), Cd(mip)(bpp)(H₂O)·H₂O (4) (H₂mip = 5-methylisophthalic acid, bpp = 1,3-di(4-pyridyl)propane) have been hydro(solvo)thermally synthesized and characterized by IR, thermogravimetric (TG) analysis, powder X-ray diffraction and single-crystal X-ray diffraction. 1 and 2 are isostructural, and two adjacent Cd centers are bridged by four carboxylate groups in μ₂-carboxylato-κ¹O_.:κ¹O′ and μ₂Ο; κ²O,O′ fashion to form a linear (Cd–O–Cd)_n chain. The adjacent (Cd–O–Cd)_n chains are further connected by mip bridges to form a 3D framework. 3 features two types of chiral layers: One left-handed and another right-handed, which lead to racemic solid-state compound. 4 exhibits a two-dimensional wave-like (2D) (4,4) layer structure with infinite 1D linear chain. In addition, the luminescent properties of 1–4 are also discussed.     

Synthesis, structure, and fluorescence of two cadmium(II)-citrate coordination polymers with different coordination architectures

Two novel Cd(II)-citrate complexes were obtained with different metal/ligand ratios through hydrothermal method. Their structures were determined by single-crystal X-ray diffraction analysis. Although their topological structures are both 2-D layer network assemblies, both central Cd(II) ions and Hcit³⁻ ligands display completely different coordination modes. In polymeric complex 1, Hcit³⁻ serves as a μ₁₀-bridged and central Cd(II) ions adopt 6- and 8-coordinated configurations. In contrast, a μ₉-bridged and 6- and 7-coordinated environments between Cd(II) and Hcit³⁻ are established in the polymeric complex 2. Two Complexes remain stable up to approximately 300 °C. The complex 1 exhibits strong fluorescent emission band at 450 nm (λ=346 nm) as well as complex 2 exhibits strong fluorescent emission band at 430 (λ=346 nm).     

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH(3))CFc (Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) or O-ferrocecarbonyl benzoic acid, o-HOOCC(6)H(4)COFc with Pb(OAc)(2).3H(2)O, Zn(OAc)(2).2H(2)O, or Cd(OAc)(2).2H(2)O) resulted in four novel ferrocene-containing coordination polymers [[Pb(mu(2)-eta(2)-OOCCH=(CH(3))CFc)(2)].MeOH](n) (1), [[Zn(o-OOCC(6)H(4)COFc)(2)(4,4'-bipy)(H(2)O)(2)].2MeOH.2H(2)O](n) (4,4'-bipy = 4,4'-bipyridine) (2), [[Cd(o-OOCC(6)H(4)COFc)(2)(bpe)(MeOH)(2)].2H(2)O](n) (bpe = 1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC(6)H(4)COFc)(eta(2)-o-OOCC(6)H(4)COFc)(bpe)](n)() (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(II) ions are bridged by tridentate FcC(CH(3))=CHCOO(-) anions, forming an infinite chain [Pb(mu(2)-eta(2)-OOC=CH(CH(3))CFc)(2)](n). In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC(6)H(4)COO(-) units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC(6)H(4)COO(-) units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(II) ions in polymer 1 and strongly influenced by Zn(II), Cd(II), or Pb(II) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.     

由不同长度柔性双咪唑配体构筑的镍(Ⅱ)配位聚合物（英文）

利用2,5-吡啶二酸分别与两种具有不同长度的柔性双咪唑配体,在同样的水热条件下合成了两例结构完全不同的镍(Ⅱ)配位聚合物Ni2(2,5-pdc)_2(L1)_2(H_2O)_2·6H2O(1),Ni(2,5-pdc)(L_2)(H_2O)·H_2O[2,5-pdc=2,5-吡啶二酸,L1=1,4-二(1-咪唑基)丁烷,L2=1,6-二(1-咪唑基)己烷](2).配合物1是三维4-连CdSO_4拓扑网格,Schlfli符号为(6~5·8).而配合物2是由一维螺旋链[Ni(L_2)]n和一维[Ni(2,5-pdc)]n链构筑而成的环-环相扣的一维链状结构.     

