An unusual mixed-valence Cu(I)-Cu(II) 3-D framework

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.     

Crystal structure and fluorescence of a new 2D layered cadmium(II) malate coordination polymer

A new two-dimensional layered cadmium coordination polymer [Cd(D,L-mal)H₂O] _n (H₂mal = malic acid) is solvothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Each Cd(II) centre is surrounded by seven oxygen atoms from three different malate ligands and one coordinated water molecular forming a pentagonal bipyramidal configuration. Furthermore, complex 1 exhibits blue intense photoluminescence property at room temperature.     

Crystal structure,thermal and fluorescent properties of a 1D Cd(II) coordination polymer based on the bis(benzimidazole) ligand

A 1D cadmium (II) coordination polymer {[Cd₂(L)₃Cl₃]·Cl} _n (1) (L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized by the hydrothermal reaction and characterized by elemental analysis, IR, TG, and X-ray single crystal diffraction. Compound 1 crystallizes in the hexagonal system, space group P63/m with a = 15.4857(11) Å, b = 15.4857(11) Å, c = 14.478(2) Å, γ = 120°, V = 3006.8(5) ų, Z = 2. In the structure of complex 1, each cadmium center is hexahedrally coordinated by three chlorine atoms and three nitrogen atoms of three distinct L ligands. A detailed analysis reveals that compound 1 exhibits a 1D chain of beads and the adjacent chains are further linked by C-H…Cl hydrogen bonding to form a 2D supramolecular framework. Furthermore, the solid-state fluorescent property of 1 is investigated at room temperature.     

Crystal structure and fluorescence of a 1D zinc(II) coordination polymer based on a semi-rigid bis(benzimidazole) ligand

A new Zn(II) coordination polymer, {[Zn(npht)(L)_0.5(H₂O)]?H₂O} _n (L = 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H₂npht = 3-nitrophthalic acid) has been hydrothermally synthesized and characterized by elemental analysis, IR, XRPD, and single-crystal X-ray diffraction. The zinc(II) coordination compound exhibits a 1D linear chain, which is further assembled into a 2D supramolecular layer via two modes of classial hydrogen bonding interactions. The fluorescence properties and thermal stability of the complex have been investigated in the solid state.     

Valence-induced assembly of Cu(I)-Cu(II) ions into different discrete coordination architectures by a disk-shaped polypyridyl ligand

The valences of metal ions were found to play key roles in controlling the formation and structures of discrete coordination architectures in a copper and disk-shaped hexa-monodentate ligand system. When Cu(I) and Cu(II) ions react with a polydentate ligand HPDQ, a hexanuclear "double-decker" like discrete "LM(3)M(3)L" coordination architecture (CuI)(6)(HPDQ)(2)(CHCl(3))(8) (complex 1), and a "LM(3)L + LM(3)" composite structure complex (Cu(NO(3))(2))(6)(HPDQ)(3) (complex 2) are formed, respectively.     

A Cu(II) coordination polymer: Crystal structure and therapeutic effect on sepsis

Unique thiocyanate-connected 1-dimensional chain Cu(II) coordination polymer (CP), namely, [Cu₂L¹(μ_1,3-SCN) (η¹SCN)]_n (1), was produced in the existence of KSCN and Cu(NO₃)₂·3H₂O utilizing an underlying multisite N,O donor Schiff base ligand (L¹H₂). [N,N′-bis(3-methoxysalicylidenimino)-1,3-daminopropane] (L¹H₂), the Schiff base ligand is a 1:2 M ratio condensation product of 1,3-diaminopropane and O-vaniline in the methanol medium. The as-created CP 1 has been investigated with various characterization approaches like powder X-ray diffraction (PXRD), fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), -thermogravimetric analysis (TGA) and single crystal X-ray diffraction (SCXRD) analyses. And the mechanism and therapeutic effect of this CP on sepsis was discussed and its specific mechanism was also assessed. First of all, for the infected animals, their survival rate was recorded after the bacterial infection and treatment of complex. Besides this, utilizing the enzyme linked immunosorbent assay (ELISA) assay, the inflammatory cytokines levels that released into plasma were determined after the exposure of compound.     

