Phthalocyanines electropolymerization

Figure 5.16. In the case of the Co and Ni complexes the back donation (w (CO))-interaction (A) plays the main role. In the case of the Cu and Zn complexes, the normal binding of CO an a Lewis acid n(CO)-dj2(>zi)(M) interaction (B) is the most important. Reprinted from Figure in the page 810 T.V. Magdesieva, I.V. Zhukov, D.N. Kravchuk, O.A. Semenikhin, L.G. Tomilova, and K.R Butina, Elec-trocatalytic CO2 reduction in methanol catalyzed by mono, di- and electropolymerized phthalocyanine complexes, Russian Chemical Bulletin, 41 (2002) 805-812. With permission of Springer, Kluwer Academic/Plenum Publishers.

In contrast to Co-porphyrin complexes, the direct four-electron reduction of 02 has been only very rarely claimed to be catalyzed by a cobalt phthalocyanine 404 407 In particular cofadal binuclear Co-Pc complexes immobilized on pyrolytic graphite catalyze only the two-electron electroreduction of 02 to H202.408,409 However, recent work has established that an electropolymerized Co-Pc derivative provides a stable four-electron reduction pathway over a wide pH range 410... 

MWCNTs were functionalized with iron phthalocyanines (FePc) to improve the sensitivity towards hydrogen peroxide. A highly sensitive glucose sensor with an FePc-MWCNT electrode based on the immobilization of GOx on poly(o-amino-phenol) (POAP)-electropolymerized electrode surface [219]. A hemin-modified MWCNT electrode to be used as a novel 02 sensor was obtained by adsorption of hemin at MWCNTs and the electrochemical properties of the electrode were characterized by cyclic voltammetry [220]. 

Rodrigues Pereira N, Obirai J, Nyokong T, Bedioui F (2005) Electropolymerized pyrrole-substituted manganese phthalocyanine films for the electroassisted biomimetic catalytic reduction of molecular oxygen. Electroanalysis 17(2) 186-190... 

Polymeric phthalocyanine films prepared from 51a have been investigated as electrocatalysts, in biological applications and as amperometric biosensors [157]. The electropolymerized films exhibited better activities than analogous low molecular weight phthalocyanine films. Some examples are given ... 

Electropolymerization of Amino-Substituted Porphyrins and Phthalocyanines (Section 6.3) [225]... 

Electropolymerization A 1 x 1cm ITO glass plate (purified with soap solution, water, ethanol) was used as the working electrode. A Pt wire counter electrode was purified with H2SO4/H2O2, water and ethanol. The Ag wire as reference electrode was polished and then cleaned with water and ethanol. The solution for the electropolymerization of the phthalocyanine derivative contains 6.30 mg (10 mol) 51a (M = Ni) and 342 mg (10" mol) tetrabutylammonium perchlorate in 10 mL dry DMF, and for the electropolymerization of the porphyrin derivative 49h (M = Zn) 7.4 mg (10 mol) 49h and 342 mg (10 mol) tetrabutylammonium perchlorate in 10 mL dry methylene chloride. 4.5 mL of one of the solutions was filled into the glass cell under a stream of nitrogen. The ITO electrode was connected to a copper holder. The potential was scanned continuously between -0.4 V and +0.8 V for 51a or 0.0 and 0.9 V for 49h, respectively, vs. SCE at a rate of 10 mV/s. For calibration of the reference electrode, the porphyrin derivatives were replaced by ferrocene (E° = 0.4 V vs. SCE) in the same electrolyte. 

Significant Recent Examples of Electropolymerized Films Doped with Phthalocyanines... 

Significant Examples of Electropolymerized Pyrroie-Substituted Phthalocyanines... 

Figure 8.8. (A) Evolution of the cyclic voltammograms of complex Co(II)-32 in DCM containing 0.1 M TBABF4 during repeated successive scans (only 15 scans are shown). Scan rate = 200 mV s , concentration 3 mM, electrode = glassy carbon. (B) Absorption spectra of poly[Co(II)-32] films on ITO electrodes prepared with 30 (curve 1), 60 (curve 2) and 120 (curve 3) electropolymerizing scans. Curve 4 corresponds to Co(II)-32 monomer in DCM solution. Reprinted from ref. [82]. Copyright (2003) Society of Porphyrins Phthalocyanines.

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