Cobalt(II) and cobalt(III) coordination polymers constructed from flexible bis-imidazole and polycarboxyl co-ligands: syntheses,crystal structures and properties

Two metal coordination polymers, namely {[Co(1,3-BIP)(OBA)]·0.5H₂O}_n (SNUT-1) and [Co₂(µ-η¹:η¹-O₂)(1,3-BIP)₂(PMA)]_n (SNUT-2), where 1,3-BIP?=?1,3-bis(imidazol)propane, H₂OBA?=?4,4′-oxybis(benzoate) and H₄PMA?=?benzene-1,2,4,5-tetracarboxylic acid, were prepared by hydrothermal methods. Single-crystal X-ray analysis revealed that the structure of SNUT-1 consists of a 3D?→?3D twofold interpenetrating network that can be described as a 4-connected uninodal net with (6⁵·8) topology. The structure of SNUT-2 consists of a 3D framework which can be described as a (4,5)-connected binodal net with (4²·6³·8⁴·10) (3³·4²·5) topology. The gas adsorption properties of SNUT-1 and photocatalytic activity of SNUT-2 for the degradation of Rhodamine B have been explored.

     

Spectral and thermochemical properties of the [Na(H2O)4] [EuL4]·0.775CH2Cl2 complex,HL = 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione

Reaction of Eu(NO₃)₃·6H₂O with 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione (HL) in the presence of NaOH affords the complex compound [Na(H₂O)₄] [EuL₄]·0.775CH₂Cl₂ (I). The spectral (UV, IR, ¹H NMR spectroscopy), and thermo-luminescent (TG-DSC-MS) properties of the complex I, as well as its fragmentation at the laser desorption ionization (LDI-MS) were studied.     

Syntheses,Structures and Luminescence Sensing Properties of Two Cd(II) MOFs Constructed from Mixed Ligands

Hydrothermally reaction of Cd(NO₃)₂·4H₂O, pimelic acid (H₂Pim) mixed with two N-containing ligands of 1,2-bis(2-methyl-imidazol-1-ylmethyl)benzene (1,2-mbix) or 1,3-bis(2-methyl-imidazol-1-ylmethyl)benzene (1,3-mbix) gave rise to two new Cd(II) MOFs, [Cd(Pim)(1,2-mbix)] (1) and [Cd(Pim)(1,3-mbix)]·H₂O (2). Both MOFs were structurally characterized by IR and UV–Vis spectra, single-crystal and powder X-ray diffraction, thermogravimetric analyses. MOF 1 shows a fourfold interpenetrating dia network. Differently, MOF 2 shows a 2D?→?3D interdigitated architecture base on the 6³ hcb layer when 1,2-mbix was replaced by 1,3-mbix. The luminescent properties of 1 and 2 have been investigated. Furthermore, the luminescent quenching experiments suggest both MOFs exhibit good selectivity and sensitivity to detect Fe³⁺ and Cr₂O₇^2? in water.

     

Syntheses,structures, and luminescence of three 4-connected zinc coordination polymers with bis(1,2,4-triazol-1-yl)propane and benzenebiscarboxylate

Three zinc(II) coordination polymers {[Zn(btp)(1,2-bdc)(H₂O)]?·?H₂O} _n (1), {[Zn(btp)(1,3-bdc)(H₂O)]?·?1.5H₂O} _n (2), and {[Zn(btp)(NO₂-1,3-bdc)(H₂O)]?·?2H₂O} _n (3) were synthesized by 1,3-bis(1,2,4-triazol-1-yl)propane (btp) and bis-carboxylate. Compound 1 is a thick 2-D network; 2 and 3 are undulated 2-D (4,4) networks. In 2 and 3, two adjacent networks interpenetrate to form a new 2-D double-layer network, which is sustained by hydrogen-bonding interactions. Compounds 1 and 2 reveal blue emission maximum at 351 and 403, respectively, in the solid state at room temperature.     

