Interesting Copper(I) Coordination Polymers of Heterocyclic Monothioether Ligand Containing Long S-Hexadecyl Chain: Syntheses,Structures and Properties

Two structurally related heterocyclic monothioether ligands containing long S-alkyl(hexadecyl) chain, 2-methyl-5-(1-n-hexadecylsulfanyl)-1,3,4-thiadiazole (L ¹ ) and 2-(1-n-hexadecylsulfanyl) pyridine (L ² ), have been designed, and two CuI complexes with these ligands, [Cu₄I₄(L¹)₂] _n (1) and [Cu₄I₄(L²)₂] _n (2), have been synthesized and characterized by IR, elemental analysis, UV–vis spectra, thermal analysis and X-ray diffraction analysis. Single-crystal X-ray analyses show that two complexes are all 1-D coordination polymer with a double-stranded stair CuI-chain. Optical diffuse-reflection spectra results complex 1 and 2 have the properties of the semiconductor.     

Hydrothermal Synthesis, Characterization of Mn(II) and Cd(II) Coordination Polymers Assembled from Semi-Rigid Oxo-Bridged Carboxylate and N-Donor Ligands

Two new metal–organic coordination polymers containing Mn(II) and Cd(II) with oxo-bridged and N-donor ligands, [Mn(oba)(2,2′-bipy)] _n (1) and {[Cd(oba)(bib)]·H₂O} _n (2) [2,3′-H₂oba = 2-(3-carboxyphenoxy)benzoic acid, 2,2′-bipy = 2,2′-bipyridine, and bib = 4,4′-bis(2-methylimidazole-1-ylmethyl)biphenyl], have been prepared and characterized by elemental analysis, Fourier infrared spectroscopy, and X-ray diffraction. Complex 1 has a 3D supramolecular network constructed from 1D zigzag chain via π–π stacking interactions. Complex 2 features 1D ladder-like chain which consists of 1D helical arrays and bib pillars. Moreover, photoluminescence properties of the bib ligand and the Cd(II) complex were investigated.     

Concomitant Crystallization of Copper(II) Sachharinato Complexes with 2-methylpyrazine as a Monomer and an One-dimensional Polymer: Syntheses,Crystal Structures,Spectroscopic and Thermal Properties

The reaction of [Cu(sac)₂(H₂O)₄] · 2H₂O with 2-methylpyrazine (mpyz) leads two complexes, concomitant crystallization of a mononuclear complex [Cu(sac)₂(mpyz)(H₂O)₂] (1) and a polymeric complex [Cu(sac)₂(μ-mpyz)]_n (2). Both complexes have been characterized by elemental analyses, magnetic measurements, FT-IR and ESR, TG-DTA and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that complex 1 consists of discrete molecules in which the copper(II) ions exhibits a square-pyramidal coordination geometry. The individual molecules of 1 are connected into a hydrogen-bonded chain structure, which is further assembled to form a three-dimensional network by π–π stacking interactions. Complex 2 is an 1D coordination polymer in which copper(II) centers are bridged by the mpyz ligand. The chains are further assembled to form two-dimensional frameworks by π–π and C–H···π stacking interactions.     

Syntheses, Structures and Properties of Two Metal–Iodide Polymers Based on a Flexile N-Donor Ligand

Two novel metal–organic frameworks based on 1,3-bis(imidazol-1-ylmethyl)-benzene (m-bix), namely [(Cu₄I₄)(bix)₂] _n (1) and [HgI₂(bix)] _n (2) have been synthesized and characterized by IR, elemental analysis, thermogravimetry, luminescent properties and X-ray crystallography. The structure of compound 1 exhibits a 1D metal–organic chain composed of Cu₄I₄ clusters and m-bix ligands, and such chains are further united together to generate a 3D supramolecular structure through inter-chain π···π interactions. In compound 2, the HgI₂-bix chains interact each other to form a layer structure through π···π interactions, then the layers are extended to 3D supramolecular architecture through intermolecular C–H···π interactions.     

