Search

Reactions of Zn(NO3)2·6H2O, 2-iodobenzoic acid (2-IBA), and 4-ethyl- or 3-chloropyridine result in the formation of binuclear neutral complexes [Zn2(2-IBA)4L2] (L = 3-ClPy (1), 4-EtPy (2)) whose structures are analyzed by X-ray crystallography. The structure of 2 has specific noncovalent I⋯I interactions.

Through precisely adjusting the pH value of reaction system, two new mixed-ligand based coordination polymers, namely [Zn(ip)0.5(bta)]n (1) and [Zn3(Hip)4(bta)2]n (2) (H2ip = isophthalic acid, Hbta = benzotriazole), have been acquired through the self-assemble reaction of Zn(II) salts in combination with H2ip and Hbta. Both compounds have high thermal stability demonstrated by the thermogravimetric analysis (TGA) experiments, and exhibit strong luminescence emission at room temperature. Their application values on the children bone growth and development were evaluated and the specific mechanism was examined simultaneously. Above all, compound 1 was more outstanding than compound 2 against the children bone growth and development by regulating the Vitamin K receptor on the bone cell surface.

By the reaction of a rigid π-conjugated H4L linker (5,5′-(1,3,6,8-tetraoxobenzo[lmn][3],[8]phenanthroline-2-7-diyl)bis-1,3-benzenedicarboxylic acid), Cu(NO3)2, and N-donor auxiliary linkers, two new Cu-based coordination polymers (CPs), namely {[Cu(L)0.5(1,4-bib)(H2O)2]·0.5H2O}n (1) and {[Cu(H2L)(4,4′-bibp)(H2O)2]}n (2) {1,4-bib = 1,4-bis(1-imidazolyl)benzene, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl} are synthesized under solvothermal conditions and characterized. Furthermore, the protective effect of compounds 1 and 2 on the sepsis mice model is evaluated and the related mechanism is explored. Firstly, the CFU counting assay is performed to detect the bactericidal effect of compounds 1 and 2 in vivo. Then, the ELISA assay is conducted to measure the release of interleukin-1β (IL-1β) and interleukin-6 (IL-6) into the plasma after treatment with the compounds.

In this current experiment, by applying the mixed-ligand synthesis method, two coordination polymers (CPs) containing Co(II) were created triumphantly with reaction between 1,3-bis(1-imidazoly)benzene (mbib) and Co(II) salts with the aid of diverse carboxylic ligands, and their chemical formulae are [Co3(opda)3(mbib)4(H2O)4]·2H2O (1, H2opda is 1,2-phenylenediacetic acid) and [Co(mpda)(mbib)]·H2O (2, H2mpda is 1,3-phenylenediacetic acid). The two compounds’ magnetic performances suggest that between the adjacent metal ions, there present the antiferromagnetic coupling. The evaluation of their treatment activity against chronic subdural hematoma was carried out and the relevant mechanism was studied simultaneously. Firstly, before the treatment of compound, the chronic subdural hematoma was generated. Furthermore, the enzyme-linked immunosorbent assay detection kit was implemented and in hematoma capsule, the anti-inflammatory cytokines level and pro-inflammatory cytokines level was detected. Additionally, the cytotoxicity of compounds 1 and 2 on the normal human cells was determined with Cell Counting Kit-8 assay. Above all, we proved compound 1 decreased the pro-inflammatory cytokines content and increased the anti-inflammatory cytokines content in the hematoma capsule, which is much stronger than that of compound 2. Both compounds 1 and 2 showed no cytotoxicity on the normal human cells.

Metformin is one of the most effective drugs for the treatment of type II diabetes. Two new mixed ligand complexes of vanadyl(ii) and chromium(iii) ions with the general formula [VOL1L2]SO4 and [CrL1L2(Cl)2]Cl, respectively, where L1 is the metformin and L2 is the glycine amino acid, have been synthesized in MeOH solvent with 1:1:1 stoichiometry and characterized by several spectroscopic techniques. The spectroscopic data suggested that the [VOL1L2]SO4 complex possesses a square pyramidal geometry, where the [CrL1L2(Cl)2]Cl complex possesses an octahedral geometry. The L1 ligand coordinated to the VO(ii) and Cr(iii) ions via the N atoms of the imino (‒C═NH) groups, where the L2 ligand coordinated via the O atom of the carboxylate group (COO) and the N atom of the amino group (NH2). The interaction of ligands L1 and L2 with the metal ions leads to complexes that have organized nanoscale structures with a main diameter of ∼14 nm for the [CrL1L2(Cl)2]Cl complex and ∼40 nm for the [VOL1L2]SO4 complex.