Two new metal-organic frameworks possessing binodal high-connected topologies based on Cd4-clusters and organic ligands

Two new compounds, [Cd₂(bptc)(bpimb)(H₂O)]?·?2H₂O (1) and [Cd₂(bptc)(bpib)]?·?4H₂O (2) (where H₄bptc?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, bpimb?=?1,3-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene, bpib?=?1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane), were synthesized by reactions of the corresponding metal salts with H₄bptc and N-containing auxiliary ligands and their structures have been determined by single-crystal X-ray diffraction. Compound 1 is built by Cd₄-clusters which further construct a 3-D (3,8)-connected framework with tfz-d notation; 2, also built by Cd₄-clusters, is a 3-D (4,8)-connected framework with (3²?·?4²?·?5²)(3⁴?·?4⁸?·?5¹²?·?6⁴) topology. In addition, the elemental analyses, infrared spectra, fluorescence, and thermogravimetric analyses for 1 and 2 are discussed.     

The complex Eu(phen)L3��5CH2Cl2 (HL is 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione): synthesis, crystal structure, and luminescent properties

A reaction of Eu(NO₃)₃·6H₂O with the novel heterocyclic ligand 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione and 1,10-phenanthroline in the presence of NaOH gave the complex Eu(phen)L₃·5CH₂Cl₂. The crystal structure of the complex was determined by single-crystal X-ray diffraction. The coordination polyhedron {EuO₆N₂} is a tetragonal antiprism. The complex shows bright orange-red luminescence in both the solid state and solution.     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个 Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H2L)(H2O)3]·H2O·0.5H4L}n(1)、{[Co(L0.5(4,4'-bpy)]·0.5H2O}n(2)和{[Co(L)0.5(pbmb)(H2O)]·H2O}n(3)(H4L=5,5'-(hexane-1,6-diyl)-bi...     

Synthesis and characterization of potassium 1,3-bis(N-methylpiperazino)propan-2-O-xanthate and the complexes of Co(II), Ni(II) and Cu(I) ions

Potassium 1,3-bis(N-methyl piperazino)propan-2-O-xanthate (LK), and its complexes with Co(II), Ni(II) and Cu(I) ions have been prepared and characterized as [CoL₂(H₂O)₂], [NiL₂(H₂O)₂]·2H₂O and CuL·2H₂O by FT-IR, ¹H and ¹³C?NMR spectroscopies, elemental analyses, magnetic susceptibility and TGA techniques.     

Two independent, 1-D metal–organic nanotubes based on rings or helical chain units

Three coordination polymers {[Mn(bte)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (1), {[Mn(btp)(NO₂-1,3-bdc)(H₂O)]·2H₂O}_n (2), and {[Mn(btb)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (3) (bte, 1,2-bis(1,2,4-triazol-1-yl)ethane; btp, 1,3-bis(1,2,4-triazol-1-yl)propane; btb, 1,4-bis(1,2,4-triazol-1-yl)butane, NO₂-1,3- H₂bdc, 5-nitroisophthalic acid) were synthesized by combination of bte, btp, and btb, conformationally flexible ligands with different spacer lengths, and the rigid [NO₂-1,3-bdc]^2?. In 1, two [NO₂-1,3-bdc]^2? anions link adjacent [Mn₂(bte)₂] rings to give an independent, 1-D metal–organic nanotube (MONT). The structure of 2 is an undulating 2-D (4,4) network. In 3, the combination of a [Mn(btb)]_n single helical chain and two [Mn(NO₂-1,3-bdc)]_n linear chains assemble an intriguing independent, 1-D MONT. An interesting structural feature of 1 and 3 is that the nitro groups of each 1-D MONT interpenetrate into two adjacent 1-D MONTs to form a 1-D → 2-D interdigitated array. 3-D architectures in 1 and 3 are assembled via hydrogen bond interactions. The luminescent properties and thermal stabilities of 1, 2, and 3 were investigated.     

A Novel Three-Dimensional Network Isophthalato-Bridged Lanthanide Complex: {Ln[C6H4(COO−)2-1,3](CH3COO−)(H2O)2}·H2O

The three-dimensional network of lanthanide (III) complexes with isophthalato (IPT) ligand, (Eu[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O 1 and {Sm[C₆H₄(COO^?)₂-1,3](CH₃COO^?) (H₂O)₂} H₂O 2, has been prepared by the hydro(solvo)thermal reaction of Eu(C1O₄)₃·6H₂O or Sm(C1O₄)₃·6H₂O, 1,3-dicyanobenzene and acetic acid in the presence of ethanol and H₂O. In the reaction, 1,3-dicyanobenzene was hydrolyzed to give IPT ligand. Single crystal x-ray analysis revealed that crystals 1 and 2 are isomorphous with the isostructural {M[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O unit. In 1 and 2, IPT acts as a bridging ligand to connect three adjacent metal atoms, forming a network like an undulating sheet paralleling the bc plane. The carboxylate from acetate bridges two adjacent metal atoms in a tridentate mode between the different sheets to extend the structure into a three-dimensional network.     

