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    Antitumor effects of novel nickel-hydrazone complexes in lung cancer cells
    (Royal Soc Chemistry, 2020) Ay, Burak; Sahin, Onur; Demir, Burcu Saygideger; Saygideger, Yasemin; Lopez-de-Luzuriaga, Jose M.; Mahmoudi, Ghodrat; Safin, Damir A.
    In this work we have synthesized and characterized two new mononuclear nickel(ii) complexes [NiLI]center dot CH3CN (1 center dot CH3CN) and [Ni(H2LII)(NCS)(2)]center dot 0.5H(2)O (2 center dot 0.5H(2)O), fabricated from a mixture of Ni(NO3)(2) and KNCS with N ',N '''-(1,2-diphenylethane-1,2-diylidene)di(picolinohydrazide) (H2LI) and 1,2-diphenyl-1,2-bis(((pyridin-2-yl)methylene)hydrazono)ethane (Lig), of which the latter one was transformed in situ into methyl-N-(3,4-diphenyl-5-(pyridin-2-yl)-4,5-dihydro-1H-pyrazol-4-yl)picolinohydrazonate (H2LII) upon coordination to the metal center under synthetic conditions in methanol. The nickel(ii) atom in the structure of complex 1 is tetracoordinated and in a N3O geometry, formed by one doubly deprotonated ligand L-I, linked through the pyridyl nitrogen atom, one of the amide nitrogen atoms, one of the imine nitrogen atoms and one of the carbonyl oxygen atoms, yielding an almost perfect square-planar coordination environment. The crystal packing of 1 center dot CH3CN is dictated by a set of weak non-covalent interactions, namely C-HMIDLINE HORIZONTAL ELLIPSISO, C-HMIDLINE HORIZONTAL ELLIPSIS pi and pi MIDLINE HORIZONTAL ELLIPSIS pi stacking interactions. The asymmetric unit of complex 2 center dot 0.5H(2)O contains two crystallographically independent complex molecules [Ni(H2LII)(NCS)(2)], namely 2-I and 2-II, which are geometrically very similar. The metal atoms are six-coordinated and in a N-6 geometry, formed by one neutral ligand H2LII, linked through two pyridyl nitrogen atoms, one amine nitrogen atom from the pyrazole ring, one imidate nitrogen and two NCS- nitrogen atoms, yielding a distorted octahedral coordination environment. The crystal packing of 2 center dot CH3CN is mainly dictated by intermolecular N-HMIDLINE HORIZONTAL ELLIPSISN, N-HMIDLINE HORIZONTAL ELLIPSISS and O-HMIDLINE HORIZONTAL ELLIPSISS hydrogen bonds, yielding a 3D framework, which is further stabilized by intermolecular pi MIDLINE HORIZONTAL ELLIPSIS pi stacking interactions. From the topological point of view, the hydrogen bonded 3D framework of 2 center dot 0.5H(2)O reveals a four-connected uninodal crb/BCT; 4/4/t5; sqc184 topology. In in vitro experiments, both complexes showed dose dependent cytotoxicity and killed A549 lung cancer cells via an apoptotic pathway. Both complexes also reduced the expression of Snail2, leading to an increase in E-cadherin expression and inhibiting the motility of the cells. The complexes were determined as potential antitumor agents.