One-dimensional zinc(II) fumarate coordination polymers

A new procedure developed for the synthesis and crystallization of various zinc(II) fumarate hydrate coordination polymers is described. In the first step, anhydrous Zn(II) fumarate, [Zn(C₄H₂O₄)] (1), is synthesized from Zn(II) acetate and fumaric acid in methanol. Subsequently, this product is used as a starting material for growing small crystals of bis–aqua Zn(II) fumarate, [Zn(H₂O)₂(C₄H₂O₄)] (2), triaqua Zn(II) fumarate monohydrate, [Zn(H₂O)₃(C₄H₂O₄)]·H₂O (3), tetraaqua Zn(II) fumarate, [Zn(H₂O)₄(C₄H₂O₄)] (4), and tetraaqua Zn(II) fumarate monohydrate, [Zn(H₂O)₄(C₄H₂O₄)]·H₂O (5). All structures were determined or redetermined by X-ray structure analyses. The hitherto unknown compound 3 exhibits a zig-zag chain structure with five-coordinate Zn(II) ions.     

Syntheses and structures of three coordination polymers based on 4-methylbenzenethiolates of Zn(II) and Cd(II) and bipyridine

Using 4-methylbenzenethiolates of Zn or Cd as precursors and 4,4′-bipyridine (4,4′-bpy) as bridges, we have synthesized three new Zn(II)/Cd(II) coordination polymers, {[Cd(4,4′-bpy)₂(NCS)₂] · 2(SC₆H₄CH₃-4)₂} _n (1), {[Zn(4,4′-bpy)(SC₆H₄CH₃-4)₂] · DMF} _n (2) and {[Zn(4,4′-bpy)(SC₆H₄CH₃-4)₂] · H₂O · 0.5CH₃OH} _n (3). Compound 1 is a 2-D sheet-like square polymer in which four 4,4′-bpy ligands and two isothiocyanate ligands complete the octahedral Cd(II) coordination sphere. Compounds 2 and 3 have similar coordination around Zn(II), but have different polymer structures. In 2, Zn(II) centers are linked via a bidentate 4,4′-bipyridine to form 1-D twisted arched chains, which is a new structural type for Zn(II). Compound 3 has 1-D zigzag chains. The 2-D sheets in 1 and 1-D chains in 2 and 3 are assembled via intermolecular C–H ··· π and C–H ··· S interactions into 3-D supramolecular networks. C–H ··· S interactions are a vital factor in constructing the sulfur-containing coordination polymers. Different coordination modes and packing schemes in 1–3 show that the guest molecule has a critical influence on formation of polymers.     

Zn(II) and Cd(II) coordination polymers assembled by di(1H-imidazol-1-yl)methane and carboxylic acid ligands

Five new Zn(II)/Cd(II) coordination polymers constructed from di(1H-imidazol-1-yl)methane (L) mixed with different auxiliary carboxylic acid ligands formulated as [Zn(L)(H(2)L(1))(2)·(H(2)O)(0.2)](n) (1), {[Zn(L)(L(2))]·H(2)O}(n) (2), {[Cd(2)(L)(2)(L(2))(2)]·2H(2)O}(n) (3), {[Cd(L)(L(3))]·H(2)O}(n) (4) and [Cd(L)(L(4))](n) (5) (H(3)L(1) = 1,3,5-benzenetricarboxylic acid, H(2)L(2) = 4,4'-oxybis(benzoic acid), H(2)L(3) = m-phthalic acid and H(2)L(4) = p-phthalic acid) have been synthesized under hydrothermal conditions and structurally characterized. Four related auxiliary carboxylic acids were chosen to examine the influences on the construction of these coordination frameworks with distinct dimensionality and connectivity. The coordination arrays of 1-5 vary from 1D zigzag chain for 1, 2D (4,4) layer for 2-4, to 2-fold interpenetrated 3D coordination network with the α-Po topology for 5. The thermal and photoluminescence properties of complexes 1-5 in the solid state have also been investigated.     

Three Cd(II) coordination polymers based on a pyridyldicarboxylate: effect of coordinated water

Abstract

By systematic change of the solvothermal synthesis, three new coordination polymers, [Cd(L)?(H₂O)]?2H₂O (1), [Cd(L)?(H₂O)]?H₂O (2), and [Cd(L)] (3), have been synthesized based on a tritopic ligand 4-(pyridin-3-yl)isophthalic acid (H₂L). Compounds 1 and 2 show very similar two-dimensional (2D) bilayers further linked by interlayer hydrogen bonds into three-dimensional (3D) supramolecular structures, while 3 displays a 3D structure constructed form one-dimensional (1D) Cd-carboxyl chains. Notably, 1 and 2 have a pair of unusual isomers with the opposite orientation of coordinated H₂O on the metal centers, leading to different hydrogen bonding interactions. Thermal stabilities and solid-state photoluminescences for 1–3 were also investigated.     

