Search results for "Paramagnetic resonance"
showing 10 items of 567 documents
Biological Activity of Flavonoids Copper Complexes
2005
Three flavonoid copper(II) complexes Cu2(quercetin)(CH3COO)3(CH3OH) (1), Cu(anthrarufin)(CH3COO)·1/2H2O (2) and Cu(naringin)(OCH3)(CH3OH)2 (3) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X-band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H2O2 or the superoxide-generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A pro…
A novel Cu(II) dimer containing oxime-hydrazone Schiff base ligands with an unusual mode of coordination: Study of magnetic, autoreduction and soluti…
2013
Abstract Synthesis of a new hydrazone based Schiff base ligand, 3-methylpyrazole-5-carbohydrazone of 2,3-butanedione monoxime (HL) is reported. The reaction of Cu(ClO4)2·6H2O with HL in any ratio in ethanol affords the dinuclear complex [CuL(EtOH)]2(ClO4)2·2H2O (1). An unusual coordination mode of the ligand was observed, in which the ligand forms stable six and five membered chelate rings around the metal centres without enolization of the carbonyl group of the hydrazone moiety. The same coordination behavior of the ligand was observed in its cobalt(III) complex. The reaction of CoCl2·6H2O in methanol with the ligand HL affords the mononuclear complex [CoL2]Cl (2). Both 1 and 2 were charac…
Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism
2009
The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…
Oxidative DNA damage of mixed copper(II) complexes with sulfonamides and 1,10-phenanthroline
2003
Abstract Mixed coordination compounds of Cu(II) with sulfonamides and 1,10-phenanthroline as ligands have been prepared and characterised. Single crystal structural determination of the complex [Cu( N -quinolin-8-yl- p -toluenesulfonamidate) 2 (phen)] shows Cu(II) ions are located in a highly distorted octahedral environment, probably as a consequence of the Jahn–Teller effect. The FT-IR and electronic paramagnetic resonance (EPR) spectra are also discussed. The mixed complexes prepared undergo an extensive DNA cleavage in the presence of ascorbate and hydrogen peroxide. Two of the complexes have higher nucleolytic efficiency than the bis( o -phenanthroline)copper(II) complex.
Synthesis of N-methyl alkylaminomethane-1,1-diphosphonic acids and evaluation of their complex-formation abilities towards copper(II)
2015
Abstract A series of N -methyl alkylaminomethane-1,1-diphosphonic acids ( 3a – g ) with a common tertiary nitrogen atom (CH 3 –N–R) bearing linear or branched alkyl, cycloheptyl or phenylalkyl R substituents was synthesized in the reaction of diethylphosphonate with triethyl orthoformate and secondary amine followed by hydrolysis, and by the Eschweiler–Clarke methylation of the alkylaminomethane-1,1-diphosphonic acids with formic acid and formaldehyde. Complex-formation abilities of 3a – g towards copper(II) in solution were studied by means of pH-potentiometry, ESI-MS spectrometry, UV–Vis and EPR methods. Evaluation of stability constants for the Cu(II) complexes of 3a – g has revealed the…
Copper(II) complexes with sulfonamides derived from 2-picolylamine and their use as chemical nucleases
2006
Reaction between 2-picolylamine (2-aminomethylpyridine) with 2-mesitylenesulfonyl and 4- tert -butylbenzene sulfonyl chlorides leads to the formation of 2,4,6-trimethyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hpmesa) and 4-ter-butyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hptbsa). These compounds react with Cu(II) salts to yield coordination compounds with CuL 2 stoichiometry. The immediate environment of the metal ion is a highly distorted tetrahedron, the sulfonamide ligands acting in a bidentate fashion. Compound Hpmesa crystallizes in monoclinic space group P 2 1 /c (number 14), with Z = 4; complex [Cu(pmesa) 2 ] crystallizes in monoclinic space group P 1 ¯ (number 2), with Z …
N-p-Amino- and N-p-nitro-phenylsulfonyl derivatives of dipeptides, a new family of ligands for copper(II). Potentiometric and spectroscopic studies
1995
The co-ordination ability of four dipeptide analogues substituted on the N-terminal amino group with p-nitrophenylsulfonyl (nps-Ala-Ala and nps-Ala-His) and p-aminophenylsulfonyl (aps-Ala-Ala and aps-Ala-His) groups was studied by potentiometric and spectroscopic (UV/VIS absorption, CD and EPR) techniques. The N-terminal sulfonyl substituent drastically changes the acidity of the sulfonamide proton making nitrogen very efficient in binding to CuII. The sulfonamide nitrogen having pK between 9 and 11 does not need any anchoring binding group to form complexes with CuII. The para substituent on the phenyl ring (amino or nitro) influences very strongly the acidity of the sulfonamide proton. Th…
Synthesis, structure, physicochemical characterization and theoretical evaluation of non-covalent interaction energy of a polymeric copper(II)-hydraz…
2019
Abstract One dimensional polymeric copper-hydrazone complex {[Cu(H0.5L)(µ1,3-SCN)]0.5ClO4·0.5MeOH}n (1) has been synthesized with Cu(ClO4)2·xH2O and N'-(1-(pyridin-2-yl)ethylidene)acetohydrazide (HL) in presence of NaSCN. The ligand and the complex have been characterized by several spectroscopic techniques (IR, UV–Vis and EPR), cyclic voltammetry and the structure of 1 has been determined by single crystal X-ray diffraction. The complex is an infinite one dimensional polymer bridged by thiocyanate. The magneto-structural correlation has been determined and the non-covalent interactions present in the molecule have been energetically evaluated by means of DFT calculations.
Magnetic and Spectroscopic Study on a New Asymmetric Mixed-valence Mn2(II,III) Coordination Compound
2015
A new dinuclear mixed-valence compound [MnIIMnIII(bttpnol)(O2C–C6H4–NO2)2]ClO4 was synthesized by using the asymmetric heptadentate ligand N-(2-hydroxybenzyl)-N,N′,N′-tris(2-pyridylmethyl)-1,3-diaminopropan-2-ol (H2btppnol). One central manganese atom assumes N3O3 and the other N2O4 coordination sphere. Both manganese ions are bridged by the alkoxy-group of the dinucleating ligand and two bidentate carboxylate groups of the nitrobenzoate ligands. The structural data show clearly that MnIII prefers the more oxygen rich donor set. Cyclic voltammetry measurements reveal that the mixed-valence state Mn2(II,III) could be reduced to Mn2(II,II) at E1/2(1) = –0.53 V and oxidized to Mn2(III,III) at …
Oxotris(oxalato)niobate(V) as counterion in cobalt(II) spin-crossover systems
2016
Abstract This work is devoted to the investigation of the thermally induced spin-crossover behavior from a high-spin state (HS, S = 3/2) at higher temperatures to a low-spin phase (LS, S = 1/2) at lower temperatures of the six-coordinate cobalt(II) complex in the compound [Co(terpy)2]3[NbO(C2O4)3]2·3CH3OH·4H2O (2). The crystal structure of 2 together with that of its counterion as tetraphenylarsonium(V) salt (AsPh4)3[NbO(C2O4)3]·9H2O (1) are also included. The spin-crossover process was followed by the thermal variation of the χMT product between 2.0 and 400 K under the warming mode, with the LS configuration being achieved at T ⩽ 200 K and the LS → HS interconversion being incomplete at 4…