1D coordination polymers of Cu(II) and Cu(II) dimers with a dicyanomethanide ligand

Several new 1D coordination polymers have been synthesised using the anionic ligand carbamoyldicyanomethanide, C(CN)₂(CONH₂)⁻ (cdm). The polymeric complexes [Cu(cdm)₂(py)₂]·2MeOH (1), [Cu(cdm)₂(4-Etpy)₂]·2MeOH (2), [Cu(cdm)₂(3,5-Me₂pzH)₂]·2MeOH (3) and [Cu(cdm)₂(3-HOCH₂py)₂]·2MeOH (4) (py = pyridine; 3,5-Me₂pzH = 3,5-dimethylpyrazole) contain Cu(II) atoms bridged by μ₂-(N,N′) cdm ligands between equatorial and axial coordination sites. The use of monodentate co-ligands brings about polymeric products, in contrast to the use previously of chelating co-ligands which facilitate the formation of discrete products. These 1D polymeric complexes are connected by hydrogen bonding between the amide functionalities and the lattice solvent. In the structures of 3 and 4 the neutral ligands also contain hydrogen bond donor groups that supplement the amide ring motif. Two other complexes have been obtained that are polymeric chains of alkoxide-bridged Cu(II) dimers. The complexes [Cu(cdm)(MeO)(2-amp)] (5) and [Cu(cdm)(dmap)] (6) (2-amp = 2-(aminomethyl)pyridine and dmap = dimethylaminopropoxide) are remarkably similar despite the different ligands that they contain. Bridging between dimers is via μ₂-(N,O) cdm ligands, consequently altering the nature of the hydrogen bonding between adjacent chains compared to the simple polymeric species 1–3.     

Crystal structure and fluorescent properties of a 2D cadmium coordination polymer

A new 2D cadmium(II) coordination polymer {[Cd(MBD)(L)]·(H₂O)₂} _n (1) (H₂MBD = 5-methoxycarbonyl-benzene-1,3-dicarboxylic acid, L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized, in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during the synthesis. In the structure of complex 1, each cadmium center is octahedrally coordinated by four O atoms from three carboxylate groups and two N of distinct L ligands. A detailed structural analysis reveales that compound 1 exhibits a unique 2D binodal (3,5)-connected (4².6⁷.8)(4².6) topology structure. Furthermore, the 2D layer is extended into a 3D network through π-π stacking interactions. The solid-state fluorescence properties of 1 are investigated at room temperature.     

Crystal structure and magnetic properties of Co(II) coordination polymer with CsCl-like topology

One Co(II) coordination polymer with 4-hydroxypyridine-2,6-dicarboxylic acid (H₃L)-[Co_1.5L(H₂O)₄]_n (1) has been fabricated under hydrothermal condition through reaction of Co(OH)₂ and H₃L with mole ratio of 1?:?1. Single-crystal X-ray diffraction analysis reveals that 1 crystallizes in triclinic space group Pī with a 1-D stair-like structure and rich hydrogen bonding interactions expand the 1-D structure to a CsCl-like 8-connected topology. Magnetic properties of 1 have been studied showing antiferromagnetic exchange interaction between Co(II) ions.     

A new 1D chiral metal-organic coordination polymer constructed by Cu(II) with L-3-Cyanophenylalanine

A new 1D chiral metal-organic coordination polymer [Cu(Cphe)₂] · 3H₂O (I) (HCphe = L-3-Cyanophenylalanine) has been synthesized in an aqueous solution and characterized by elemental analysis, thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD), infrared spectroscopy (IR) and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic space group P2₁. The adjacent copper(II) atoms are linked by Cphe ligands to form a 1D zigzag chain, which is further connected via strong hydrogen bonds to form a 3D supramolecular framework. The unit cell parameters for I are: a = 12.0201(8), b = 6.1495(4), c = 14.8576(10) Å, β = 94.1720(10)°, V = 1095.00(13) ų, and Z = 2.     

Synthesis,structure, and properties of a new 3D hydrogen-bonded porous coordination polymer

A new coordination polymer, [Cd(HMal)(Bipy)(H₂O) · 2H₂O (I) (H₃Mal is malic acid, Bipy is 4,4′-bipyridine), has been synthesized from H₃Mal and Bipy under hydrothermal conditions and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C₁₄H₁₆N₂O₇Cd) crystallizes in the orthorhombic system, space group Ibam. The adjacent cadmium(II) atoms were first interconnected by the HMal ligands via carboxylate oxygen atoms and its adjacent hydroxyl group to generate an infinite zigzag [Cd(HMal)] _n chain, which are further linked by Bipy ligands to form a 2D wavelike layer. Interestingly, the adjacent layers are further connected via hydrogen bonds, giving rise to a 3D porous framework with a cross-sectional area of 11.690 × 9.326 Ų. The unit cell parameters for I: a = 8,457(1), b = 22.030(7), c = 23.066(7) V = 4297(2) ų, Z = 4.     