Structural and Magnetic Properties of One-Dimensional Squarate Bridged Coordination Polymers Containing 2-Aminomethylpyridine Ligand

Three novel one-dimensional (1D) coordination polymers with general formula {[M(μ-sq)₂(amp)₂]·H₂O}_n [M=Cu(II) (1), Zn(II) (2)] and [Cd(μ-sq)₂(amp)₂]_n (3) [sq: Squarate; amp:2-aminomethylpyridine] have been prepared and spectroscopically studied. Each metal (II) ion in 1–3 is octahedrally coordinated by two sq and two amp ligands. The amp ligands are N,N′ coordinated, while the sq ligands bridge the metal centers forming 1D linear chain structure. The individual chains are linked by O–H···O hydrogen bonds involving the hydrogens of water molecules (1–2), amino hydrogens and squarate O atoms (1–3). The hydrogen bonded layers are further assembled into three-dimensional supramolecular networks by weak aromatic π–π interactions. EPR results indicate that the ground state of the paramagnetic electron in 1 and Cu²⁺ doped complexes 2–3 is d_{x² - y²} d_{{x^{2} - y^{2} }} . Magnetic measurements reveal that complex 1 shows paramagnetic behavior.     

Synthesis, Characterization and Thermogravimetric Analysis of Two Dicyclohexyl-18-crown-6 Pd, Pt Isomaleonitriledithiolate Complexes

Two organic–inorganic hybrid dicyclohexyl-18-crown-6 complexes, [K(DC18C6-B)]₂[Pd(i-mnt)₂] (1) and [K(DC18C6-A)]₂[Pt(i-mnt)₂] (2) (DC18C6-A=cis-syn-cis-dicyclohexyl-18-crown-6, A isomer; DC18C6-B = cis-anti-cis-dicyclohexyl-18-crown-6, B isomer; i-mnt=1,1-dicyanoethene-2,2-dithiolate, isomaleonitriledithiolate), were synthesized by the reaction of dicyclohexyl-18-crown-6 with K₂(i-mnt) and PdCl₂ or K₂PtCl₄ respectively. These were characterized by elemental analysis, FT–IR, UV–Vis spectroscopy and single crystal X-ray diffraction. In complex 1, two [K(DC18C6-B)]⁺ complex cations and one [Pd(i-mnt)₂]²⁻ complex anion formed a neutral molecule through two K–N coordination bonds. The resulting molecule adopted a 1D chain arrangement via K N weak interactions. Complex 2 showed a 1D chain-like structure that was assembled by two [K(DC18C6-A)]⁺ complex cations and one [Pt(i-mnt)₂]²⁻ complex anion through N–K–N interactions. An erratum to this article can be found at     

Hydrothermal Synthesis of Metal–Organic Coordination Polymers Constructed from Asymmetric Semi-rigid V-shaped Dicarboxylate and Nitrogen-Contained Mixed Ligands

Three new coordination polymers, [Ni(2,4′-oba)(1,10-phen)] _n (1), {[Ni (2,4′-Hoba)₂(4,4′-bipy)(H₂O)₂]·2H₂O} _n (2) and [Zn(2,4′-oba) (4,4′-bipy)] _n (3) (2,4′-H₂oba = 2-(4-carboxyphenoxy)benzoic acid, 1,10- phen = 1,10-phenanthroline, and 4,4′-bipy = 4,4′-bipyridine) have been obtained by hydrothermal synthesis. The framework structures of these polymeric complexes have been determined by single-crystal X-ray diffraction studies. Complex 1 exhibits double-helical chains formed by π–π stacking interactions from the phenyl rings of the 1,10-phen ligands. Complex 2 forms a two-dimensional supramolecular architecture directed by hydrogen bonding. Complex 3 exhibits a three-dimensional structure; Schl?fli symbol of {4⁴·6¹⁰·8}. The luminescent property of compound 3 is discussed.     

