Syntheses and characterizations of a novel 1,2,3,4-tetrahydroquinazoline and a Co(III) complex

The 2-furan-2-yl-1,2,3,4-tetrahydroquinazoline-2-carbaldehyde oxime (HL) and complex of tridentate ligand containing oxime, imine, and amine donors resulting from reactions with cobalt(II) salt have been synthesized and characterized by spectral methods (FT-IR, NMR, UV-Vis, mass), elemental analysis, magnetic susceptibility, molar conductivity, and thermal analysis (TG, DTA) techniques. The molecular structure of HL was elucidated from single-crystal X-ray diffraction. X-ray crystallographic analysis shows that the molecule crystallizes in the monoclinic system, space group C2/c. In the complex, chloride was not coordinated as confirmed by conductivity measurements. The metal is coordinated to the oxime, imine, and amine nitrogen atoms and decomposes with loss of the organic ligand and halogen to leave metal oxide. The metal to ligand ratio was 1?:?2 by elemental analysis and mass spectrum.     

含偶氮苯与噻吩结构单元的共轭聚合物合成及酸致变色性质

以1,3-二(二苯膦基)丙烷二氯化镍(Ⅱ)作催化剂[Ni(dpp)Cl2],通过2,5-二溴噻吩格式试剂与4,4′-二碘偶氮苯共聚得到了一种新型共轭聚合物.采用红外光谱、核磁共振氢谱对聚合物的结构进行表征并通过紫外-可见吸收光谱、荧光光谱、X-射线衍射、热失重分析(TGA)、差热分析(DTA)等测试手段对聚合物的性能进行了详细的研究.紫外可见光谱分析结果表明,聚合物在384 nm处显示了偶氮苯发色团的特征吸收峰,相对于单体红移34 nm.在聚合物的氯仿溶液中观察到酸致变色现象,即分别加入CF3COOH和CH3SO3H后,溶液颜色由黄色分别变成墨绿色和紫色,而加入三乙胺溶液后溶液恢复到初始颜色.在25℃下测得的特性粘数为0.53 dL/g.热失重分析结果显示,该聚合物具有较好的热稳定性.     

Synthesis, photophysical and electrochemical properties of a mixed bipyridyl-phenanthrolyl ligand Ru(II) heteroleptic complex having trans-2-methyl-2-butenoic acid functionalities

In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid)-2,2'-bipyridine) (L(1)) and 5-(trans-2-methyl-2-butenoic acid)-1,10-phenanthroline (L(2)), with the corresponding mixed-ligand heteroleptic Ru(II) complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II) complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL(1)L(2)(NCS)(2)] exhibits broad and intense metal-to-ligand charge transfer (MLCT) absorption with a high molar extinction coefficient (λ(max) = 514 nm, ε = 69,700 M(-1) cm(-1)), better than those of individual single-ligand complexes, [Ru(L(1))(2)(NCS)(2)] and [Ru(L(2))(2)(NCS)(2)], and a strong photoluminescence intensity ratio in the red region at λ(em) = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.     

Synthesis and characterization of cobalt(II) and zinc(II) complexes of poly(3-nitrobenzyli dene-1-naphthylamine-co-succinic anhydride)

The cobalt(II) and zinc(II) complexes of poly(3-nitrobenzylidene-1-naphthylamine-co-succinic anhydride) were synthesized by the reaction of THF solution of the alternating copolymer with aqueous solution of cobalt(II) and zinc(II) acetates. The metal complexes were characterized by elemental analysis, magnetic measurements, IR, UV–Vis. and ¹H NMR spectral studies. The elemental analysis of the metal polymer complexes suggests that the metal to ligand ratio is 1:2. Conductance measurements indicate the non electrolytic nature of both the complexes. Electronic spectrum and magnetic moment studies are taken into account for the geometry of cobalt complex. Thermal analysis data of the two metal–polymer complexes were reported. XRD data revealed the nanocrystalline nature of both the complexes. The SEM studies give the surface morphology of the complexes.     