Synthesis, structure, and fluorescence of the novel cadmium(II)-trimesate coordination polymers with different coordination architectures

Three novel complexes, Cd3tma2*13H2O (1), Cd3tma2*dabco*2H2O (2), and Cd3Htma3*8H2O (3) (tma = trimesate), of cadmium(II)-trimesate coordination polymers are obtained from hydrothermal reaction. 1 (C18H32O25Cd3) crystallizes in the monoclinic C2/c space group [a = 18.985(2) A, b = 7.3872(6) A, c = 20.432(2) A, = 97.1660(10), and Z = 4]. 2 (C24H22N2O14Cd3) crystallizes in the monoclinic P2(1)/c space group [a = 10.1323(2) A, b = 19.5669(5) A, c = 13.15880(10) A, = 108.9810(10), and Z = 4]. 3 (C27H28O26Cd3) belongs to the trigonal P31c space group [a = 15.7547(3) A, b = 15.7547(3) A, c = 7.93160(10) A, and Z = 2]. The Cd(II) centers in the three complexes are bridged by tma ligands in the coordination fashion of unidentate, bridging unidentate, bidentate, chelating bis-bidentate, chelating/bridging bis-bidentate, or chelating/bridging bidentate to form the T-shaped molecular bilayer motif for 1, chicken-wire-like motif for 2, and honeycomb-like porous structure for 3, respectively, in which the T-shaped molecular bilayer motif and chicken-wire-like motif are further interlinked in interdigitating or alternating fashion to construct the different coordination architectures. These three complexes exhibit strong fluorescent emission bands at 355 nm (lambda(ex) = 220 nm) for 1, 437 nm (lambda(ex) = 365 nm) for 2, and 353 nm (lambda(ex) = 218 nm) for 3 in the solid state at room temperature.     

Topological diversification of two new Cd(II) photoluminescent coordination polymers via auxiliary N-donor ligands

Two new cadmium(II) coordination polymers, [Cd₂(nda)₂(L₁)] _n (1) and [Cd(nda)(L₂)_0.5] _n (2), were hydrothermally synthesized with 1,4-naphthalenedicarboxylic acid (H₂nda) and auxiliary N-donor coligands [L₁?=?1,5-bis(2-methyl-imidazol-1-yl)pentane and L₂?=?4,4′-bis(2-methyl-imidazol-1-ylmethyl)biphenyl]. Single-crystal X-ray diffraction analyses showed that the topological networks are different when the N-donor ligands are changed. Compound 1 showed a (4¹⁶.6⁵) topology and 2 showed a twofold interpenetrating pcu topology.     

Two new Pb(II) coordination polymers derived from fatty dicarboxylates and phenanthroline derivatives: syntheses,structures, and properties

Two new Pb(II) coordination polymers, [Pb(3-pdip)(L₁)]?·?0.5H₂O (1) and [Pb(4-pdip)(L₂)] (2) [L₁?=?heptane diacid, L₂?=?hexane diacid, 3-pdip?=?2?-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, 4-pdip?=?2?-(4-pyridyl)imidazo[4,5-f]1,10-phenanthroline], have been obtained from hydrothermal reactions of Pb(II) nitrate with two flexible fatty carboxylic acids and two phenanthroline derivatives. Single-crystal X-ray diffraction analysis reveals that 1 is a 1-D staircase-like double chain coordination polymer extended by binuclear [Pb₂N₄O₈] subunits and pairs of L₁ ligands. Compound 2 exhibits a 2-D (4,4) network based on bi-metallic [Pb₂N₆O₈] units and (L₂)₂/(4-pdip)₂ double linkers. Furthermore, adjacent chains of 1 and layers of 2 are extended into 3-D supramolecular networks by π–π stacking interactions between aromatic rings of phenanthroline groups. The organic carboxylic acids with different lengths show great influence on the shapes of Pb(II)-carboxylate double chains. Phenanthroline derivatives possessing different sites of N-donors (3-pyridyl and 4-pyridyl) determine the final coordination frameworks of 1 and 2. Photoluminescence and thermal stabilities of 1 and 2 were also investigated.     