Syntheses, Structures, and Luminescent Properties of Two Novel Coordination Polymers with Poly-Carboxylate and N-Heterocyclic Ligands

Two novel metal–organic coordination polymers {[Pb(CIPT)(1,4-BDC)]·2H₂O} _n 1 and {[Zn₂(IPDT)₂(1,4-BDC)₂(H₂O)].3H₂O} _n 2 [CIPT = 2-(3-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,4-BDC = terephthalic acid, IPDT = 4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)-2,6-dimethoxyphenol] were obtained from hydrothermal reaction and characterized by elemental analysis, thermogravimetric (TG) analysis, IR and single-crystal X-ray diffraction. Both of the two coordination polymers exhibit one-dimensional (1D) infinite chain structures through non-covalent interactions, and the existence of hydrogen bonds interactions lead the 1D chain to 2D layer structures. It is noteworthy that the existence of hydrogen bonds reinforces the structural stability of the complexes 1 and 2, which can be proved by TG analysis. The photoluminescent study of coordination polymer 1 shows that it exhibits fluorescent emission band at 637 nm, which is red-shifted by 46 nm relative to the free ligand CIPT.     

Ring-opening polymerization of (CH3)2Si[CpMo(CO)3]2, a molecule with an –Si(CH3)2– bridge between two cyclopentadienyl ligands

The (CH₃)₂Si[CpMo(CO)₃]₂ complex (1) was synthesized and used to explore ring-opening polymerization (ROP) as a method to prepare high molecular weight polymers containing Mo–Mo bonds along their backbones. Attempts to initiate ROP of 1 using n-BuLi or PtCl₂ did not yield any polymers. The X-ray crystal structure of 1 shows that the Si center is not strained, and it is suggested that no ROP occurred because 1 is less strained than other organometallic ROP monomers, such as the silicon-bridged ferrocenophanes. Thermal ROP (TROP) of 1 was successful and yielded a polymer (M _w = 210,000 g mol⁻¹) containing both Mo–Mo single bonds and Mo≡Mo triple bonds. When CO_(g) is passed over the polymer in the solid state, the Mo≡Mo triple bonds are converted to Mo–Mo single bonds. Attempts to increase the yield of the TROP polymer by increasing the reaction times led to polymer decomposition. The decomposition is likely caused by the weakness of the Mo–Mo bond, cleavage of which causes the polymer to degrade.     

A Mixed Valence Copper Cyanide 3D-supramolecular Coordination Polymer Containing 1,10-Phenathorline Ligand as a Potential Antitumor Agent, Effective Catalyst and Luminescent Material

The structure of the 3D-supramolecular coordination polymer (SCP) _∞³{[Cu^Ι(CN)·2(phen)·Cu^ΙΙ(CN)₂·(phen)]·5H₂O}, 1 contains the [Cu^Ι(CN)·2(phen)], [Cu^ΙΙ(CN)₂·(phen)] molecular complexes and five water molecules which are connected with each other by hydrogen bonds. The most intriguing feature in the structure of 1 is the unusual supramolecular interactions, including hydrogen bonds which involve the terminal cyanide and the phenanthroline (phen) ligands and π–π stacking which generate a unique 3D-supramolecular architecture in the solid state. The emission spectrum of 1 displays a band centered at 420 nm which was assigned to S_o-T transition in the CuCN fragments. This band suffers a shift to longer wavelength by about 30 nm than that of CuCN itself. The emission bands at 435, 450, and 475 correspond to the close laying π–π* transitions of the coordinated phen. The main band at 435 nm exhibits a red shift than that of phen by about 70 nm which makes it attractive as luminescent sensor. Also, the SCP 1 was used as heterogeneous catalyst for the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant. The reaction is first order with respect to the MY dye. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine the in vitro antitumor activity of the SCP 1 on human breast cancer cell line, MCF7. The cytotoxicity of the SCP 1 is more efficient than that of the Doxorubicin (DOX) drug. The thermal stability has been also investigated.     