Mixed-ligand lanthanide complexes constructed by flexible 1,3-propanediaminetetraacetate and rigid terephthalate

Abstract

Coordination polymers (CPs) of mixed-ligand lanthanide complexes [Ln₂(1,3-pdta)(TPA)(H₂O)₂]_n·nH₂O [Ln?=?La, 1; Ce, 2; Pr, 3; Nd, 4] (1,3-H₄pdta = 1,3-propanediaminetetraacetic acid; H₂TPA?= terephthalic acid) were hydrothermally synthesized with flexible 1,3-pdta and rigid TPA ligands. Moreover, lanthanide propanediaminetetraacetates [Ln(1,3-Hpdta)(H₂O)]_2n·nH₂TPA·xH₂O [Ln?=?Sm, 5; Gd, 6] with multi-layered structures were also obtained. In 1–4, both 1,3-pdta and TPA coordinate with lanthanide ions through carboxyl oxygen and nitrogen atoms. In 5 and 6, only 1,3-Hpdta coordinates with the central lanthanide ion, where one nitrogen atom in 1,3-Hpdta is protonated, and TPAs are crystallized as H₂TPA with the central multi-layered structures of [Ln(1,3-Hpdta)(H₂O)]_2n through very strong hydrogen bonds [2.504(4) Å]. Solid-state ¹³C NMR analysis of 1 revealed the coordination of carboxyl groups. However, the methylene groups of 1,3-pdta showed an obvious upfield shift, which can be attributed to the effects of the phenyl ring in TPA ligand. The successful synthesis of these mixed-ligand lanthanides provides a rational design of such lanthanide CPs with flexible and rigid ligands.     

Investigation on the thermal decomposition some heterodinuclear NiII-MII complexes prepared from ONNO type reduced Schiff base compounds ( M II=ZnII, CdII)

N,N′-bis(salicylidene)-1,3-propanediamine (LH₂), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH₂), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH₃), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH₂) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH₂) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH₄ (L^HH₂, LDM^HH₂, LOH^HH₂, LAC^HH₂ and LACDM^HH₂). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF media. The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of only one complex were obtained and its structure determined using X-ray diffraction, NiLAC^H·CdBr₂·DMF₂, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX₂·DMF₂] structure (ligand=L^H2−, LDM^H2−, LOH^H2−, LAC^H2−, LACDM^H2−, M=Zn^II, Cd^II, X=Br⁻, I⁻). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition at this temperature.     

Three double- or triple-stranded chains constructed from different cobalt(II) salts and a flexible bis-triazole ligand

Three coordination compounds, {[Co(btrp)₂(H₂O)₂]?·?NO₃?·?H₂O} _n (1), {[Co(btrp)₂(H₂O)₂]?·?H₂O?·?2H₂btc} _n (2), and {[Co(btrp)₃]?·?2ClO₄} _n (3) (btrp?=?1,3-bis(1,2,4-triazol-1-yl)propane; H₃btc?=?benzene-1,3,5-tricarboxylic acid), have been prepared via solvothermal method and characterized by single-crystal X-ray diffraction and elemental analyses. Compound 1 possesses a 1-D double-stranded chain composed of ribbons of 20-membered cycles. Binuclear water clusters link adjacent nitrate anions to form a 1-D supramolecular helix in the structure. Compound 2 has a 1-D double-stranded chain wherein free H₂btc ligands constitute 1-D negative chains through classical hydrogen-bonding interactions (O–H?···?O). Compound 3 exhibits a triple-stranded 1-D chain. For 1–3, 3-D supramolecular structures are consolidated by interchain weak hydrogen-bonding interactions as well as electrostatic interactions.     