Four mixed-ligand metal(II) complexes with the molecular formulae [M(ofl)(bipy)]NO3�H2O and [M(ofl)(phen)]NO3�H2O were synthesized by the reaction of Co(II) and Ni(II) with ofloxacin (Hofl) in the presence of 1,10-phenanthroline (phen) / 2,2`-bipyridine (bipy) (1:1:1 molar ratio). The data obtained from elemental analysis, molar conductance, spectral infrared, reflectance spectra and magnetic studies gave information about the coordination of the ligands and the geometry of the metallic ion. The results suggest that Hofl is deprotonated and bidentately bound to the metal ion through the pyridone oxygen and the carboxylato oxygen while phen and bipy act as neutral bidentate ligands coordinated through the nitrogen atoms. Tetrahedral geometry is proposed for all complexes. Thermal analysis data led to useful information concerning the composition, dehydration and thermal behaviour of the complexes. Ofloxacin and the metal complexes were tested for antibacterial activity and also for antioxidant activity. The variations of physicochemical parameters were monitored, which explain the antibacterial behaviour of these compounds. The interactions between metal complexes and bacterial receptors have lower energy values compared to the ofloxacin ligand. The molecular docking studies allow the identification of the biological target and the predictions of the bonds between the studied compounds and the receptors of E. coli (3t88), S. aureus (3q8u) and P. aeruginosa (4lkd).

Two mixed-ligand coordination polymers with the chemical formulae {[Cu3(Hdpc)2(tib)2(H2O)2]·2H2O)}n (1, H3dpc = 2,6-di(4-carboxylphenyl)pyridine-4-carboxylic acid, tib = 1,3,5-tris(1-imidazolyl)benzene)) and [Cu(trans-chda)2(bimb)2·2H2O]n (2, H2chda = 1,4-cyclohexane(dicarboxylic)acid, bimb = 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene) are successfully prepared by the reaction of Cu(NO3)2·3H2O with different O-donor carboxylic acid and N-donor co-ligands under the solvothermal conditions. Furthermore, the treatment effect of the two compounds on the acute pancreatitis is evaluated in the biological experiment. Firstly, RT-PCR is performed to measure the relative expression level of the key genes of E. coli. Moreover, the inflammatory levels of the patients are evaluated by the ELISA detection of inflammatory cytokines, IL-1β, and TNF-α.

The reaction of dimethyltin(IV) dichloride (DMT) with homopiperazine (HPIP) was studied. The equilibria of the complexes formed in solution were investigated. The complexes detected are of 1:1 stoi...

Two novel mixed-ligand coordination polymers, {[Co(tdc)(btrp)]·0.67DMF}n (1) and {[Zn2(bimb)2(tdc)2]·2H2O}n (2) involving 2,5-thiophenedicarboxylate (H2tdc), and bitopic flexible N-donor ligands, 1,3-bis(1,2,4-triazol-1-yl)propane (btrp) and 1,4-bis((1H-benzo[d]imidazol-1-yl)methyl)benzene (bimb), have been synthesized by the hydrothermal method and characterized via IR, elemental analysis, thermal analysis, and powder X-ray diffraction. The biological functional studies were performed; the treatment activity of the compounds on periodontitis and the specific mechanism was explored. First, the real-time RT-PCR was carried out to determine the inflammatory genes nf-κb and p53 relative expression in periodontal mucosal cells after treating with compounds 1 and 2. Then, the level of the inflammatory cytokine in the gingival crevicular fluid after treating with compounds was also determined by the ELISA detection kit.

New mixed ligand complexes of nickel(II) were synthesized by using dibasic H/5-bromo-/5-chloro-/4-hydroxy-2-hydroxybenzophenone-thiosemicarbazones (L1–4H2) and [Ni(PPh3)2Cl2]. The ligands and complexes were characterized by cyclic voltammetry, infrared, 1H and 31P NMR spectroscopy techniques. Crystallographic analyses of the 5-bromo-substituted (2) and 5-chloro-substituted (3) complexes as representatives were performed and so confirmed the ONS chelate structure and presence of PPh3 as co-ligand in the complexes. To reveal the antioxidant properties of the compounds, TEAC values (by CUPRAC method) were determined along with free radical-scavenging activity (by DPPH method). The compounds bearing 4-hydroxy substituent, L4H2 and complex 4 were the most effective compounds. The relationship between structure and antioxidant capacity in the context of benzophenone substituents and nickel(II) center was evaluated. Electrochemical results revealed that all complexes displayed metal-centered and ligand-centered redox processes. The antioxidant capacities of complexes were well correlated to electrochemical parameters.

A novel mixed ligand Cu(II) complex of 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 8-hydroxyquinoline was synthesized and spectroscopically characterized. The phenolate oxygen bridged dinuclear (polymorph 1) and solvent-induced mononuclear (polymorph 2) forms were obtained using DMSO and acetic acid solvents. The solvato supramolecular isomeric forms (P and P21/a) of the complex are confirmed by the single crystal X-ray diffraction method. In polymorph 1, a hydrogen-bonded one-dimensional network is constructed by C–H⋯O contacts, whereas, in polymorph 2, a two-dimensional ladder-like architecture is formed by the interplay of C–H⋯O, C–H⋯F and F⋯F contacts. The vital role of distinct non-covalent interactions in the establishment of a unique structural topology is analysed by Hirshfeld surfaces, 2D fingerprint plots, QTAIM and the NCI index model. The anisotropies in the three-dimensional structural topology are visualized through their energy frameworks and evidenced by their interaction energies. The electronic structures of the polymorphs were optimized by density functional theory calculations to explore their coordination stability and chemically reactive parameters. Polymorph 1 exhibits potential antibacterial activity against methicillin-resistant Staphylococcus aureus with a minimum inhibitory concentration of 8 μg mL−1. Further, polymorphs were docked to penicillin-binding protein 2, where polymorph 1 had a binding score of −10.0 kcal mol−1, greatly supporting the in vitro results.