Two Novel Bimetallic Cyano-Bridged Coordination Polymers Containing the 2,2′-(Ethylenedioxy)bis (Ethylamine): Syntheses,Structural, Thermal and Magnetic Properties

Two new cyano bridged bimetallic polymeric complexes, [Ni(edbea)Ni(CN)₄]·1/2H₂O (1) and [Cu(μ-edbea)(μ-CN)₂ Ni(CN)₂]·H₂O (2) [edbea = 2,2′-(ethylenedioxy)bis(ethylamine)] have been synthesized by adding metal chloride (M = Ni^II and Cu^II), and edbea into [Ni(CN)₄]²⁻ in water–ethanol solution and then characterized by elemental analysis, infrared (IR) and electron paramagnetic resonance (EPR) (for only complex 2) spectra, variable temperature magnetic measurement, and thermal gravimetric analysis. The X-ray diffraction crystal structure of complex 2 shows a 2D polymeric chain –edbea(N5,O1)–Cu1–N1C1–Ni(CN)2–C4N6–Cu1–(N6,O2) edbea– in which the Cu^II centers are linked by two cyano and one edbea. The powder EPR spectrum of the complex 2 has shown that Cu^II ions are located in rhombically distorted octahedral sites. The magnetic properties of the coordination polymers have been studied in temperature range of 15–300 K. The magnetic behaviors investigation of complexes 1 and 2 indicated the presence of a very weak antiferromagnetic interaction.     

A Novel Bimetallic Chain Based on [Mo(CN)<Subscript>8</Subscript>]<Superscript>3−</Superscript> and Yb<Superscript>3+</Superscript> Ions as Building Blocks in Which Containing Many Intriguing Structural Features

A novel Mo^V–Yb^III bimetallic chain, {[Yb^III(bpy)₂(DMF)(H₂O)][Mo^V(CN)₈]·0.5bpy·4.5H₂O}_n (1) (DMF = N,N′-dimethylformamide; bpy = 2,2′-bipyridine), has been constructed by the reaction of [Mo(CN)₈]³⁻ with Yb³⁺ and 2,2′-bipyridine. Complex 1 is confirmed as a host–guest supramolecular structure by X-ray structural analysis. The neighboring chains interact with each other with two types of hydrogen bonds and two types of π···π interactions. Thus complex 1 has a unique 3D network. Magnetic analysis of 1 indicates the presence of a strong Yb^III single-ion effect owing to spin–orbital coupling within this system.     

An Infinite Sandwich-Type Copper (I) Coordination Polymer Containing 2-D Double Chains Layers Structure Intercalated with the Terephthalic Acid Layers

A high-quality single crystal structure of a new coordination polymer having the formula [Cu₂(μ-SO₄)(μ-bpy)₂ · (H₂ta)] _n (1) (H₂ta = terephthalic acid; bpy = 4,4′-bipyridine) was obtained when the in situ reaction of CuSO₄ · 5H₂O with H₂ta and bpy ligands under solvothermal conditions (H₂O/ethanol) were carried out. The results of the structural characterization show that Cu(I) ions are bridged by 4,4′-bipyridine to form infinite 1-D chains, which are further linked through the sulfate groups to form a 1-D double chain structure. The extensive hydrogen-bonding interactions between the sulfate anions and free terephthalic acid molecules have an important effect in generating the 2-D layer structures and finally an infinite 3-D sandwich-type coordination polymer. In addition, the luminescent properties of coordination polymer 1 are also discussed.     

One-Dimensional Cobalt(II) and Zinc(II) Succinato Coordination Polymers with Nicotinamide: Synthesis, Structural, Spectroscopic, Fluorescent and Thermal Properties

Cobalt(II) and zinc(II) succinato (suc) coordination polymers with nicotinamide (nia), {[Co(μ-suc)(H₂O)₂(nia)₂] · 2H₂O} _n (1) and {[Zn(μ-suc)(H₂O)₂(nia)₂] · 2H₂O} _n (2) have been synthesized and characterized by elemental analyses, magnetic moments, IR and TG-DTA. Single-crystal X-ray analyses of 1 and 2 reveal that these complexes are isostructural and crystallize in triclinic space group Complexes 1 and 2 are 1-D coordination polymers, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centers through the carboxylate groups. The 1D chains are further assembled to form 3D networks by strong N–H···O and OW–H···O hydrogen bonds. IR spectra confirm the coordination modes of both suc and nia ligands, while TG-DTA data are in agreement with the crystal structures. Fluorescent analysis in the solid state shows that all complexes display intraligand (π–π*) emissions of nia.     