Microwave Synthesis of Copolymers Based on Itaconic Acid Moiety and Their Utility for Scavenging of Copper (II) and Lead (II)

We report here the preparation of the two copolymers, itaconic acid-methyl methacrylate and itaconic acid-acrylamide, in different ratios using microwave irradiation in the presence of azobisisobutyronitrile (AIBN) as initiator and 2-butanone as a solvent. All the prepared copolymers were characterized by different techniques; FT-IR, thermal analysis and elemental microanalysis. The thermal stability property of the prepared copolymers correlated with the changing of the itaconic acid ratio, as the ratio of itaconic acid increased, the crystallinity of the copolymer decreases. The itaconic acid-based copolymers also showed a good scavenging behavior in alkaline media for Cu (II) and Pb (II). The chelation behavior of both Cu (II) and Pb (II) complexes were checked using FT-IR, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC).     

Immobilization of ruthenium(II) salen complexes on poly(4-vinylpyridine) and their application in catalytic aldehyde olefination

Two Ru(II)(salen)(PPh₃)₂ complexes grafted on poly(4-vinylpyridine) have been synthesized and characterized. An elemental analysis shows that both grafted samples contain ca. 0.6 wt % Ru. FTIR spectra confirm the formation of metal-salen complexes attached to the carrier polymer by an interaction between the ruthenium(II) compounds with the pyridine nitrogen atoms of the poly(4-vinylpyridine). Immobilization of both Ru(II) salen complexes on the polymer increases their thermal stability as demonstrated by TG-MS analysis. The grafted materials were applied as catalysts for the olefination of various aldehydes at 60 °C under an inert gas atmosphere, showing comparable yields as their homogeneous congeners and high trans-selectivities. The ruthenium(II) compound with a larger salen ligand shows a better recyclability and selectivity than the derivative with the smaller ligand.     

Study of free-radical copolymerization of itaconic acid/2-acrylamido-2-methyl-1-propanesulfonic acid and their metal chelates

The monomer reactivity ratios for itaconic acid (IA)/2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in N,N-dimethylformamide solution using the benzoyl peroxide (Bz₂O₂) as an initiator with different monomer-to-monomer ratios in the feed were investigated by studying the resulting copolymer composition via elemental analysis. Composition results were summarized and various methods were employed to estimate the monomer reactivity ratios including the use of the Error-in Variables-Model method using a computer program, RREVM. The estimates of the reactivity ratios from the EVM method are found to be r_IA = 0.4636 and r_AMPS = 0.0357. These values suggest that IA is more reactive than AMPS and the copolymer will be richer in IA units. Cu(II) and Ni(II) chelates of the copolymers were prepared and the formation constants of each complex were determined by the mole-ratio method using the UV-vis spectroscopy. UV-vis studies showed that the complex formation tendency increased in the followed order: Cu(II) > Ni(II). The copolymers and their metal chelates were characterized by FT-IR spectra and SEM analysis. Also, thermal stabilities of the copolymers and their metal chelates were investigated using TGA and DSC analysis.     

Preparation,characterization and thermal stability of poly[2-(Dimethylamino)ethyl acrylate]

Poly[2-(dimethylamino)ethyl acrylate] (PDAEA) and polymer complexes of 2-(dimethylamino)ethyl acrylate (DAEA) with nickel(II), copper(II), iron(III) and cobalt(II) chlorides were prepared and characterized by means of IR, electronic spectra and elemental analysis. The thermal stability of the homopolymer was compared with those of the polymer complexes, and the order of stability was given. The activation energies of the polymer complexes were calculated.     