A novel Co(II)-based metal-organic framework (MOF) {[Co2(TCPP)(BPY)](DMF)3}n (1) with a pillared structure based on 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H4TCPP) and 4,4'-bipyridine (BPY) is designed and synthesized via the solvothermal reaction. Furthermore, a green-hand grinding technique is implemented to reduce the particle size of complex 1 to generate nanoscale 1 (denoted as nano-1 hereafter). After the construction of the acute cerebral infarction animal model, the infarct area of the brain is measured after 2 weeks of treatment with the compound. Then, ELISA is performed to detect the content of hs-CRP and IL-1b and TNF-a in the serum.

In the current study, two new mixed-ligand coordination polymers with the chemical formulae of {[Cu(oba)(4-bpdb)]·CH3OH}n (1) and {[Co3(oba)3(4-bpdb)(DMF)2]·4H2O}n (2) (H2oba = 4,4'-oxybis-benzoate, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) are synthesized under solvothermal conditions. Both structures are analyzed by single crystal X-ray diffraction along with the elemental analysis. Their prevention activity on the acute kidney injury in patients with acute cerebral hemorrhage is evaluated and the protentional mechanism is revealed. Firstly, the Nagl content in urine is measured. Secondly, the inflammatory response in glomerular epithelial cells is detected by real-time RT-PCR.

A reaction of the N-donor ligand 1,3-di(1H-imidazol-1-yl)benzene (dimb) with Co(NO3)2·6H2O and the V-shaped carboxylate ligand biphenyl-3,4',5-tricarboxylic acid (H3bpt) under hydro- or solvothermal conditions yields two new Co(II)-based coordination polymers with the chemical formulas {Co3(dimb)2(bpt)2(H2O)4]}n (1) and [Co2(dimb)2(Hbpt)2]·H2O (2). Furthermore, the treatment effect of compounds 1 and 2 against cardiac arrest induced by anesthesia is evaluated. Firstly, ELISA is used to detect the content of cardiac troponin T and B brain natriuretic peptide after treatment with the compounds. Moreover, RT-PCR is conducted and the relative expression level of Sirt1 in the rat myocardial tissue is measured.

The combined use of P(2-MeOC6H4)3 (L1) and TMEDA as ligands effectively prevents defect formation in palladium-catalyzed direct arylation polymerization (DArP) to give donor–acceptor type alternati...

The interaction of triethanolamine (TEA) with Cu(II) salts of salicylic, cinnamic and succinic acids was studied for the first time. The structure of the synthesized complexes was investigated by single-crystal X-ray diffraction. TEA complexes with Cu(II) salicylate (1) and cinnamate (2) are binuclear mixed ligand complexes, but interaction of TEA with Cu(II) succinate leads to the formation of cationic mononuclear complex—[Cu(TEA)2](C4H4O4) (3). Cu(II) complexes 1–3 were also characterized by physicochemical and spectroscopic methods. Their antimicrobial activity was investigated.

A series of mixed-ligand Cu(II) complexes of the type: (i) [Cu(l-pro)(diimine)(H2O)n](ClO4) (n = 0 or 1), where l-pro is l-proline and diimine is 2,2′-bipyridine (bpy; 1), (ii) 4,4′-dimethy...

Tris(glycinato)Mn(III) and its mixed ligand complexes with azido-, thiocyanato-, chloro- and bromo- groups have been synthesized and characterized by UV–Vis spectrophotometry, IR spectropho...

Initially, a novel series of mixed ligand Pd(II) complexes of 2H[1,4]benzothiazin-3(4H)-one (Hbto) and diamine or phosphine ligands were successfully prepared with yields of 61 to 92%. The treatment of Na2PdCl4 with Hbto in acetone with 1:2 Pd to Hbto ratio affords cis-[PdCl2(Hbto)2] (1) that delivers an appropriate entry into mixed-ligand Hbto complexes. The complex (1) was used as a precursor for preparation the complexes of the type [Pd(Hbto)2(κ2-diamine)]Cl2; (diamine = en (2a), bipy (2b), phen (2c)) and [Pd(Hbto)2(κ2-diphosphine)]Cl2; (diphosphine = dppm (3a), dppe (3b), dppp (3c), dppf (3d)). Likewise, the mono phosphine (PPh3) was used to prepare the contrast complex with complex (1), however, to dissipate the suspicion that define complex [Pd(Hbto)2(PPh3)2]Cl2 is present in the cis or trans structure, two methods were used to prepare this complex, both of which demonstrated that the cis is the preferred structure for the complex [Pd(Hbto)2(PPh3)2]Cl2 (4). For all as-prepared complexes, the characterization techniques (molar conductivity, IR, 1H-, 13C-{1H}, 31P-{1H}NMR and elemental analyses) prove that the Hbto links to Pd(II) in a mono-dentate fashion through the exocyclic oxygen atom. To benefit from the complexes prepared, some as-prepared complexes (1), (2b) and (4) have been evaluated for their H2 storage at 77 K after measuring the N2 adsorption/desorption isotherms in order to get some information about BET surface areas of the samples. The results demonstrate that the selected prepared complexes were all able of storing the H2 and among the complexes (1), (2b) and (4), (2b) was the best one and was able to store 5.4 wt% of H2 under 70 bar and 77 K.