Syntheses,Crystal Structures,and Magnetic Properties of Two Cobalt Coordination Polymers Constructed From 1,3‐Bis(2,4‐dicarboxyphenyl) Benzene and Bis(imidazole) Linkers

Abstract. The 3D cobalt(II) coordination polymers [Co_1.5(HDDB)(1,4‐bib)_1.5(H₂O)]_n ( 1 ), and {[Co₂(DDB)(1,3‐bib)₂(μ₂‐H₂O)] · H₂O}_n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H₄DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (6³)₄(6⁵ · 8⁸ · 10²) net, and complex 2 is an unprecedented dinuclear [Co₂(COO)(μ₂‐H₂O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(3² · 4³ · 5⁴ · 6³ · 7 · 8²) net. Additionally, the magnetic properties of 2 were investigated.     

Cd(II) MOFs based on cadmium/carboxylate units and 4,4′-bis(benzoimidazol-1-yl)bibenzene: syntheses,structures, and luminescence

Solvothermal reactions of CdCl₂·2.5H₂O with 4,4′-bis(benzoimidazol-1-yl)bibenzene (bimbb) and 1,4-benzenedicarboxylic acid (1,4-H₂bdc), 4,4′-biphenyldicarboxylic acid (4,4′-H₂bpdb), 5-methyl-1,3-benzenedicarboxylic acid (5-Me-1,3-H₂bdc), or 1,3,5-benzenetricarboxylic acid (H₃btc) afforded four 3-D metal–organic frameworks, {[Cd₂(1,4-bdc)₂(bimbb)₂]·H₂O}_n (1), {[Cd₂(4,4′-bpdb)₂(bimbb)(H₂O)₂]} _n (2), [Cd₂(5-Me-1,3-bdc)₂(bimbb)] _n (3), and {[Cd₃(btc)₂(bimbb)(H₂O)₂]·2H₂O} _n (4). Complexes 1–4 were characterized by elemental analysis, IR spectroscopy, powder X-ray powder diffraction, and single-crystal X-ray diffraction. 1 possesses a 3-D framework with 2-D undulated (8,4) layers which are further connected by bimbb pillars. 2 forms a 3-D pillared-layer framework constructed through 2-D undulated (4,4) layers and bimbb pillars. 3 has 1-D ribbons of [Cd₄(5-Me-1,3-bdc)₄] _n which are linked by bimbb to form a 3-D structure. 4 exhibits a 3-D pillared-bilayer framework consisting of (6,3) double-decker [Cd₉(btc)₆(μ-OH₂)₆] _n layers and bimbb pillars. The Schläfli symbols for the four frameworks are (4²·6³·8)(4²·6⁵·8³) (1), (4⁴·6⁶) (2), (4⁴·6²)(4⁶·6⁴) (3), and (6³)(6¹⁰) (4). The photoluminescent properties of 1–4 were also investigated.     

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO₂(C₆H₄N₂O₄)₂(H₂O)], and 3, [Th(C₆H₄N₂O₄)₄(H₂O)₅]·H₂O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO₂(C₆H₄N₂O₄)₂(H₂O)], and 4, [Th(C₆H₅N₂O₄)(OH)(H₂O)₆]₂·2(C₆H₅N₂O₄)·3H₂O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO₂(C₁₃H₁₅N₄O₂)₂(H₂O)]·2H₂O and 6, [UO₂(C₁₁H₁₁N₄O₂)₂(H₂O)]·4.5H₂O feature 1,3-bis(4-N¹-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N¹,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO₂(C₁₁H₁₁N₄O₂)₂(CuCl₂)(H₂O)]·2H₂O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO₂]²⁺ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.     