Synthesis of a ruthenium(II) polypyridine complex with 1,10-phenanthrolineselenazole as ligand and investigation of its G-quadruplex DNA-binding properties

A new Ru(II) complex, [Ru(bpy)₂L](ClO₄)₂ (bpy?=?2,2′-bipyridine, L?=?1,10-phenanthrolineselenazole), has been synthesized and structurally characterized by elemental analysis, ESI-MS, and ¹H NMR. The interaction of human telomeric oligomer 5′-AG₃(T₂AG₃)₃-3′ with the Ru(II) complex was explored by competition FRET experiment, ?uorescence titration, circular dichroism spectroscopy, thermal denaturation, polymerase chain reaction stop assay, and TRAP assay. The Ru(II) complex can selectively bind to G-quadruplex DNA. The results indicated that the complex not only induces a remarkable conformational change of human telomeric DNA, but also has the ability to stabilize the G-quadruplex.     

Synthesis and characterization of a Ru(II) complex with functionalized phenanthroline ligands having single-double linked anthracenyl and 1-methoxy-1-buten-3-yne moieties

Two series of bidentate polypyridine ligands, made of phenanthroline chelating subunits having substituted mono-and di-anthracenyl groups, and 1-methoxy-1-buten-3-yne at the 4 and 7-positions with the corresponding heteroleptic Ru(II) complex have been synthesized and characterized. The complex is formulated as [(Ru(L(1))(L(2))(NCS)(2))], (where L(1 )= 4-(9-dianthracenyl-10-(2,3-dimethylacrylic acid)-7-(9-anthracenyl-10-(2,3-dimethylacrylic acid)-1,10-phenanthroline and L(2) = 4,7-bis(1-methoxy-1-buten-3-yne)-1,10-phenanthroline). The Ru(II) complex shows characteristic broad and intense metal-to-ligand charge transfer (MLCT) bands absorption and appreciable photoluminescence spanning the visible region. The ligands and complex were characterized by FT-IR, 1H, 13C NMR spectroscopy, UV-Vis, photoluminescence and elemental analysis (see in supplementary materials). The anchoring groups in both ligands have allowed an extended delocalization of acceptor orbital of the metal-to-ligand charge-transfer (MLCT) excited state.     

Synthesis and characterization of novel ferrocene-containing pyridylamine ligands and their ruthenium(II) complexes: electronic communication through hydrogen-bonded amide linkage

Tris(2-pyridylmethyl)amine (TPA) derivatives with one or two ferrocenoylamide moieties at the 6-position of one or two pyridine rings of TPA were synthesized. The compounds, N-(6-ferrocenoylamide-2-pyridylmethyl)-N,N-bis(2-pyridylmethyl)amine (Fc-TPA; L1) and N,N-bis(6-ferrocenoylamide-2-pyridylmethyl)-N-(2-pyridylmethyl)amine (Fc2-TPA; L2), were characterized by spectroscopic methods, cyclic voltammetry, and X-ray crystallography. Their Ru(II) complexes were also prepared and characterized by spectroscopic methods, cyclic voltammetry, and X-ray crystallography. [RuCl(L1)(DMSO)]PF(6) (1) that contains S-bound dimethyl sulfoxide (DMSO) as a ligand and an uncoordinated ferrocenoylamide moiety exhibited two redox waves at 0.23 and 0.77 V (vs ferrocene/ferrocenium ion as 0 V), due to Fc/Fc(+) and Ru(II)/Ru(III) redox couples, respectively. [RuCl(L2)]PF(6) (2) that contains both coordinated and uncoordinated amide moieties showed two redox waves that were observed at 0.27 V (two electrons) and 0.46 V (one electron), assignable to Ru(II)/Ru(III) redox couples overlapped with the uncoordinated Fc/Fc(+) redox couple and the coordinated Fc/Fc(+), respectively. In contrast to 2, an acetonitrile complex, [Ru(L2)(CH(3)CN)](PF(6))(2) (3), exhibited three redox couples at 0.26 and 0.37 V for two kinds of Fc/Fc(+) couples, and 0.83 V for the Ru(II)/Ru(III) couple (vs ferrocene/ferrocenium ion as 0 V). In this complex, the redox potentials of the coordinated and the uncoordinated Fc-amide moieties were discriminated in the range of 0.11 V. Chemical two-electron oxidation of 1 gave [RuIIICl(L1+)(DMSO)](3+) to generate a ferromagnetically coupled triplet state (S = 1) with J = 13.7 cm-1 (H = -JS(1)S(2)) which was estimated by its variable-temperature electron spin resonance (ESR) spectra in CH(3)CN. The electron spins at the Ru(III) center and the Fe(III) center are ferromagnetically coupled via an amide linkage. In the case of 2, its two-electron oxidation gave the same ESR spectrum, which indicates formation of a similar triplet state. Such electronic communication may occur via the amide linkage forming the intramolecular hydrogen bonding.     