Mixed-ligand polymeric and binuclear silver(I) complexes with azaheterocyclic ligands and the closo-decaborate anion of the composition [Ag2L[B10H10]]n and [Ag2L2[B10H10]] (L = bipy, bpa, and phen) are synthesized and studied by IR-spectroscopy and X-ray powder diffraction. The complexes are prepared by the reaction between [Ag2[B10H10]] and ligand L in organic solvents. It is found that polymeric and binuclear complexes are selectively formed depending on the solvent used. When the reaction proceeds in acetonitrile, polymeric complexes are isolated. When DMF is used, binuclear complexes are formed which explains by the complete dissociation of the starting [Ag2[B10H10]] complex. The structures of [Ag2(bipy)[B10H10]]n and [Ag2(bpa)2[B10H10]]·DMF are determined by X-ray diffraction.

A new mixed-ligand diorganotin(IV) complex, [μ-(4-dpe){Me2Sn(cup)2}2] (1), was synthesized by reacting dimethyltin(IV) dichloride with 1,2-di(4-pyridyl)ethylene (4-dpe) and ammonium N-Nitroso-N-phenylhydroxylamine (cup). The prepared complex was fully characterized by PXRD, 1H, 13C and 119Sn NMR, IR, and UV spectra and elemental analysis (CHN). The structural analysis of complex 1 by X-ray diffraction showed that this compound consists of centrosymmetric binuclear units that crystallize in the monoclinic system with the space group of P21/c. Thermal behavior of this complex was interrogated by thermogravimetric and differential thermal analysis (TGA and DTA) under air atmosphere. The study of thermal behavior and luminescence properties of prepared diorganotin(IV) complex exhibited that this complex can be used as a emitting layer in the preparation of optical devices. The prepared coordination compound was used in two different concentrations in the manufacture of two light-emitting diodes (OLEDs).

The last decade has witnessed tremendous advances in the design of anticancer gold complexes containing tertiary phosphines, a class of ligands that have significantly contributed to the development of metal complexes owing to their stabilizing effect. The promising in vitro antiproliferative properties of the phosphine-containing organogold compound auranofin [1-(thio-kS)-2,3,4,6-tetra-O-acetyl-β- d -glucopyranose](triethylphosphine-kP)gold(I), originally used to treat rheumatoid arthritis, inspired the extensive application of monodentate phosphines in the development of anticancer gold complexes. Meanwhile, the use of diphosphine ligands promoted advances in the preparation of chelated gold complexes as well as mixed-metal and mixed-ligand complexes that have superior anticancer activity. The present report summarizes the current state of knowledge of diphosphine ligands in the development of anticancer gold complexes, and explores challenges and opportunities in designing gold-containing mixed-metal and mixed-ligand complexes that have anticancer action.

Mixed ligand complexes [Cu(phen)(Lap)2] (1) and [Co(dppeO)(Lap)2] (2) were synthesized from the reaction of lapachol (Lap) with [Cu(phen)Cl2] or [Co(dppe)Cl2] in the presence of Et3N. Complexes (1) and (2) were fully characterized by X-ray crystallography, elemental analyses, and infrared spectroscopy. Antiproliferative activities of complexes (1) and (2) against several tumor cell lines were also determined alongside those of [Cu(Lap)2(EtOH)2] (3) and [Co(Lap)2(EtOH)2] (4).

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.

A mixed ligand approach has been applied for the synthesis of a series of Zn(II) and Cd(II) coordination polymers, namely CP1 [{Zn(3-bpna)(bdc)}·CH3OH]α, CP2 [{Cd(3-bpna)(oba)}·DMF·H2O]α, CP3 [{Cd(3-bpna)(5-nipa)}·2DMF]α, CP4 [{Zn2(dpmndi)(oba)3}·4H2O]α, CP5 [{Zn(dpmndi)0.5(oba)·DMF}·DMF·H2O]α and CP6 [{Cd(dpmndi)(bdc)}·DMF]α, which are constructed by the reactions of the ligand 3-bpna or dpmndi and Zn(NO3)2·6H2O or Cd(NO3)2·4H2O in the presence of different dicarboxylate ligands, specifically terephthalic acid, 4,4′-oxydibenzoic acid and 5-nitroisophthalic acid, as a co-ligand under solvothermal conditions. These coordination polymers were structurally characterized and display 1D, 2D and 3D network structures. Moreover, their fluorescent behavior was also investigated and the results are found to be very promising.