Metal(II) Nicotinamide Complexes Containing Succinato,Succinate and Succinic Acid: Synthesis,Crystal Structures,Magnetic, Thermal,Antimicrobial and Fluorescent Properties

Four novel divalent transitional metal succinates (suc) with nicotinamide (nia), {[M(μ-suc)(H₂O)₂(nia)₂]·2H₂O} _n [M = Mn (1), Ni (2)], [Cu(suc)(nia)₂] (3) and [Ni(H₂O)₄(nia)₂](suc)·(H₂suc) (4), have been synthesized and characterized by elemental analyses, IR and TG-DTA. X-ray analyses of 2 and 4 reveal that they crystallize in a triclinic space group P[`1]. P\bar{1}. Complex 2 is a 1-D coordination polymer, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centres through the carboxylate groups. 4 contains the [Ni(H₂O)₄(nia)₂]²⁺ complex cations, uncoordinated suc and H₂suc species, which are connected into a two-dimensional layered structure by the combination of N–H⋯O and OW–H⋯O hydrogen bonds. This is one of the scarce examples encountered in coordination chemistry, which contains uncoordinated suc and H₂suc at the same time. The spectroscopic and structural analysis, luminescent and magnetic properties and the antimicrobial activities of the synthesized complexes were investigated.     

Synthesis,Structure and Voltammetric Studies of Copper(II) Polymer with DNA Interaction: The First 1-D Coordination Polymer Alternately Bridged by Oxalate and Oxamidate Ligands

A novel one-dimensional copper(II) complex formulated as [Cu₂(dmaeoxd)(ox)] _n ·nH₂O (dmaeoxd = N,N′-bis[2-(dimethylamino)ethyl]oxamide, ox = oxalate), which represents the first coordination polymer alternately bridged by oxalate and oxamidate ligands, has been synthesized and characterized by elemental analysis, conductivity measurement and IR spectra. The single-crystal X-ray analysis reveals that the [Cu₂(dmaeoxd)]²⁺ building blocks are bridged by oxalate groups to form a neutral 1-D coordination polymer, which involves hydrogen bonds with lattice water molecules and results in a three dimensional supermolecular structure. The voltammetric studies of the copper(II) polymer with DNA interaction are preliminarily investigated.     

Hydrothermal Synthesis and Crystal Structures of Cd(II)-Based 1D Coordination Polymer and Mn(II) Coordination Complex with Mixed N- and O-donor Ligands: [Cd2(4-4′-bpy)2(pa)4]n·0.25(H2O) and [Mn(4-4′-bpy)2(pa)(H2O)3]ClO4·2(H2O)

Two new complexes, [Cd₂(4-4′-bpy)₂(pa)₄] _n ·0.25H₂O (1) (pa = phenylacetate), and [Mn(4-4′-bpy)₂(pa)(H₂O)₃]ClO₄·2H₂O, (2), have been obtained from hydrothermal reaction of Cd(NO₃)₂·4H₂O and Mn(ClO₄)₂·6H₂O with a mixture of the ligands, 2-phenylmalonic acid (2-phmalH₂) and 4-4′-bipyridine (4-4′-bpy). The pa is formed in situ by decarboxylation of phenylmalonic acid. These complexes have been characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis and single-crystal X-Ray diffraction. The Cd(II) center is seven-coordinate and linked via pa ligands to form a binuclear complex in the asymmetric unit of 1. A ladder-like 1D chain of binuclear units is formed by Cd(II)–N coordination bond through 4-4′-bpy ligands. Complex 2 consists of a mononuclear manganese center based on a distorted octahedral geometry and exhibits a supramolecular structure containing hydrogen bonds and extensive π···π and C–H···π interactions.     

