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Ironporphyrins characterization studies by paramagnetic resonance and UV-vis techniques

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Author(s):
Ednalva Aparecida Vidoto
Total Authors: 1
Document type: Doctoral Thesis
Press: São Carlos.
Institution: Universidade de São Paulo (USP). Instituto de Física de São Carlos (IFSC/BT)
Defense date:
Examining board members:
Otaciro Rangel Nascimento; Eduardo Ernesto Castellano; Amando Siuiti Ito; Marcel Tabak; Maria Cristina Terrile
Advisor: Otaciro Rangel Nascimento
Abstract

Synthetic iron porphyrins are complex systems that have been largely studied. Difficulties to obtain structural information, chemical reactions and ligands of the central ions have been a subject to investigate details of these systems. In this work, a systematic characterization of one series of fluorophenyl iron porphyrins is presented. Mono-, di-, tri- and tetrafluorophenyl substituents called FeTF5PP, FeTF10PP, FeTF15PP, and FeTF20PP, respectively, are included in this series. Iron porphyrins were studied as a function of dichloromethane, methanol solvents and several of their mixture in volume. These systems were characterized by Ultraviolet- Visible and Electron Paramagnetic Resonance Spectroscopes. From iron porphyrin solutions, dissolved in dichloromethane, aliquots of methanol were added up to 50% in volume of these two solvents. With this titration, we found different species because of the methanol coordination to the iron porphyrins. We also observed the structures modification revealed by the EPR spectroscopy, as a function of different numbers of fluorophenyl substituents. The EPR spectroscopy also revealed the existence of the super hyperfine interactions not observed before. It was found for FeTFloPP between the central ion and the axial ligand chlorine Cl - ion, besides the hyperfine interaction between iron and the nitrogen of the pyrrole ring. For FeTF20PP only the super hyperfine interaction, Fe-C1 was found. These interactions were not observed for the other iron porphyrins (AU)