Interaction of iridium(III) nitro-aqua complexes with 1,10-phenanthroline is studied. Complex anions [Ir(phen)(NO2)4]− and [Ir(phen)(OH)(NO2)3]− are isolated in the solid phase. The complex Na[Ir(phen)(NO2)4](phen)(H2O) is structurally characterized for the first time. Crystallographic data: $$a = 8.0752(5)\acute{\overset{\circ}{\mathrm{A}}}$$ , $$b = 11.690(7)\acute{\overset{\circ}{\mathrm{A}}}$$ , $$c = 14.012(7)\acute{\overset{\circ}{\mathrm{A}}}$$ , α = 105.55(2)°, β = 91,99(2)°, γ = 103,71(2)° space group P-1, Z = 2, ρcalc = 1,936 g/cm3. The coordination sphere of the iridium atom has a distorted octahedral geometry. The obtained structure contains an island motif consisting of the pairs of complex anions [Ir(phen)(NO2)4]− linked to each other by sodium cations.

With an aim to obtain a new supramolecular compound based on Keggin-type polyoxometalates with mixed-ligand: [Cu(I)(phen)2]2{[Cu(II)]2(phen)4PTA}[H3PMoV4MoVI8O40] (phen = 1,10-phenanthroline, PTA = terephthalic acid) has been synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR, X-ray single crystal diffraction, TG analyses and XPS. In the title compound, the Keggin-type phosphomolybates anions, butterfly-shaped [Cu(I)(phen)2]+ subunits and dumbbell-shaped {[Cu(II)]2(phen)4PTA}2+ subunits are alternately connected to form chiral helical chains via hydrogen bonds along b axis, and the adjacent chiral helical chains are connected in the way of sharing butterfly-shaped [Cu(I)(phen)2]+ subunits and dumbbell-shaped {[Cu(II)]2(phen)4PTA}2+ subunits to form 3D supramolecular reticular framework. As expected, the title compound with mixed-ligands (phen and PTA) has been successfully synthesized, inconceivably, the title compound also contains mixed-valence Cu (Cu(I) in butterfly-shaped [Cu(I)(phen)2]+ subunits; Cu(II) in dumbbell-shaped {[Cu(II)]2(phen)4PTA}2+ subunits). The preliminary analyses show that mixed-valence Cu(I/II) may be due to the reduction of Cu(II) (from CuCl2) to Cu(I) (in butterfly-shaped [Cu(I)(phen)2]+ subunits) by N-containing compound. The successful results of this work provide a new idea that supramolecular materials with attractive structures and novel properties, which could be designed and synthesized by introducing of mixed-ligands into the supramolecular materials. Additionally, the electrocatalytic property of the title compound to H2O2 has been studied.

Co+2, Ni+2, Cu+2 as well Zn+2 compounds mixed ligand from 8-hydroxyquinoline(8-HQ) also tributylphosphine (PBu3) have been attended at aquatic ethyl alcohol for (1:2:2) (M:8-HQ:PBu3). Produced complexes have been identified by utilizing atomic absorption flame, FT-IR as well UV-Vis spectrum manners also magnetic susceptibility as well as conductivity methods. At addendum antibacterial efficiency from the ligands as well complexes oboist three species about bacteria have been as well examined. Ligands and their complexes show good bacterial efficiencies. Of the gained datum the octahedral geometry was proposed into whole prepared complexes.

A library of 26 mixed ligand UiO-66 analogs was synthesized, characterized, and screened for catalytic degradation of the chemical warfare agent (CWA) simulant dimethyl 4-nitrophenylphosphate (DMNP). The MOFs were screened and compared to physical mixtures of the same single component MOFs. Several of the MOFs display higher catalytic activity than the parent UiO-66 and other single ligand UiO-66 analogues.

For the first time, we report a cost-effective mixed-metal (Na/Cu) mixed-ligand (flexible/rigid) metal–organic framework H1.5[Na0.5Cu2(L1)(L2)(H2O)]·5.5H2O (Na/Cu-MOF; H2L1 = 4,4′-(4-(4H-1,2,4-triazol-4-yl)phenylazanediyl)dibenzoic acid; and H4L2 = citric acid). The 3D microporous framework of the Na/Cu-MOF consists of 10.28 A × 10.07 A quadrilateral channels and 14.52 A × 6.72 A triangular channels, which exhibits highly efficient photocatalytic H2 generation (4650 μmol g−1 h−1) under visible-light irradiation. Emission quenching and transient photocurrent experiments confirm the charge separation and transfer process for the possible reaction mechanism in the photocatalytic system. Control experiments using a similar single-metal single-ligand MOF [Cu2(L2)(H2O)2] (Cu-MOF; H4L2 = citric acid) have been performed for comparison, which demonstrates the potential of mixed-metal mixed-ligand MOFs in the practical utilization of light.

