EPR and Optical Absorption Studies of VO2+ Doped Trisodium Citrate Dihydrate Single Crystals
The electron paramagnetic resonance of VO2+ doped trisodium citrate dihydrate (Na3C6H5O7·2H2O) single crystals and powder has been examined at room temperature. The angular variation of the EPR spectra has shown that two different VO2+ complexes are located in different chemical environments, each environment containing two magnetically inequivalent VO2+ sites in distinct orientations occupying substitutional positions in the lattice and showing a very large angular dependence. The crystalline field around the VO2+ ion is nearly axial. The optical absorption spectrum shows three bands, centered at 24631, 16892, and 12195 cm−1. The spin Hamiltonian parameters and the molecular orbital coefficients are calculated from the EPR and optical data, and result are discussed. Keywords EPR; Trisodium Citrate; Absorption the Spectrum; Vanadyl Ion
Oxovanadium(IV) complexes based on S-alkyl-thiosemicarbazidato ligands. Synthesis, characterization, electrochemical, and antioxidant studies
Reaction of VOSO4 with 2-hydroxy-napthaldeyde-S-R-thiosemicarbazones (R: methyl, ethyl, propyl or allyl) and salicyl aldehyde yielded five-coordinate oxovanadium(IV) complexes having a N1,N4-diarylidene-S-R-thiosemicarbazidato structures. The compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H-NMR, and electron paramagnetic resonance (EPR) spectra. The X-band EPR signals were recorded from powder forms and also in solution. All the complexes have a single asymmetric line shape and theoretical fit studies prove the presence of axial symmetry around the paramagnetic vanadium ions. A computer simulation of the EPR spectrum of each complex was carried out to derive the related EPR parameters. Cyclic voltammograms of the complexes exhibited two metal-based reversible redox peaks around 500 and −800 mV corresponding to one electron oxidation/reduction of VIVO/VVO and VIVO/VIIIO, respectively. The reductive response in the 50–350 mV region was assigned to ligand reduction. Antioxidant activities of the compounds were determined with CUPric Reducing Antioxidant Capacity, 2,2-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid, and 1,1-diphenyl-2-picrylhydrazyl assays. The test results indicated that the antioxidant capacity of the compounds increases with the carbon number of saturated hydrocarbon chain on sulfur atom. GRAPHICAL ABSTRACT
Optical rotatory dispersion and absolute configuration—III
Abstract Optical rotatory dispersion measurements on pyrrolidine, piperidine, and tetrahydro-isoquinoline alkaloids indicate that the absolute configuration of the α-asymmetric center may be assigned directly from the dispersion curve, provided either that the nitrogen atom is not protonated, or that the compound contains a chromophore absorbing above 200 mμ.