A chelating resin containing bis(2-benzimidazolylmethyl)amine: synthesis and metal-ion uptake properties suitable for analytical application

A new stable chelating resin was synthesized by incorporating the bis(2-benzimidazolyl methyl)amine into Merrifield polymer through CN covalent bond and characterized by elemental analysis, IR and thermal study. The sorption capacity of the newly formed resin for Ag(I), Cu(II), Fe(III), Hg(II) and Pb(II) as a function of pH have been studied. The resin exhibits no affinity for alkali or alkaline earth metals. In column operation it has been observed that Ag(I) in trace quantities can be separated from different complex matrices and Hg(II) can be removed from the river water spiked with Hg(II) at usual pH of natural waters.     

Synthesis and Crystal Structure of a Novel 1D Mercury（II） Iodide Coordination Polymer Containing 40-Membered Macrocycle

A mercury coordination polymer [Hg3(TizT)2I6]n (Mr = 1921.72, TizT = 2,4,6- tri(imidazole-1-yl)-1,3,5-triazine) containing a 40-membered macrocycle which was constructed by four TizT ligands and four mercury(II) iodide molecules had been synthesized by the reaction of HgI2 with TizT. The complex was characterized by elemental analysis, FT-IR, 1H NMR spectra and X-ray crystallography. The crystal of the complex belongs to the monoclinic system and C2/c space group with a = 35.840(5), b = 8.169(5), c = 14.980(5) , β = 104.466(5)°, Z = 4, V = 4247(3) 3, Dc = 3.006 g·cm-3, μ = 15.223 mm-1, F(000) = 3384, Rint = 0.0504, wR = 0.0833 and constructs a chair-like conformation of cyclohexane one by one, which forms a 1-D polymer through the fashion of fused ring aromatic hydrocarbon. The hydrogen bonds and π-π interactions shape the 2-D network structure. The two compounds excited weak fluorescence.     

含稀土铕(Ⅲ)配位聚合物的研究——铕(Ⅲ)噻吩甲酰三氟丙酮苯乙烯丙烯酸共聚物的研究

研究了铕 (Ⅲ )和噻吩甲酰三氟丙酮 (HTTA)形成的有机配合物与苯乙烯 丙烯酸共聚物 (PSAA)在不同pH值时发生配位反应得到配位聚合物NaEu(Ⅲ ) TTA PSAA的 3种样品 (a)、(b)、(c) .红外光谱、紫外光谱、X光电子能谱、DTA TG等测试手段证实Eu3+ 分别与PSAA、TTA- 发生配位 .元素分析和电导率测定结果证明了配位组成和结构在不同的pH条件下发生变化 .结果表明 ,配合物试样 (a)、(b)、(c)中Eu3+ 的含量分别为11 89%、12 5 5 %和 13 4 1% .由于配合物中存在着Eu3+ 分别与TTA- 和PSAA分子中羧基的配位作用并进一步交联 ,因此配合物样品均不溶于大部分有机溶剂 ,只能溶于N ,N 二甲基甲酰胺和丙三醇和异丙醇的混合溶剂 ,而且耐热性能均提高 .该配合物均是褐色固体 .荧光光谱表明 ,样品在常温、紫外光下发出强的红光 ,主要是Eu离子的5D0 →7F2 的跃迁 .讨论了溶剂、pH值对配合物荧光强度的影响 .当pH =10时 ,合成的配合物有最好的荧光性质 .     

