Electrochemistry of manganese phthalocyanine in nonaqueous media

Lever, Annabelle; Minor, P. C.; Wilshire, J. P.

doi:10.1021/ic50222a035

Cited by 101 publications

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“…Curve 1 in Figure 2c is related to the thinner film (prepared by 15 electropolymerizing scans). It shows a reversible couple of peaks centred at À 0.17 V (vs. Ag/AgCl) which can be related to the Mn III /Mn II redox process of the phthalocyanine, by reference to the behaviour of the monomer complex either in DCM (data not shown) or in DMF [20] solution, and to previously reported studies of Mn phthalocyanine in various conditions [21]. It is noteworthy that there is a loss of reversibility of the observed redox process, as the film grows (curves 2 and 3).…”

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confidence: 59%

Electropolymerized Pyrrole-Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen

et al. 2005

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We report for the first time on the electroassisted biomimetic activation of molecular oxygen by a newly prepared electropolymerized polypyrrole-manganese phthalocyanine film. The prepared films and their intervention in the electroassisted catalytic reduction of molecular oxygen were analyzed by cyclic voltammetry and UV-visible spectrophotometry on optically transparent electrodes. The obtained results demonstrate the probable existence of the key-steps responsible for the suggested formation of the highly reactive manganese oxo intermediate. Keywords:Manganese phthalocyanine, Polypyrrole film, Electropolymerization, Molecular oxygen, SpectroelectrochemistryThe development of efficient chemical systems operating according to the catalytic cycle of substrate oxidation by cytochrome P-450, which involves the high valent metal-oxo intermediate, is a subject of intense research [1 -4]. Most of the reported models use iron or manganese porphyrins or Schiff bases and iodosylbenzene, hydrogen peroxide and alkylhydroperoxides, peroxyacids as oxygen donors [2]. In the last decade, we and others have shown that the strategy for mimicking the enzymatic system can be elegantly tuned by using polymeric porphyrins designed from electropolymerizable suitably substituted-pyrrole complexes [5]. Also, we and others have provided the first and rare examples involving the electroassisted activation of molecular oxygen by manganese porphyrins and Schiff bases as enzyme models, either in solution or supported electropolymerized films, for the catalytic oxidation of selected hydrocarbons [6 -17]. In that case, the use of "activator" such as acetic acid or benzoic anhydride is needed and the proposed mechanism suggested the generation of the metal-oxo active species, in view of the modifications of the cyclic and hydrodynamic voltammograms [6 -19].In a very recent paper, we have reported on the synthesis and spectroelectrochemical characterization of a new family of pyrrole-substituted metallophthalocyanines [20]. As part of our work devoted to the electrochemical elaboration and characterization of biomimetic models, we are reporting here on the first results obtained with an electropolymerizable pyrrole-substituted manganese phthalocyanine, noted Mn(TPhPyrPc) (see structure, Fig. 1). We show preliminary study of the electrochemical preparation of the polypyrrole-based manganese phthalocyanine films and the characterization by cyclic voltammetry and UV-visible spectrophotometry. We also provide first insights in the intervention of the manganese center in the electroassisted catalytic reduction of molecular oxygen in dichloromethane.Electropolymerization of Mn III TPhPyrPc was achieved on a vitreous carbon electrode in dichloromethane (DCM) þ 0.1 mol L À1Bu 4 NBF 4 solution containing 3 mmol L À1 of the complex by repeated potential scans between 0.2 Vand þ 1.2 V (vs. Ag/AgCl) at 200 mV/s, as we have recently shown in the case of the cobalt analog [20]. The build up of the electropolymerized film can be followed by the increa...

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confidence: 59%

Electropolymerized Pyrrole-Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen

et al. 2005

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“…Metal phthalocyanine species exhibit rich electrochemical behavior due to the accessibility of a range of oxidation states centred on the ligand, and, for many transition metal ions, on the metal [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Further, phthalocyanine species have been modified by the use of a wide range of substituents at the peripheral benzene rings [15].…”

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Derivation of metallophthalocyanine redox potentials via Hammett parameter analysis

Lever

1993

Inorganica Chimica Acta

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“…The remaining reductions (Red 3 at −1.30 V and Red 4 at −1.81 V) are proposed as Pc based processes. These assignments are in agreements with the similar MnPcs in the literature . In situ spectral changes also supported these assignments.…”

Section: Resultsmentioning

confidence: 88%

Electropolymerization of Metallophthalocyanines Carrying Redox Active Metal Centers and their Electrochemical Pesticide Sensing Application

2017

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In this study, modified electrodes were constructed with the electropolymerization of metallophthalocyanines (MPcs) carrying redox active metal cations and electropolymerizable substituents. Then these electrodes were tested as selective and sensitive electrochemical pesticide sensors. Incorporation of the redox active Co(II) (CoPc(MOR‐NAF)), Cl–Mn(III) (MnPc(MOR‐NAF)), and Ti(IV)O (TiOPc(MOR‐NAF)) metal cations into Pc cavity increased the redox activity of Pc ring. Moreover, redox active and electropolymerizable 5‐{[(1E)‐(4‐morpholin‐4‐ylphenyl)methylene]amino}‐1‐naphthoxy substituents (MOR‐NAF) on the Pc ring triggered coating of the complexes on the electrode surface with the electropolymerization reactions. Therefore, modified electrodes GCE/MPc(MOR‐NAF) were constructed with the electropolymerizations of MPcs. These electrodes illustrated reasonable redox activity and conductivity for the potential applications in different fields of the electrochemical technologies. Pesticide sensing measurements indicated that changing the metal center of the complexes significantly altered their sensing activities. Among the complexes, GCE/CoPc(MOR‐NAF) electrode behaved as the most sensitive and selective electrode and it sensed the parathion with good selectivity and sensitivity. GCE/CoPc(MOR‐NAF) electrode showed a wider linear range (0.075‐5.75 μmoldm−3) and smaller LOD (0.025 μmoldm−3) and higher sensitivity (3.46 Acm−2M−1) for the parathion sensing. Although GCE/TiOPc(MOR‐NAF) electrode also sensed the parathion with a high sensitivity, its selectivity was poor and the linear range of this sensing was very narrow. Differently GCE/Cl–MnPc(MOR‐NAF) electrode only sensed eserine with reasonably sensitivity.

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Electrochemistry of manganese phthalocyanine in nonaqueous media

Cited by 101 publications

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Electropolymerized Pyrrole-Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen

Electropolymerized Pyrrole-Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen

Derivation of metallophthalocyanine redox potentials via Hammett parameter analysis

Electropolymerization of Metallophthalocyanines Carrying Redox Active Metal Centers and their Electrochemical Pesticide Sensing Application

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