Two novel luminescent Cd(II)–organic frameworks, [Cd2(2-abpt)(Hbtca)(H2btca)0.5(H2O)]n (1) and {[Cd3(2-abpt)(btca)1.5]·H2O}n (2) (2-abpt = 3,5-di(2 -pyridyl)-4-amino-1,2,4-triazole, H4btca = 1,2,4,5-benzenetetracarboxylic acid), were hydrothermally synthesized from a rigid aromatic carboxylate ligand and a pyridine ligand containing free amino groups. 1 exhibits a novel (4,4,5,5)-c 2D layer architecture with 1D pipe-like chains. 2 shows a 3D framework with an unprecedented (4,4,4,6,7)-c topology. Their structural differences mainly stem from the various coordination modes of the rigid aromatic carboxylate ligand. Luminescence sensing experiments exhibit that 1 can highly sensitively and selectively detect TNP in DMF and H2O. Moreover, test paper was developed to detect TNP as a convenient and practicable approach. In addition, 1 shows highly sensitive and selective sensing of Cu2+. The possible detection mechanisms of 1 towards TNP and Cu2+ have been discussed. These experimental results suggest that 1 should be a potential sensor for TNP and Cu2+.

A new series of water soluble mixed ligand complexes [MII(L)(bpy)AcO].nH2O M = Cu, (n=1) (1); Co (2), Mn (3), Ni (4) (n=4) and Zn (5) (n=2) have been synthesized from 2-(2-Morpholinoethylimino)methyl)phenol Schiff base ligand (HL) and 2,2�-bipyridine in a 1:1:1 molar ratio. The resulting complexes were characterized by spectral techniques. The spectral data of these complexes suggest an octahedral geometry. In vitro antioxidant activity results of DPPH assay, hydroxyl radical, super oxide and nitric oxide for complexes (1-5) were compared with ligand (HL) and in vitro antimicrobial activities of all compounds were examined against selected bacterial and fungal strains which indicate that the complexes exhibit higher antimicrobial activity than free ligand (HL). Gel electrophoresis results indicated that, complexes (1) and (2) have exhibited more DNA cleavage efficiency than others. The intrinsic binding constant (Kb) values for the complexes (1-5) observed by electronic absorption technique were in the order of (1) ] (4) ] (5) ] (2) ] (3) and DNA binding affinity values for these complexes obtained by viscosity measurements were in the order of ethidium bromide ] (1) ] (2) ] (3) ] (4) ] (5).

International audience; A mixed-ligand bis(dithiolene) gold complex is isolated from scrambling reaction of two neutral radical symmetric complexes. Its asymmetric character translates into specific structural and electronic properties including larger electrochemical and optical band gaps than those of both precursors.

Two mixed ligand complexes containing acesulfame (acs) and 3-aminopyridine (3-ap) ligands of Mn(II) and Co(II) were synthesized. The obtained compounds were characterized by various analysis methods. The geometries of complexes, C18H28MnN6O12S2 (1) and C18H32CoN6O14S2 (2), are distorted octahedra. Coordination of metal cations is provided by two molecules of 3-ap and four water ligands. In both structures, the 2+ charge of the metal required two monoanionic acs molecules located outside the coordination sphere. Complex 1 contains no hydrate water, while 2 contains two molecules of hydrate water. The crystal system of 1 is monoclinic and space group P2(1)/c, while the crystal system of 2 is triclinic and space group P-1. Data on the removal of hydrate and crystalline waters in structures from thermal analysis curves support the described molecular structures. The bending vibrations of the bonds obtained from the FT-IR spectra match the crystal structure described. As a result of thermal analysis of both complexes, it was determined that the relevant metal cations remained in the reaction vessel as oxide (MnO and CoO) residues. WOS:000626933900001 2-s2.0-85102252527

A Cu(II) coordination polymer with the composition of [Cu2(L)2(4,4��-bipy)2]n��2 n(ClO4) (1, HL = 4-methyl-L-phenylalanine and 4,4��-bipy is 4,4��-bipyridine), was successfully obtained by the reaction of the mixed ligand of HL and 4,4��-bipy with Cu(ClO4)2 �� 6H2O under solvothermal condition. The as-synthesized compound not only has high thermal stability until 275��C but also excellent photocatalytic activity for the methyl blue solution degradation under the irradiation of ultraviolet light. Furthermore, the compound���s treatment activity on the diabetes was determined and its relevant mechanism was also studied. The cytotoxicity or hemolysis toxicity (HC50) of the synthesized compound was also evaluated in this research.

Two rationally designed strategies for covalent bonding of fluorescent dyes in coordination polymer nanoparticles aiming to achieve bifunctional fluorescent nanostructures have been developed. The first strategy was based on the synthesis of the coordination polymers structured as nanoparticles by coordination of CoII ions to two different catechol ligands containing free functional chemical groups (dopamine and 3,4‐dihydroxybenzaldehyde), and a bis(imidazole)‐based ligand (1,4‐bis(imidazole‐1‐ylmethyl)benzene, bix). Subsequently, different dyes, namely fluorescein isothiocyanate (FITC), 1‐pyrenebutanoic acid hydrazide (PBH) or Alexa Fluor® 568 (A568), could be sequentially attached to the surface of the nanoparticles. The second strategy was focused on the prefunctionalization of catechol ligands with the corresponding dyes and, afterwards, the coordination with the metal ions in presence of bix. In vitro studies demonstrated the internalization of the bifunctional nanoparticles and the persistence of the fluorescent properties after cell uptake without dye leaching., This work was supported by the project MAT2015‐70615‐R and BIO2016‐78057‐R from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO) and by FEDER funds. K. W thanks Generalitat de Catalunya for her fellowship (Beca F1 2013). F. N. thanks Universidad Nacional del Sur for supporting her postdoctoral stay. R.S. thanks the Ministerio de Educación, Cultura y Deporte for the predoctoral grant PFU14/03170. The ICN2 is funded by the CERCA programme/Generalitat de Catalunya and supported by the Severo Ochoa programme of the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, grant no. SEV‐2013‐0295).