Crystal structure and magnetic properties of a new heterometallic complex of Pd(II)-Cu(II) with 1-aminoethylidene-1,1-diphosphonic acid

A heterometallic complex of Pd(II)-Cu(II) with 1-aminoethylidene-1,1-diphosphonic (AEDP) acid (C₄H₂₂CuN₂O₁₆P₄Pd) _n (I) is synthesized. Single crystals of compound I are obtained; its crystal structure is determined by X-ray crystallography. The crystals are orthorhombic, space group Pbcn, a = 18.366(3) Å, b = 9.7661(17) Å, c = 20.198(4) Å, V = 3622.8(11) ų, Z = 8, d _x = 2.376 g/cm³. The compound crystallizes as a coordination polymer; the square environment of Pd(II) is formed by nitrogen atoms of amino groups and oxygen atoms of phosphonic groups, while at two non-equivalent copper atoms the octahedral environment is formed by oxygen atoms of phosphonic groups and water molecules. The crystal structure of compound I is characterized by the formation of a branched network of hydrogen bonds. Based on the analysis of the temperature dependence of the magnetic susceptibility it is found that for the heterometallic complex of Pd(II)-Cu(II) with AEDP antiferromagnetic interactions between the paramagnetic centers are dominant.     

New 3-D La(III)-Cu(II)-containing coordination polymer with a high potential porosity

A new 3-D coordination polymer containing both 3d and 4f ions has been designed. Its chemical formula is La2[Cu(pba)]3(H2O)8 . 8H2O. It crystallizes in the quadratic system, space group I41/a with a = 42.4947(9) Angstrom, c = 16.3378(3) Angstrom, and Z = 16. Its crystal structure can be described as a 3-D molecular framework exhibiting a complex network of interconnected zigzaglike channels. Once crystallization water molecules are removed, this compound presents a high potential porosity and a low density. The porosity has been evaluated using Connolly's algorithm.     

Self-assembly of a 1D heterotrimetallic Cu(II)-Sr(II)-Na(I) propeller-like chiral coordination polymer with ferromagnetic interactions

Self-assembly of metalloligand [CuL](-)(H(3)L =N-5-bromosalicylaldehydeglycyl-l-tyrosine) with Sr(2+) and Na(+) results in a 1D micro(2)-carboxylate- and H(2)O-bridged heterotrimetallic chiral coordination polymer [[Na(CuL)(3)Sr(H(2)O)(3)].9H(2)O]](n), which exhibits weak ferromagnetic exchange interactions and optical activity.     

Synthesis and characterization of a new pyrrolidine containing sulfur ligand and the transition metal complexes of Co(II), Ni(II) and Cu(I)

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

A novel three-dimensional coordination polymer constructed with mixed-valence dimeric copper(I,II) units

A novel three-dimensional coordination polymer with a mixed-valence localized copper(I,II) dimeric unit, [Cu2(4-pya)3]n (4-pya = 4-pyridinecarboxylate), was hydrothermally synthesized via a simultaneous in-situa redox and hydrolysis reaction of Cu(II) and 4-cyanopyridine and crystallographically characterized to be a twofold interpenetrated three-dimensional coordination network with a cubic [Cu16(4-pya)12] building unit.     

Electronic structure and properties of camphorimine Cu(I) coordination polymers

The first Cu(I) coordination polymer with an aromatic‐substituted camphorimine ligand [(CuCl)(μ‐Cl) (Cu(H₂NC₆H₄NC₁₀H₁₄O)]_n was obtained from reaction of CuCl with 3‐(4‐aminophenylimino)‐1,7,7‐trimethylbicyclo[2.2.1]heptan‐2‐one (H₂NC₆H₄NC₁₀H₁₄O). The electronic and the surface properties (studied by X‐ray photoelectron spectroscopy) are consistent with two distinct coordination environments for the copper(I) atoms—tetrahedral and linear—for the polymer family [(CuCl)(μ‐Cl){Cu(YNC₁₀H₁₄O)}]_n. DFT band calculations reveal that the highest energy bands are more localized on the copper(I) tetrahedral sites than on the copper(I) linear sites. The redox properties of [(CuCl)(μ‐Cl){Cu(YNC₁₀H₁₄O)}]_n [Y = NMe₂ ( 2b ), NH₂, and H₂NC₆H₄NC₁₀H₁₄O ( 2a )] studied by cyclic voltammetry show that the oxidation potentials of the two copper centers are in fact indistinguishable. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cu(II)-脱乙酰壳聚糖配位聚合物的配位数

IR,ESR和XPS的测试结果表明,脱乙酰壳聚糖(简记CS)膜在铜氨水溶液浸渍过程中Cu(II)既与CS发生配位反应形成Cu(II)-CS配位聚合物,也产生吸附作用。ESR谱示出CuCl~2.2H~2O与Cu(II)-CS膜中的Cu(II)均含有一个单电子,可以利用XPS的Shake-up效应研究Cu(II)-CS配位聚合物的配位数,所得结果为4。又以同样的方法研究Cu(II)-聚乙烯醇(简记PVA)配位聚合物的配位数,发现Cu(II)是以低自旋状态的dsp^2杂化空轨道与PVA的羟基氧配位,其配位数也是4,这与资料所报道的一致,从而间接地验证了此方法研究Cu(II)-CS配位聚合物配位数的可靠性。