Synthesis, crystal structures, and electronic spectra of (1,8-naphthyridine)Re(CO)3Cl and [(1,8-naphthyridine)Cu(DPEPhos)]PF6

Two 1,8-naphthyridine (nap) metal complexes (nap)Re^I(CO)₃Cl (1) and [(nap)Cu^I(DPEPhos)]PF₆ (2) were synthesized and characterized by NMR-, emission, and absorption spectroscopy, elemental analysis, mass spectrometry, and X-ray structural analysis. In both complexes, the nap ligand coordinates with both N atoms to the metal centre in a bidentate manner. 1 and 2 exhibit a broad phosphorescence in solid state at T = 300 K, which is completely quenched in solution at r.t. In addition, the gas-phase structures of both complexes were optimized at the B3LYP/6-31G(d,p) level of theory.     

Complexes Containing N-(2-hydroxyethyl)-ethylenediamine with Tetracyanometallate (II): Synthesis, IR Spectra, Thermal Behavior, Crystal Structure, Magnetic Properties and Catalysis

Two novel cyano-bridged Ni²⁺ and Cu²⁺ compounds, {[M²⁺(hydeten)₂(μ-CN)₂Ni(CN)₂] _n , M²⁺ = Ni²⁺ (c1) and Cu²⁺ (c2), N-(2-hydroxyethyl)-ethylenediamine (hydeten), were prepared and characterized by elemental analysis, IR spectroscopy and thermoanalytical measurements. The one-dimensional polymeric structure of c2, which was determined by X-ray diffraction techniques, was formed with a 2,2-TT-type chain, –Cu(hydeten)₂-NC-Ni(CN)₂-CN-Cu(hydeten)₂-, linkages. Also, while the EPR spectra and magnetic properties of complexes c1 and c2 with [Ni(hydeten)₂Pd(CN)₄] (c3) and [Cu(hydeten)₂Pd(CN)₄] (c4) [Karadağ, Z Kristallogr 222:39, 2007] were investigated, the catalytic activity of c3 and c4 was studied. The EPR spectra of c2 and c4 showed that Cu²⁺ was located in tetragonal distorted octahedral sites (D _4h ) and the ground state of the paramagnetic electron was d _{x² - y²} d_{{ x^{2} - y^{2} }} . The magnetic behavior exhibited weak antiferromagnetic interactions in all the complexes. Also, the catalytic properties of c3 and c4, which were assigned with Suzuki and Heck coupling reactions, showed that they did not have catalytic effects.     

Synthesis, Structure and Cyclic Voltammetry Studies of a 2D Sheet-like μ3-Hydroxyl- and μ2-, μ4-Oxamidato-Bridged Copper(II) Complex

A novel 2D sheet-like copper(II) complex formulated [Cu₆(trans-oxen)₃(μ₃-OH)₂(H₂O)₂]_n-(ClO₄)_4n^.2nH₂O (1), where H₂oxen is N,N’-bis(2-aminoethyl)oxamide, has been synthesized and characterized by elemental analysis, IR and UV–visible spectroscopy, and single-crystal X-ray diffraction. 1 crystallizes in triclinic space group P-1 with crystallographic data: a = 10.299(2) ?, b = 10.833(2) ?, c = 11.781(2) ?, α = 69.95(3)°, β = 81.10(3)°, γ = 62.44(3)°, and Z = 2. In the crystal structure, the cation [Cu₆(trans-oxen)₃(μ₃-OH)₂(H₂O)₂]_n⁴ⁿ⁺ exhibits a two-dimensional sheet-like structure for Cu(II) ions bridged both by trans-oxen and hydroxyl groups. Each Cu(II) ion is located in a slightly distorted square-pyramidal environment. The hydroxyl group bridges three [Cu(oxen)Cu]²⁺ dications in which one oxen²⁻ is μ₂-bridge while the other two act as never before reported μ₄-bridge. Perchlorate anions and H₂O molecules are inserted between the sheets and bridge the 2D cations via N–H···O and O–H···O hydrogen bonds to form an infinite three-dimensional system. The cyclic voltammetric behavior of 1 and the influence of counter ions on structure are preliminarily investigated.