A Cd(II)-based one-dimensional coordination polymer (1-D CP), [Cd2(mes)2(4-phpy)4] (1), was prepared using mesaconic acid (H2mes) and 4-phenyl pyridine (4-phpy) mixed ligand system. Compound 1 has been characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) pattern and single crystal X-ray diffraction (SCXRD) techniques. Structural elucidation reveals a 1-D chain which contains a 14-membered metal-ligand ring composed of two mes ligands and two Cd(II) centers. Further, the 1-D chains are assembled into a two-dimensional (2-D) supramolecular network by C–H···π(metal-ligand ring) interactions. The fluorescence lifetime of 1 shows a good range of average lifetime. The theoretical band gap has also been calculated by density functional theory (DFT) computations, which shows that 1 may possess semiconducting properties.

The new mononuclear [Co(dbz)Cl2] (dbz = bis(2-benzimidazolyl)ethane) complex has been studied by magnetic measurements and variable-temperature, variable-field magnetic circular dichroism (MCD) spectroscopy, accompanied by theoretical modelling. The values of the zero-field splitting parameters obtained from different experimental techniques are compared with the quantum-chemical calculations.

An important challenge, in the medicinal chemistry field, is the research of novel forceful drugs to overcome tumor-acquired resistance. The c-Kit tyrosine kinase receptor (TKR) represents a suitable target for the carcinogenesis control of gastro-intestinal stromal (GIST), leukemia, and mastocytosis tumors; nevertheless, several hotspot mutations of the protein limit the efficacy of a few clinical administered TKRs inhibitors. In this study, a new in silico protocol based on ligand and structure-based combined method is proposed, with the aim to identify a set of new c-Kit inhibitors able to complex c-Kit mutated proteins. A recent and freely available web-server DRUDIT is used for the ligand-based method. The protocol application allows for identifying a new generation of potential TKR inhibitors, which, in silico, complex the V654A and T670I mutated proteins and potentially overcome resistant mutations (D816H). The structure-based analysis is performed by Induced Fit Docking (IFD) studies. The comparison between the explored ligands and well-known drugs highlights the possibility to overcome tumor-acquired resistance. The best-selected structures (630705 and SML1348) provide valuable binding affinities with the mutated c-Kit forms (respectively T670I and V654A).

A new Zn(II) metal-organic framework (MOFs), [Zn(BTC)(HME)]·(DMAc)(H2O) (1, H3BTC =1,3,5-benzenetricarboxylic acid, HME = protonated melamine, DMAc = N,N-dimethylacetamide), has been synthesized un...

By using pyrazine (pz) and its derivatives 2,3-naphthalenylphenazine (npz) and 2,3-diphenylpyrazine (dpz), one Lindqvist- and six Keggin-based compounds, [AgI2(npz)4(W6O19)]·npz ( 1 ), [AgI2(npz)3(HPW12O40)] ( 2 ), [AgI3(npz)4-(PMo12O40)] ( 3 ), [AgI4(pz)5(SiMo12O40)] ( 4 ), [AgI4(npz)2(pz)(PMoVMo11VIO40)] ( 5 ), [AgI4(npz)4(dpz)2(H2O)2(SiW12O40)] ( 6 ) and {AgI5KI2(npz)4(dpz)2[H(PWVW11VIO40)2]} ( 7 ), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analyses. In compound 1 , there is a distorted “I”-type [Ag(npz)2]+ subunit with two npz arranging vertically. Two [Ag(npz)2]+ subunits support the [W6O19]2− anion symmetrically. In compound 2 , there are [Ag2-(npz)3]2+ clusters with one linking and two terminate npz, which are further linked by [PW12O40]3− anions to form a “sunrise”-like chain. In compound 3 , there exist a discrete [Ag2(npz)3]2+ cluster and a mono-supporting anion [AgI(npz)- (HPW12O40)]−. In compound 4 , there are two kinds of cycles in honeycomb-like Ag-pz layer: six-membered cycle I and eight-membered cycle II. An anion dimmer linked by a AgI ion embeds in bigger cycle II. In compound 5 , one pz and two npz are connected by four AgI ions to build a linear [Ag4(npz)2(pz)]4+ subunit. The PMo12 anions link the linear subunits alternately and a 1D chain is formed. In compound 6 , there exists discrete [Ag2(npz)2(dpz)(H2O)]2+ subunit and Keggin anion. In compound 7 , the Keggin-K inorganic chains are connected by AgI-npz-dpz subunits to form a 2D layer. The adjacent layers are further linked by anions to build a 3D framework. Moreover, we also have investigated the electrochemical and photocatalytic properties of 1 -- 7 .

Acyclic nucleoside phosphonates (ANPs) are of medical relevance and deserve detailed chemical characterization. We focus here on 1-[2-(phosphonomethoxy)ethyl]cytosine (PMEC), (S)-1-[3-hydroxy-2-(ph...

