Conductive Electroactive Polymers substitution

Tetra(o-aminophenyl)porphyrin, H-Co-Nl TPP, can for the purpose of electrochemical polymerization be simplistically viewed as four aniline molecules with a common porphyrin substituent, and one expects that their oxidation should form a "poly(aniline)" matrix with embedded porphyrin sites. The pattern of cyclic voltammetric oxidative ECP (1) of this functionalized metal complex is shown in Fig. 2A. The growing current-potential envelope represents accumulation of a polymer film that is electroactive and conducts electrons at the potentials needed to continuously oxidize fresh monomer that diffuses in from the bulk solution. If the film were not fully electroactive at this potential, since the film is a dense membrane barrier that prevents monomer from reaching the electrode, film growth would soon cease and the electrode would become passified. This was the case for the phenolically substituted porphyrin in Fig. 1. 

In the most important series of polymers of this type, the metallotetraphenylporphyrins, a metalloporphyrin ring bears four substituted phenylene groups X, as is shown in 7.19. The metals M in the structure are typically iron, cobalt, or nickel cations, and the substituents on the phenylene groups include -NH2, -NR2, and -OH. These polymers are generally insoluble. Some have been prepared by electro-oxidative polymerizations in the form of electroactive films on electrode surfaces.79 The cobalt-metallated polymer is of particular interest since it is an electrocatalyst for the reduction of dioxygen. Films of poly(trisbipyridine)-metal complexes also have interesting electrochemical properties, in particular electrochromism and electrical conductivity.78 The closely related polymer, poly(2-vinylpyridine), also forms metal complexes, for example with copper(II) chloride.80... 

In all cases, the films were obtained by oxidative electropolymerization of the cited substituted complexes from organic or aqueous solutions. The mechanism of metalloporphyrin Him formation was suggested to be a radical-cation induced polymerization of the substituents on the periphery of the macrocycle. As it was reported for the case of polypyrrole-based materials ", cyclic voltammetry and UV-visible spectroscopy with optically transparent electrodes were extensively used to provide information on the polymeric films (electroactivity, photometric properties, chemical stability, conductivity, etc.). Based on the available data, it appears that the electrochemical polymerization of the substituted complexes leads to well-structured multilayer films. It also appears that the low conductivity of the formed films, combined with the cross-linking effects due to the steric hindrance induced by the macrocyclic Ugand, confers to these materials a certain number of limitations such as the limited continuous growth of the polymers due to the absence of electronic conductivity of the films. Indeed, the charge transport in many of these films acts only by electron-hopping process between porphyrin sites. 

Structural modifications of polyaniline have mainly been exploited to achieve improved processability and environmental stability. In general, the substituted polyanilines can be obtained via oxidative polymerization of the corresponding monomer. However, inductive and steric effects can make such monomers difficult to polymerize [42]. Several substituted polyanilines have been prepared by varying the nature (alkyl, alkoxy, halogen, etc.) and the position (2- vs 3-, 5-positions) of the substituent [24, 27-32, 34, 37, 43, 44]. These studies have shown that regardless of the nature and position of the substituent group, there is an adverse effect on polymerization and the properties of the polymer such as conductivity and electroactivity. To overcome these limitations, various synthetic methods have been developed to prepare self-doped sulfonated polyanilines. These methods involve controlled postpolymerization modifications by synthetic reactions on the whole polymer and copolymerization of less reactive monomers with aniline as described below. 

Conductive polymer films on electrodes have been prepared by electrochemical polymerization of electroactive monomers such as a pyrrole-substituted mediator, or by evaporating solutions containing preformed polymer. Examples of electrocatalyses reported include the oxidation of alcohols by pyrrole-substituted 2,2,5,5-tetramethyl-3-pyrroline-l-oxyl [26] and organohalide de-halogenation by pyrrole-substituted 4,4 -bipyridinium salt [27]. The preparation of mediator-modified electrode by evaporating solutions of preformed polymers was carried out by dip-coating polymers including mediators on electrode surface or by covalent attachment of mediators to dip-coated polymers on electrode surfaces. Examples of the former electrocatalyses are selected from the several reports on the oxidation of NADH by dopamine... 

The electrochemical polymerization of Ti-electron-rich aromatics, such as aniline, pyrrole and thiophene, to obtain electrically conducting polymers is well-known. Some reports describe the polymerization of amino-, pyrrolyl- and hydroxy-substituted tetraphenylporphyrins and suitable substituted phthalocyanines (for reviews see [230,231]) (anodic electropolymerization of 2,9,16,23-tetraaminophthalocyanine (M = Co(II), Ni(II)) [231,232] and 2,9,16,23-tetra(l-pyrrolylalkyleneoxy)phthalocyanines (M = 2H, Zn(II), Co(II) [232])) under formation of polymers 53 and 54 shown as idealized structures. Depending on the reaction conditions the film thicknesses are between around 50 nm and several pm. The films remain electroactive at the electrochemical potential so that oxidation or reduction current envelope grows with each successive potential cycle. Electrochromism, redox mediation and electrocatalysis of the electrically conducting films are summarized in [230,231]. 

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