RESUMEN
Two new coordination assemblies were prepared by combining the open and close forms of 1,2-bis(5-carboxyl-2-methyl-3-thienyl)perfluorocyclopentene (H2dae) with [Mn2(saltmen)2(H2O)2](PF6)2, where H2saltmen = 2,2'-((1 E,1' E)-((2,3-dimethylbutane-2,3-diyl)bis(azaneylylidene)) bis(methaneylylidene))diphenol. From X-ray diffraction analyses, the complexes had the following formula: [Mn2(saltmen)2(dae-open)] (1open) and [Mn(saltmen)(dae-close)]·H2O·Et3N (1close). Both complexes crystallized in the C2/ c monoclinic space group. In 1open, dae-o2- behaves as a bidentate ligand attached to the outer Mn-saltmen monomer via the oxygen atom of carboxylato groups, whereas in 1close, the dae-c2- ligand behaves as a monodentate ligand attached to the external Mn-saltmen dimer by only one carboxylato group of the photochromic ligand. The complexes showed reversible photochromic responses to UV/vis light and showed single-molecule magnet-like behavior. The relaxation times and energy barriers of the metal complexes are clearly affected by UV/vis irradiation.
RESUMEN
Hg(II), Cd(II) and binuclear Zn(II) complexes derived from the tetradentate N(1)-ethyl-N(2)-(pyridine-2-yl) hydrazine-1, 2-bis (carbothioamide) ligand (H2PET) have been prepared and characterized by conventional techniques. The isolated complexes acquired the formulas, [Hg(HPET)(H2O)2Cl]â H2O, [Cd(HPET)Cl] and [Zn2(HPET)(PET)(OAc)]â H2O, respectively. IR data revealed that the ligand behaves as monobasic tridentate through (CN)py, (C-S) and new (NC)azomethine(∗) groups in both Hg(II) and Cd(II) complexes. In the binuclear Zn(II) complex, the behavior of ligand contains two types, where H2PET acts as dibasic tetradentate via (CN)py, both deprotonated (C-SH) and the new (NC)azomethine(∗) towards two Zn atoms and also it acts as monobasic tridentate via (CS), deprotonated (C-SH) and (CN)py towards the same Zn atoms. An octahedral geometry for Hg(II) complex and tetrahedral geometry for both Cd(II) and Zn(II) complexes were proposed. The bond lengths, bond angles, HOMO, LUMO and dipole moment have been calculated by DFT using materials studio program to confirm the geometry of ligand and its metal complexes. The association constant of the ligand and the stability constants of its complexes as well as the thermodynamic parameters were calculated by pH metric measurements at 298, 308 and 318K in 50% dioxane-water mixture, respectively. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant (using ABTS and DPPH methods), anti-hemolytic, and cytotoxic activities of the compounds have been tested.
Asunto(s)
Antioxidantes/química , Cadmio/química , Complejos de Coordinación/química , Mercurio/química , Semicarbacidas/química , Zinc/química , Animales , Antineoplásicos/química , Antineoplásicos/farmacología , Antioxidantes/farmacología , Cadmio/farmacología , Línea Celular Tumoral , Complejos de Coordinación/farmacología , Concentración de Iones de Hidrógeno , Ligandos , Mercurio/farmacología , Ratones , Modelos Moleculares , Semicarbacidas/farmacología , Zinc/farmacologíaRESUMEN
Cr(III), Mn(II) and Fe(III) complexes derived from the quadruple potential dithione heterocyclic thiosemicarbazide ligand (H(2)PET) have been prepared and characterized by conventional techniques. The isolated complexes were assigned the formulae, [Cr(HPET)(H(2)O)(2)Cl(2)]·3H(2)O, [Mn(HPET)(H(2)O)Cl](2) and [Fe(HPET)(H(2)O)(2)Cl(2)]·H(2)O, respectively. IR data revealed that the ligand behaves as monobasic bidentate through (C=N)(py) and (C-S) groups in both Cr(III) and Fe(III) complexes. In the binuclear Mn(II) complex, H(2)PET acts as NSNS monobasic tetradente via (C=N)(py), (C-S), (C=S) and the new azomethine, (N=C)(*) groups. An octahedral geometry for all complexes was proposed. The bond lengths, bond angles, HOMO, LUMO and dipole moment have been calculated by DFT using materials studio program to confirm the geometry of H(2)PET and its metal complexes. The ligand association constant and the stability constants of its complexes in addition to the thermodynamic parameters were calculated from pH metrically at 298, 308 and 318°K in 50% dioxane-water mixture, respectively. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant (using ABTS and DPPH methods), anti-hemolytic, and cytotoxic activities of the compounds have been tested.