The present work describes the results of treatment of two pentacoordinated copper(II) complexes with 1,10-Phenanthroline (PHEN). During the course of the reaction, in situ generated PHEN-Cu complex has mediated the ligand transformations. In spite of the structural similarities of the precursor complexes used, structurally distinct unusual mixed ligand complexes viz. dichlorido (3-methyl [1,2,4] triazolo[3,4-b] [1,3] benzothiazole) 1,10-phenanthroline copper(II) and dichlorido-µ-N,N-benzimidazolato dibenzimidazole di-1,10-phenanthroline dicopper (II) chloride are formed. These complexes are characterized by IR, ESI-MS, EPR and UV–Vis spectral studies. X-ray crystal structures of both the complexes are described. Further, the observed results have inspired the synthesis of 3-methyl [1,2,4] triazolo[3,4-b] [1,3] benzothiazole, by a new synthetic approach.

A mixed ligand complex of Ni(II) with 3-imidazoline nitroxide and iso-propanol [NiL2(i-C3H7OH)2] is sensitive to atmospheric moisture. It is determined that at a high humidity, the air contacts with the mother solution of the compound in iso-propanol with the precipitated [NiL2(i-C3H7OH)2] crystals leads to their spontaneous transformation into [NiL2(H2O)]·i-C3H7OH crystals whose structure is described in the present paper.

The new mixed ligand copper(II) complexes [Cu(HL)(H2O)(A)]·2H2O (1, NaH2L = sodium (Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)benzenesulfonate, A = dimethylsulfoxide, [Cu(HL)(H2O)(B)] (2, B = 1,3,4-thiadiazol-2-amine), [Cu(HL)(H2O)(Y)]·1/2CH3OH (3, C = hexamethylenetetramine) and [Cu(HR)2(H2O)2](H2L)2 (4, HR = methyl picolinimidate derived from 2-cyanopyridine) were synthesized and characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses. These compounds act as homogenous catalysts for the cyanosilylation reaction of a variety of both aromatic and aliphatic aldehydes with trimethylsilyl cyanide affording the corresponding cyanohydrin trimethylsilyl ethers in high yields (up to 85–99 %) in methanol and at room temperature.

Four isostructural 3D lanthanide metal-organic frameworks (Ln-MOFs) {[Ln(L)(ox)0.5(H2O)2]·H2O}n (Ln = Pr 1, Nd 2, Sm 3 and Eu 4) were constructed by 5-hydroxyisophthalic acid (H2L) and oxalate (ox) through solvothermal methods, which show a (4,5)-connected tcs net with the point symbol of (44·62)(44·66). Compound 4 exhibits an intense red fluorescence in solid state and is an excellent dual-functional recyclable luminescent sensor which can sense acetone and Cu2+ with high sensitivity and selectivity simultaneously.

The mixed ligand copper(I) derivative [Cu(PPh3)2(κ2-O,O″-lact)] (1) (lact = l -(+)-lactate) has been prepared and fully characterized. NMR studies indicated the occurrence of a fluxional behavior involving the lactate anion, in solution. The α-hydroxycarboxylate ligand is responsible for the generation of a catemeric O–H⋯O(CO) H-bonding network that strongly influences the photophysical properties of 1, in the solid state. Indeed, when irradiated with UV light the title compound shows a bright phosphorescence, which as suggested by DFT calculations is strictly related to the abovementioned H-bonding network.

A copper(II) complex of (R)-N-(2-pyridylmethyl)pipecolate (pmpi) was prepared, and its structure was revealed by X-ray crystal structure analysis. Mixed ligand complexes were then prepared from this complex and (R)- and (S)-N-(t-butoxycarbonyl)leucinate (BocLeu). The (R)-BocLeu complex is less soluble in aqueous acetonitrile and more soluble in acetone than the (S)-BocLeu complex, and the reason was discussed on the basis of their structures. Recrystallization of the reaction mixture consisting of Cu(II) ion, pmpi, and (RS)-BocLeu from aqueous acetonitrile gave the (R)-BocLeu complex and that from acetone gave the (S)-BocLeu complex.

The nonferrous metals in blast furnace dust, especially zinc, which used to be categorized as hazardous components for blast furnace, are worthy of recovery in this economy. In this paper, a novel processing for extracting zinc from blast furnace dust by using a coordination reaction between the organic ligand and zinc ions was proposed. When blast furnace dust was leached in a 0.2 M iminodiacetic acid (Ida) solution at 20 °C for 2 h with a liquid-to-solid ratio of 10 mL/g, the leaching rates of zinc and iron were 62.78% and 6.07%, respectively. To accomplish the maximum separation of zinc from iron during the leaching process, a mixed-ligand complex leaching system consisting of Ida as the primary ligand and ammonium as the secondary ligand was developed. The optimal conditions for the leaching process with a mixed-ligand complex leaching system were investigated. We found that 65.58% of zinc was extracted by the solution with Ida:NH 4 Cl:NH 3 ·H 2 O at 0.2:2:2 M and a 20:1 liquid-to-solid ratio at 40 °C for 2 h.