Liquid-crystalline zinc(II) and iron(II) alkyltriazoles one-dimensional coordination polymers

Several series of unidimensional coordination polymers of formula [Zn(C(n)H(2n+1)trz)(3)](Cl)(2)·xH(2)O (n = 18, 16, 13, 11, 10, trz = 4-substituted-1,2,4-triazole), [Zn(C(18)H(37)trz)(3)](ptol)(2)·xH(2)O, [Fe(C(n)H(2n+1)trz)(3)](X)(2)·xH(2)O (n = 18, 16, 13, 10; X = Cl(-) or ptol(-), where ptol(-) = p-tolylsulfonate anion), and [Fe(C(18)H(37)trz)(3)](X)(2)·xH(2)O (X = C(8)H(17)PhSO(3)(-) and C(8)H(17)SO(3)(-)) are reported with their thermal, structural, and magnetic properties. Most of these materials exhibit thermotropic lamellar mesophases at temperatures as low as 410 K, as confirmed by textures observed by polarized optical microscopy. The corresponding phase diagrams deduced by differential scanning calorimetry are also reported. All iron-containing materials present a spin crossover phenomenon that occurs at temperatures ranging from 242 to 360 K, only slightly below the mesophase temperature domain, and remains complete and cooperative, even for the longer alkyl substituents. The use of stable diamagnetic Zn(II) analogues proves to be very useful to characterize the comparatively less stable and less crystalline Fe(II) analogues.     

Malonato-bridged hexamethylenetetramine coordination polymers containing Mn(II) and Cu(II)

Two malonato-bridged hexamethylenetetramine coordination polymers, M₂(hmt)(H₂O)₂(mal)₂ [hmt?=?hexamethylenetetramine, mal?=?malonate(2-), M?=?Mn (1), Cu (2)] were prepared and structurally characterized. The isostructural complexes are orthorhombic, space group Imm2, with a?=?7.104(1), b?=?15.982(3), c?=?7.702(1)?Å, Z?=?2, D _calc?=?1.862?g?cm^?3(1) and a?=?6.962(3), b?=?15.500(7), c?=?7.627(3)?Å, Z?=?2, D _calc?=?2.047?g?cm^?3for 2. The transition metals are octahedrally coordinated by one nitrogen atom of an hmt ligand and five oxygen atoms of a water molecule and three malonate anions. The latter coordinate in chelating/bis-monodentate mode to give 2D layers with a (4,?4) topology, and which are pillared by bridging bidentate hmt ligands to generate an open 3D framework with channels extending in the [001] direction. Over the temperature range 5–300?K, 2 behaves paramagnetically, following the Curie–Weiss law χ_m(T???θ)?=?4.521(6)?cm³mol^?1K with a Weiss constant θ?=??4.8(2)?K.     

Inorganic coordination polymers. VIII. Cobalt(II) and zinc(II) phosphinate polymers and copolymers

The preparation, properties, x-ray powder patterns, and TGA curves are given for cobalt(II) dimethyl-, methylphenyl- and diphenylphosphinate. The polymeric character of cobalt(II) methylphenylphosphinate is demonstrated by its colligative properties and melt indexes. These cobalt(II) phosphinates along with hybrid copolymers of zinc(II) or cobalt(II) were prepared by the reaction of the metal acetate with the appropriate phosphinic acid or mixture of phosphinic acids. A consideration of the hybrid copolymers leads to the conclusion that both the zinc(II) and cobalt(II) dimethyl- and diphenylphosphinates are likewise polymeric. Thermal stability is discussed in terms of the structures suggested, and it is shown that crystallinity is related to polymer symmetry.     

Hydrothermal synthesis,crystal structures,and photoluminescent properties of two cadmium(II) coordination polymers derived from dicarboxylates and N-donor ligands

Two metal coordination polymers, [Cd(ipa)(L₁)(H₂O)]_n (1) and [Cd(ipa)(L₂)]_n (2) [H₂ipa?=?isophthalic acid, L₁?=?3,5-bis(imidazole-1-yl)pyridine and L₂?=?3,5-bis(benzoimidazo-1-ly)pyridine], have been synthesized and structurally characterized by IR, elemental analysis, XRD, and X-ray single-crystal diffraction. Complex 1 shows a twofold cds topological net and 2 features a 3-D pcu topological net. Luminescent properties of 1 and 2 were investigated in the solid state at room temperature.