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Electroactive polymeric material with condensed structure on the basis of magnesium(II) polyporphine

Abstract : Previous publication of the authors presented evidences that electroch emical oxidation of Mg(II) porphine (fully unsubstituted porphyrin, MgP) in acetonitrile (AN) at a very low potential leads to deposition of films at electrode surface corresponding to typical electroactive polymers, with their reversible transition betwee n the electronconducting and insulating states depending on the electrode potential/oxidation level ("film of type I"). It is demonstrated in the actual publication that these films in contact with a monomer-free solution are subject to an irreversible transformation to quite a different material ("film of type II") under the influence of a higher positive potential (above 0.5-0.6 V vs. Ag/Ag + in AN). Films with the same properties may also be obtained directly by electrooxidation of the monomer, MgP, at a sufficiently high potential. Films of type II possess a high redox activity and electronic conductivity within the whole potential interval of above 3 V in the width. Their grayish color is related to a constant absorption intensity within the whole range of wavelengths studied (320-1000 nm). On the basis of a combination of experimental observations (ATR IR ad XPS) and literature data the molecular structure of this new material is assumed to be polymer chains of directly linked porphine units (with a par tial loss of Mg cations), probably with multiple bonds (meso-meso and β-β type) between the neighboring units.
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Submitted on : Monday, November 8, 2021 - 10:44:26 PM
Last modification on : Thursday, January 20, 2022 - 11:38:03 AM


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Mikhail Vorotyntsev, Dmitry Konev, Charles Devillers, Igor Bezverkhyy, Olivier Heintz. Electroactive polymeric material with condensed structure on the basis of magnesium(II) polyporphine. Electrochimica Acta, Elsevier, 2011, 56 (10), pp.3436-3442. ⟨10.1016/j.electacta.2010.10.039⟩. ⟨hal-03420011⟩



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