Synthesis, structural, spectral, thermal and antimicrobial studies of palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes derived from N,N,N,N-tetradentate macrocyclic ligand

Palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes of general stoichiometry [PdL]Cl(2), [PtL]Cl(2), [Ru(L)Cl(2)]Cl and [Ir(L)Cl(2)]Cl are synthesized with a tetradentate macrocyclic ligand, derived from 2,6-diaminopyridine with 3-ethyl 2,4-pentanedione. Ligand was characterized on the basis of elemental analyses, IR, mass, and (1)H NMR and (13)C NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, mass, electronic spectral techniques and thermal studies. The value of magnetic moments indicates that all the complexes are diamagnetic except Ru(III) complex which shows magnetic moments corresponding its one unpaired electron. The macrocyclic ligand and all its metal complexes were also evaluated in vitro against some plant pathogenic fungi and bacteria to assess their biocidal properties.     

Synthesis,Crystal Structure,Photophysical and Redox Properties of a Novel Ru（Ⅱ） Complex with Carbazole-grafted 2-（2-Pyridyl）benzimidazole

A novel Ru(Ⅱ) complex [(bpy)2Ru(PBC)](PF6)2 (PBC = N-[4-(9-carbazole)butyl]-2-(2-pyridyl)benzimidazole) has been synthesized and verified by 1H NMR, elemental analysis and X-ray crystallography. The crystal (C48H40F12N8P2Ru, Mr = 1119.89) belongs to the triclinic system, space group P1, with a = 13.128(4), b = 13.814(4), c = 14.184(4) , α = 84.112(6), β = 88.473(6), γ = 78.196(6)°, Z = 2, V = 2504.6(13) 3, Dc = 1.485 g/cm3, F(000) = 1132, R = 0.0750 and wR = 0.1896. The Ru atom adopts a distorted-octahedral coordination geometry with the bond distances and bond angles falling in normal ranges. The complex shows an intense metal-to-ligand charge transfer (1MLCT) (dπ(Ru) →π*(L)) transition (ε ~1.2×104 dm3mol-1cm-1) at 457 nm in the UV-Vis absorption spectrum and a strong red phosphorescence at 632 nm in the CH3CN solution at ambient temperature. An efficient intramolecular energy transfer process from the carbazole unit to the [(bpy)2Ru(PB)]2+ emissive center exists by selective optical-simulation. Its electrochemical behavior shows multiplicate redox processes based on the metal center, the grafting carbazole moiety and the 2-(2-pyridyl)benzimidazole unit.     

Synthesis and properties of poly(aniline-co-azidoaniline)

Copolymers of polyaniline and o-azidoaniline were synthesized by chemical oxidative polymerization. The copolymers were characterized by powder X-ray diffraction (XRD) and UV/Vis and FT-IR spectroscopy. Thermal activation of the azido chromophore in the copolymer caused it to react and cross-link into adjacent polymer chains. The cross-linking of the copolymers was indicated by the depletion of the azido band in the FT-IR spectrum. The effects of the cross-linking were studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and four-probe conductivity. The TGA showed that the thermal stability of the copolymers is improved due to cross-linking. However, the increased thermal stability is accompanied by a decrease in electrical conductivity due to the loss of conjugation detected by UV/Vis spectroscopy and a loss of crystallinity due to the azido substituents, which was demonstrated by XRD.     