Cd(II) and Cu(II) coordination polymers based on a multidentate N-donor ligand: syntheses,crystal structures,optical band gaps,and photoluminescence

Four Cd(II)- and Cu(II)-containing coordination polymers (CPs) based on a multidentate N-donor ligand and varied dicarboxylate anions, [Cd(3,3′-tmbpt)(p-bdc)]·2.5H₂O (1), [Cd(3,3′-tmbpt)(m-bdc)]·2H₂O (2), [Cu(3,3′-tmbpt)(m-bdc)]·H₂O (3), and [Cu(3,3′-tmbpt)(p-bdc)]·2H₂O (4), where 3,3′-tmbpt = 1 ? ((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, p-H₂bdc = 1,4-benzenedicarboxylic acid, and m-H₂bdc = 1,3-benzenedicarboxylic acid, have been prepared hydrothermally. The structures of the compounds were determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra and elemental analyses. Compound 1 exhibits a 3-D twofold interpenetrating framework with a 6⁵·8 CdSO₄ topology. Compound 2 is a 2-D layer containing meso-helical chains with a 4⁴·6² sql topology. Compound 3 shows a 1-D → 3-D interdigitated architecture while 4 displays a 2-D → 3-D interdigitated architecture. The structural differences of the compounds indicate that the dicarboxylate anions and the central metal ions play important roles in the resulting structures of CPs. Optical band gaps and solid-state photoluminescent properties have also been studied.     

A polyoxoniobate constructed from Lindqvist-type hexaniobates and copper coordinated cations

A new organic–inorganic hybrid polyoxoniobate [Cu(1,3-dap)₂(H₂O)][(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]?·?4(1,3-dap)·20H₂O (1) (1,3-dap?=?1,3-diaminopropane) has been synthesized by the diffusion method and structurally characterized by elemental analyses, infrared spectrum, ultraviolet spectroscopy, and single crystal X-ray diffraction. Crystal structure analysis reveals that 1 consists of a dimeric dumbbell anion [(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]^2?, a copper coordinated cation, four 1,3-dap ligands and 20 crystal water molecules. Neighboring units are combined via hydrogen bonds forming a 3-D supramolecular framework.     

Studies on mono- and dinuclear bisoxime copper complexes with different coordination geometries

Two new mono- and dinuclear Cu(II) complexes, namely [CuL¹]·0.5H₂O (1) and [(Cu₂(L²)₂)(DMF)]·0.5DMF (2) (H₂L¹ = 1,2-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)]methylene-aminooxy}ethane; H₂L² = 1,3-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)] methyleneaminooxy}propane), have been synthesized and characterized by X-ray crystallography. The unit cell of complex 1 contains two crystallographically independent but chemically identical [CuL¹] molecules and one crystalline water molecule, showing a slightly distorted square-planar coordination geometry and forming a wave-like pattern running along the a-axis via hydrogen bonding and π···π stacking interactions. Complex 2 has a dinuclear structure, comprising two Cu(II) atoms, two completely deprotonated phenolate bisoxime (L²)²⁻ moieties (in the form of enol), and both coordinated and hemi-crystalline DMF molecules. Complex 2 has square-planar and square-pyramidal geometries around the two copper centers, whose basic coordination planes are almost perpendicular and form an infinite three-dimensional supramolecular network structure involving intermolecular C–H···N, C–H···O, and C–H···π(Ph) hydrogen bonding and π···π stacking interactions of neighboring pyrazole rings.     

3D sandwich-like frameworks constructed from silver chains: synthesis and crystal structures of six silver(I) coordination complexes

The reaction of AgNO₃ with combinations of 4,4′-bipyridine (bpy), 1,2-di(4-pyridyl)ethane (dpe), 1,3-bis(4-pyridyl)propane (bpp), succinic acid (H₂su), terephthalic acid (H₂tp), 2,2′-diphenylaminedicarboxylic acid (H₂dpadc), and naphthaleneacetic acid (Hnaa) in aqueous alcohol at room temperature produces block-like crystals of [Ag₃(bpy)₃](su)·10H₂O, [Ag₂(bpy)₂](tp)·6H₂O, [Ag₂(dpe)₂(H₂O)₂](dpadc)·H₂O, [Ag₆(dpe)₆(H₂O)₄](tp)₃·12H₂O, [Ag(bpp)](naa), and [Ag₂(bpp)₂](dpadc)·6H₂O. All six compounds consist of 1D infinite silver-bpy/dpe/bpp cationic chains, interspersed with organic carboxylate anions that provide charge compensation in the crystal structures. The lattice water molecules are situated among the framework of the crystal structure and show rich hydrogen-bonding interactions {except for [Ag(bpp)](naa)}, which help to orientate of the organic carboxylate anions in the crystal packing.