Search results for "Paramagnetic"

Two new supramolecular architectures of singly phenoxo-bridged copper(II) and doubly phenoxo-bridged manganese(II) complexes derived from an unusual …

2009

International audience; Two new coordination complexes {[(L)Cu2('-L)(NO3)(CH3OH)0.3(H2O)0.7]·NO3}[Cu(L)(NO3)(CH3OH)] (1) and [Mn2(-L)2(H2O)(1-N3)2(CH3OH)] (2) derived from (E)-N-(2-hydroxy-3-methoxybenzylidene)acetohydrazide [LH] have been synthesized. The new potentially tetradentate ONOO donor hydrazone ligand [LH] has shown considerable metal ion selective phenoxo bridging in 1 and 2. It has coordinated copper(II) ions in its tridentate as well as in tetradentate fashion whereas for manganese(II) ions it solely showed its tetradentate character. In 1 the two adjacent pentacoordinate copper(II) centers are connected by a rare single phenoxo linkage of the hydrazone ligand whereas 2 is a d…

Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization.

2005

The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Cl- anion on the cobalt corrole…

Crystal and molecular structure of tris(mepirizole) copper(II) hexafluorophosphate [mepirizole = 4-methoxy-2-5-methoxy-3-methyl-1h-pyrazol-1-yl)-6-me…

1992

Abstract The X-ray crystal structure of Cu(mep)3(PF6)2 [mep = mepirizole or 4-methoxy-2-(5-methoxy-3-methyl-1H-pyrazol-1-yl)-6 methylpyrimidine], obtained from stoichiometric quantities of mep, Cu(NO3)2 and KPF6 in water/ethanol solution was determined. The trisbidentate Cu(mep)32+ cation is observed for the first time. One of the three mep molecules is disordered over two sets of positions related by crystallographic symmetry. The mep molecules exhibit two different conformations A and B: conformation B, which is observed for the first time, derives from the usual conformation A by rotating the pyrimidine ring by 180° around the central CN bond and rotating by 180° the methoxy group bonde…

Coordination abilities of l-glutamic acid γ-monohydroxamic acid towards copper(II) in the absence and presence of some aliphatic amines

2012

Abstract Solution equilibrium studies on the Cu 2+ –(A)–(Glu-γ-ha) ternary systems ((A) = polyamine: ethylenediamine (en), diethylenetriamine (dien), N , N , N ′, N ″, N ″-pentamethyldiethylenetriamine (Me 5 dien); (Glu-γ-ha) =  l -glutamic-γ-hydroxamic acid) have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods. The obtained results suggest the formation of the heteroligand complexes with [Cu(A)(Glu-γ-ha)] + stoichiometry in all studied systems. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(Glu-γ-ha)] + species in which Glu-γ-ha acts as a tridentate ligand, the geometry slightly deviated from square pyramidal for [Cu(dien)(Glu-γ-ha)]…

Structural, magnetic, and spectroscopic comparative studies on four new derivatives of DIMMAL (2-di1H-2-imidazolylmethylmalonate): a novel generator …

2005

This paper reports the synthesis, structure solution, and magnetic characterization of four new DIMMAL-containing compounds (H 2 DIMMAL = 2-di1H-2-imidazolylmethylmalonic acid), H 2 DIMMAL.H 2 O (1), Na 2 (DIMMAL).5H 2 O (2), [Cu(HDIMMAL) 2 ] (3), and [Cu 2 (DIMMAL) 2 (H 2 O) 2 ].2H 2 O (4). Compound 1, containing two carboxylates and two protonated imidazole rings, adopts the dizwitterion configuration. These monohydrate MBBs pack together into a 3D array driven, as in the other three cases herein reported, by a combination of multiple-path H-bonds and aromatic-aromatic interactions. Compound 2 consists of centrosymmetric Na + tetramers in which four NaO 6 distorted octahedra are interconn…

Dinitrogen complexation with main group radicals

2011

In this report we present data from hyperfine sublevel correlation spectroscopy (HYSCORE), an electron paramagnetic resonance (EPR) spectroscopic technique, that reveals weak but distinct interactions between several main group element radicals and physically dissolved dinitrogen in solution. These interactions are the basis for a well-defined coordination of N2 to the paramagnetic centers. The complexes formed are primarily of the van der Waals-type but also feature a non-negligible orbital overlap between dinitrogen and the radicals' SOMO. Our spectroscopic findings are strongly supported by experiments with isotope-labeled 15N2, spectral simulations and quantum chemical and density funct…

1980

Formation and behaviour of radiation induced free radicals in statistical copolymers from vinyl hydrosulfide and styrene (1:1, 1:4, and 1:10) were investigated by means of ESR spectroscopy. The corresponding homopolymers were also included in these studies. After γ-irradiation of the copolymers at 77 K and subsequent annealing to 293 K it was possible to detect thio radicals. Their relative yields were found to increase with increasing styrene content. Investigations regarding the thermal behaviour of the radiation induced radicals in the copolymers allowed the assumption of two mechanisms responsible for the formation of the thio radicals: First, the formation takes place via ion radicals …

DNA interaction of new copper(II) complexes with sulfonamides as ligands

2007

New copper(II) complexes with sulfonamide ligands have been prepared and characterized. Sulfonamide ligands were prepared through a reaction between 8-aminoquinoline and either 2-mesitylene (Hqmesa), 4-tert-butylbenzene (Hqtbsa), or alpha-toluene (Halphaqtsa) sulfonyl chlorides. The structural analysis carried out for complex [Cu(alphaqtsa)(2)] indicated that the local environment of the Cu(II) cation is between a square planar and a tetrahedral geometry, with stacking of the benzene rings of the sulfonyl ligands between neighbor molecules. Powder EPR spectra at room temperature gave rhombic spectra for the [Cu(alphaqtsa)(2)] and [Cu(qmesa)(2)] complexes and an axial spectrum for the [Cu(qt…

EPR spectroscopic characterization of persistent germyl-substituted Pb(III)- and Sn(III)-radicals.

2010

In this report we present the synthesis and the detailed electron paramagnetic resonance (EPR) spectroscopic characterization of novel trivalent lead- and tin-based radicals comprising sterically demanding germyl substituents. The investigated radicals are derived from the recently reported trihypersilyl-substituted tetryl radicals *PbHyp3 and *SnHyp3. The tetryl radicals *Pb(Ge(SiMe3)3)3 (8), *Pb(Ge(SiMe3)3)2Si(SiMe3)3 (9), *PbGe(SiMe3)3(Si(SiMe3)3)2 (10), and *Sn(Ge(SiMe3)3)3 (11) show substitution patterns derived from stepwise (9, 10) or complete (8, 11) substitution of hypersilyl groups (Hyp = Si(SiMe3)3) in *PbHyp3 and *SnHyp3 by homologous hypergermyl groups (Hge = Ge(SiMe3)3). They …

The 5/2,3/2 Spin Admixture in the Chloroiron(III) Derivative of the Sterically Crowded 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin

1999

Despite similar ring deformations in solution and in the solid state, the chloroiron(III) derivative of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin ([FeCl(oetpp)], shown schematically) prepared in this study exhibits only a very weak quantum-mechanical admixture of spin S=3/2 (only 4-10 %) with spin S=5/2. In contrast, for the variety of [FeCl(oetpp)] studied earlier by other researchers a 40 % contribution of the S=3/2 state was found.