Photoinduced cleavage and DNA-binding of the Ruthenium(II) polypyridyl complex [Ru(phen)<Subscript>2</Subscript>(ipbd)](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

A novel ruthenium(II) polypyridyl complex [Ru(phen)₂{ipbd)](ClO₄)₂ (ipbd = 3-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)-1-benzodioxane, phen = 1,10-phenanthroline} has been synthesized and characterized by elemental analysis, ES-MS and ¹H-NMR spectra. The interaction of the complex with calf thymus DNA (CT-DNA) was investigated by absorption titration, fluorescence spectra, thermal denaturation, viscosity measurements, circular dichroism and photoinduced cleavage. The results suggest that the complex intercalates into the CT-DNA base pairs. Upon irradiation, this novel Ru(II) complex can cleave the plasmid pBR 322 DNA from the supercoiled form I to the open circular form II.     

Novel metal complexes of 3-acetylcoumarin-2-hydrazinobenzothiazole Schiff base: Design,structural characterizations,DNA binding,DFT calculations,molecular docking and biological studies

Five new Cu (II), Zn (II), Pd (II), Ru (III) and Ag(I) complexes, derived from the 3-acetylcoumarin-2-hydrazinobenzothiazole Schiff base (Hachbt), have been synthesized and characterized. The structures were established with the aid of elemental analyses (C, H, N), FT-IR, ¹H-NMR, ESR, UV–visible and ESI-mass spectra. The complexes were also investigated by magnetic susceptibility, thermal gravimetric analysis (TG-DTA) and cyclic voltammetry measurements. The results suggest that the Schiff base ligand behaves in two different ways: neutral mono/bidentate or mono-negative bi/tridentate. The calf thymus DNA (CT DNA) binding affinities of Hachbt and its complexes have been examined by UV–visible spectroscopy. The antifungal activity of the compounds was also screened against two fungal species of wood-decay basidiomycetes using the agar dilution method. Different complexes caused a reduction in the fungal colony diameters at a media concentration of 100 μg/ml. The best antifungal activity was observed for the Pd (II) and Ag(I) complexes with a 60% and 79% reduction, respectively. The effect of the complexes on the ability of the same fungi to decolorize poly-R dye on agar plates was also tested. All of the complexes showed an enhanced effect on the decolorization ability and the Cu (II) and Ru (III) complexes exhibited the strongest effect at a media concentration of 5 μg/ml. Theoretical studies were performed for all the complexes using the DFT/B3LYP/6–31 + g(d) basis set for calculations on the ligand atoms and LAN2DZ for the Pd (II) complex. The optimized geometries were found to be in a good agreement with the proposed structures. The molecular docking calculations show that the binding affinity of the Pd (II) complex is −309.170-309.2 kcal/mol, which suggests complexation with the DNA minor groove.     

Synthesis and crystal structure of a new copper (II) complex,designed to produce efficient successor of Cu2O,toward synergy of adsorption and photodegradation of MB

A new copper (II) coordination complex formulated as [Cu (dipic)(phen)(2-MePy)]. 2H₂O ( 1 ) where phen = 1, 10-phenanthroline, dipic²⁻ = pyridine-2,6-dicarboxylato and 2-MePy = 2-methyl pyrrole was synthesized through a simple and environment-friendly reaction under ultrasound irradiation. Also, complex 1 was synthesized by hydrothermal process at 120 °C for 3 days. The corresponding structure of complex 1 was characterized by elemental analysis, atomic absorption spectroscopy (AAS), inductively coupled plasma (ICP), conductivity measurement, Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, ultraviolet–visible spectroscopy (UV–Vis), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM) and fluorescence. The crystal structure of the hydrothermally synthesized complex was characterized by single crystal X-ray diffraction (SC-XRD(, which revealed a triclinic structure. In the remainder of this study, the Cu₂O nanoparticles have been prepared via thermal decomposition of hydrothermal and ultrasound complexes and characterized by ICP, FT-IR, powder X-ray diffraction (XRD), SEM and N₂ adsorption/desorption. Adsorption and visible-light-driven photocatalytic capabilities of two synthetic Cu₂O were investigated in the removal of MB from water. The result showed that the synthesized catalysts have good catalytic activity and the photocatalytic degradation is more effective in dye removal of MB compared with the adsorption.