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    Öğe
    Novel lanthanide(III) complex [LaL2(NO3) (H2O)2]•5H2O with 2-pyridine carboxaldehyde isonicotinoyl hydrazine exhibiting a 3D supramolecular topology 3,6T49
    (Elsevier, 2020) Ay, Burak; Yildiz, Emel; Sahin, Onur; Mahmoudi, Ghodrat; Kubicki, Maciej; Perumal, Venkatesan; Percino, Judith
    A new coordination compound, namely [LaL2(NO3)(H2O)(2)]center dot 5H(2)O (1), has successfully been synthesized from La(NO3)(3)center dot 6H(2)O, 2-pyridinecarboxaldehyde isonicotinoylhydrazone (HL) and NaOH, as a deprotonated agent, in the CH3OH medium under mild solvothermal conditions at 120 degrees C. Both HL and 1 were characterized by FTIR spectroscopy and elemental analysis. Complex 1 was also studied by the simultaneous TG-DSC, powder and single crystal X-ray diffraction analyses. According to the single crystal diffraction analysis, the lanthanum (III) ion adopts a deca-coordinated mode, and five lattice water molecules exist in the asymmetric unit. The crystal structure of 1 is mainly stabilized by strong O-H center dot center dot center dot N and O-H center dot center dot center dot O and weak pi/pi and C-H center dot center dot center dot p interactions. As a result of hydrogen bonding, a 3D supramolecular structure is formed with a binodal (3,6)-connected network with a 3,6T49 topology having point symbol of {4 center dot 6(2)}{4(7)center dot 6(5)center dot 8(3)}. As evidenced from the Hirshfeld surface analysis of [LaL2(NO3)(H2O)(2)], intermolecular H center dot center dot center dot H (40.1%), H center dot center dot center dot C (15.4%), H center dot center dot center dot N (12.2%) and H center dot center dot center dot O (20.3%) contacts occupy an overwhelming majority of a molecular surface of the complex molecule. Highly favoured intermolecular C center dot center dot center dot C (6.5%) and C center dot center dot center dot N (4.0%) contacts also play a vital role in the supramolecular structure of complex. Upon heating, complex 1 decomposes in few steps, consistently losing lattice water molecules, coordinated water molecules followed by the decomposition of organic ligands, yielding La(NO3)(3) followed by the formation of a final residue La2O3. (C) 2020 Elsevier B.V. All rights reserved.
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    Öğe
    One-Pot hydrothermal synthesis of 1D copper (II) coordination polymers involving in-situ decarboxylation
    (Elsevier, 2019) Ay, Burak; Sahin, Onur; Yildiz, Emel
    One-Dimensional Copper(II) coordination polymers with the formula [Cu(2-pyc)(2)](n)center dot nH(2)O (1) (2-Hpyc: Picolinic acid) and [Cu(1,10-phen)(SO4)(H2O)(2)](n) (2) (1,10-phen: 1,10-phenanthroline) have been co-synthesized under hydrothermal conditions in the same medium. The coordination polymers characterized by elemental analysis, FT-IR spectroscopy, TG analysis, ICP-OES, PXRD and single crystal X-ray diffraction. The compound 1 crystallizes in triclinic system, space group P-1, the compound 2 crystallizes in monoclinic system, space group C2/c. In 1, the Cu(II) ions are further joined by picolinic acid ligands, generating 1D coordination polymer running parallel to the [100] direction, while the Cu(II) ions are further joined by sulfate ligands, generating 1D coordination polymer running parallel to the [001] direction in 2. Notably, the 2-Hpyc ligand is in situ generated by decarboxylation of the 2,6-pyridinedicarboxylic (2,6-pydc) acid ligand under hydrothermal conditions. Thermal stability, luminescence and electrical conductivity properties of 1 and 2 have been investigated.
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    Öğe
    Synthesis, characterization, electrical conductivity and luminescence properties of two copper(II) complexes with tridentate N2O chelating ligands containing imine bond
    (Elsevier Science Bv, 2018) Gonul, Ilyas; Ay, Burak; Karaca, Serkan; Sahin, Onur; Serin, Selahattin
    In the present study, we describe the synthesis and characterization of two tridentate N2O donor ligands, namely, (E)-2-(((2-(diethylamino)ethyl)imino)methyl)-6-methoxyphenol (HL1) and (E)-2-(((2-(diethylamino)ethyl)imino)methyl)-6-ethoxyphenol (HL2), and their copper(II) complexes, [Cu(L-1)(CH3COO)] (1), [Cu(L-2)(CH3COO)] (2). They have been synthesized under conventional methods and characterized by elemental analysis, FTIR, H-1 and C-13 NMR, ICP-OES, TGA and GC/MS analysis. For the morphological analysis field emission scanning electron microscopy (FESEM) was used. The geometry of the copper(II) complexes was determined by single crystal X-ray diffraction analysis. The copper(II) ions are in distorted square-pyramidal coordination environments. Complexes crystallize in monoclinic space group, P2(1)/c. The electrical conductivity and luminescence properties of 1-2 have been investigated. (C) 2017 Elsevier B.V. All rights reserved.