Formation of Cd(II) and Hg(II) complexes in ternary systems with cytidine 5_-monophosphate (CMP) and diamines (en, tn, Put) has been studied. In Hg(II)/CMP/diamine systems the formation of heteroligand compounds is accompanied by the occurrence of non-covalent interactions and the formation of molecular complexes. The presence of polyamine in ternary systems does not change the metal-nucleotide mode of coordination. Similarly as in the binary Hg(II)/CMP system, the metallation involves the donor endocyclic nitrogen N(3) atom and CMP phosphate group. On the other hand, in the Cd(II)/CMP system, the introduction of a polyamine changes the coordination mode of the nucleotide. Phosphate group, inactive in binary systems, takes part in the complexation in ternary systems. In systems of cadmium(II) ions, CMP and diamines, only molecular complexes are formed, in which the polyamine is in the outer coordination sphere. In contrast to Cd(CMP)(H2tn) and Cd(CMP)(H2Put) compounds, in Cd(CMP)(H2en) species the phosphate group of nucleotide does not take part in the metallation, i.e. the metal ion coordinates with CMP, through the atom N(3) of the nucleotide, and the phosphate group is involved in non-covalent interactions with en.
Four new thiocyanato bridged heteropolynuclear complexes with general formula [Cu(diamine)2]3[Cr(NCS)6]2_nH2O, where diamine = N-ethylethylenediamine (N-Et-en), N-isopropylethylenediamine (N-Pri-en), N-methyl-1,3-propanediamine (N-Me-tn), 1,3-diaminopentane (C-Et-tn), were prepared by treatment of corresponding cationic [Cu(diamine)2]2+ complex with [Cr(NCS)6]3-in aqueous solutions. Solid products were formulated as [Cu(N-Et-en)2]3[Cr(NCS)6]2, [Cu(N-Pri-en)2]3[Cr(NCS)6]2_2H2O, [Cu(N-Me-tn)2]3[Cr(NCS)6]2_H2O and [Cu(C-Et-tn)2]3[Cr(NCS)6]2_H2O and characterized by spectroscopic methods, magnetic measurements and thermal analysis. The formation of end-to-end thiocyanato bridges between tetragonal Cu(II) and octahedral Cr(III) is evident from IR and electronic spectra. The EPR spectra measured at room temperature on solid samples show broad, symmetric signal at g = 2.01-2.03. Variable-temperature magnetic susceptibility measurements reveal the presence of weak antiferromagnetic interactions in [Cu(N-Pri-en)2]3[Cr(NCS)6]2_2H2O and [Cu(C-Et-tn)2]3[Cr(NCS)6]2_H2O. Thermal decomposition after dehydration is multistage and yields CuO and CuCrO2 as final products.
Heteropolynuclear complexes of the type [M(diamine)2]3[Cr(NCS)6]2_nH2O, where diamine = N-methylethylenediamine (N-Me-en), 1,2-diaminopropane (pn); M = Ni(II), Cu(II) have been prepared by reacting [Cr(NCS)6]3- with the corresponding cationic [M(diamine)2]2+ complex in an aqueous solution. They have been characterized by elemental analysis, IR, UV-VIS, EPR, variable temperature magnetic susceptibility and thermal analysis. Spectroscopic studies reveal thiocyanato bridges between M(II)-Cr(III) centres. The parameters determined from temperature dependence on magnetic susceptibility (80-300 K) indicate moderate antiferromagnetic interactions for Ni(II)-Cr(III) and negligibly small or very weak ones for Cu(II)-Cr(III) systems. Magnetic studies suggest also presence of diamagnetic Ni(II) ions in the structure of Ni(II)-pn-Cr(III) complex. Thermal analysis shows higher thermal stability of Ni(II)-Cr(III) than Cu(II)-Cr(III) compounds. The process of thermal decomposition after dehydration is multistage and yields NiO + NiCr2O4and CuO + CuCrO2 as final products, respectively.
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Praca dotyczy badań wpływu rodzaju diaminy podwajającej cząsteczką barwnika szeregu dwu- i czterofunkcyjnych czerwieni reaktywnych, pochodnych kwasu 1-amino-8-hydroksynaftaleno-3,6-disulfonowego (kwas H), na ich właściwości fizyko-chemiczne oraz aplikacyjno-użytkowe.
EN
Dissertation concerns researches on influences of diamine doubled the dye molecule of several di- and tetrafunctional reactive red dyes based on 1-amine-8-hydroxynephthalene-3,6-disulphonic acid (H acid) on their physic-chemistry and application characteristic. The investigations showed that substantivity of the dyes resulted from structure of whole dye molecule has significant influences on the degree of dye exhaustion and the fixation yield. The presence in the dye molecule four reactive groups increases the fixation ratio. The presence of the reactive groups differed from reactivity widens range of optimal temperatures and pH of the dyebath.
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