Polymerization electropolymerization

Instead of chemical oxidative polymerization, electropolymerization can also be considered. A recent study shows that slow but efficient electropolymerization is possible if anilinium-exchanged zeolite Y is subjected to oxidative treatment at the electrode-electrolyte interface. Cyclic voltammetric signatures of the polymerization suggest that it occurs mostly through one dimer (p-aminodiphenylamine) which imdergoes oxidative polymerization. Electrochemical polymerization of aniline in zeolite molecular sieves was studied. A zeolite-modified electrode showed shape-selectivity for 12-molybdophosphoric acid. 

Polymerization of thiophenes can be carried out in many different ways and the most commonly used methods can be generalized into three categories (i) electropolymerization, (ii) metal-catalyzed coupling reactions and (iii) chemical oxidative polymerization. Electropolymerization is a widely used method to prepare insoluble films of PTs and represents a simple and efficient way to study the optical and electronic properties of PTs [4], although it is rarely used in the preparation of electroluminescent materials. In 1980, Yamamoto et al. reported the Ni-catalyzed polycondensation of 2,5-dibromothiophene 1. The latter was allowed to react with Mg in THF, affording 2-magnesiobromo-5-bromothiophene 2, which in the presence of Ni(bipy)Cl2 (bipy = 2,2 -bipyridyl) produced PT 3 (Scheme 19.2) [15], In the same year, Lin and Dudek described another example of a metal-catalyzed route to unsubstituted PT 3, exploiting acetylacetonates of Ni, Pd, Co and Fe as catalysts [16]. 

Electrochemical polymerization (electropolymerization) has been recognized as a useful technique for the preparation of pinhole-fiee membranes (1,2) that have found numerous applications in electrocatalysis, amperometric biosensors, etc. These membranes are prepared by the electrodeposition of a polymeric film on the surface of an electrode that is immer in a solution of an appropriate monomer. In order for polymerization to occur, groups that can be electrochemically oxidized or reduced to form a polymer need to be present in the monomer. 

Oxidation of P-nicotinamide adenine dinucleotide (NADH) to NAD+ has attracted much interest from the viewpoint of its role in biosensors reactions. It has been reported that several quinone derivatives and polymerized redox dyes, such as phenoxazine and phenothiazine derivatives, possess catalytic activities for the oxidation of NADH and have been used for dehydrogenase biosensors development [1, 2]. Flavins (contain in chemical structure isoalloxazine ring) are the prosthetic groups responsible for NAD+/NADH conversion in the active sites of some dehydrogenase enzymes. Upon the electropolymerization of flavin derivatives, the effective catalysts of NAD+/NADH regeneration, which mimic the NADH-dehydrogenase activity, would be synthesized [3]. 

Bipyridyl,4-methyl-4 -vinyl-electrochemical polymerization, 6,25 electropolymerization, 6,16 Bipyridyls bis(ZV-oxide) metal complexes, 2, 496 metai complexes, 2, 89, 90,93 steric effects, 2, 90 2,2 -Biquinolyl... 

This means that we can follow the empirical kinetics of the electropolymerization process, at a constant overpotential (Fig. 6), by tracking the weight of the rinsed and dried polymer film,37 41 as we do in homogeneous polymerization processes of conducting or nonconducting poly-... 

These facts are different demonstrations of the same event degradation reactions occur simultaneously with electropolymerization.49-59 These reactions had also been called overoxidation in the literature. The concept is well established in polymer science and consists of those reactions between the pristine polymer and the ambient that promote a deterioration of the original polymeric properties. The electrochemical consequence of a strong degradation is a passivation of the film through a decrease in the electrical conductivity that allows a lower current flow at the same potential than the pristine and nondegraded polymer film did. Passivation is also a well-established concept in the electrochemistry of oxide films or electropainting. 

The final conclusion from the different kinetic studies that simultaneously followed productivity, consumed current, storage capacity of the obtained films, and the current efficiency in generating electroactive polymer in the final film is that any electropolymerization of conducting polymers occurs together a partial degradation of the electroactive polymer. The final film is a mixed material. From the kinetic studies we know the variables that increase or deplete the degradation reaction in relation to the polymerization reaction. 

The final conclusion of this short discussion is that electropolymerization is a fast method (a film of about 5 //mean be obtained by polarization in 1 rnin) that uses a complex mechanism (Fig. 12) in which electropolymerization, cross linking, degradation, and chemical polymerization can coexist to produce a mixed material with a cross-linked and electroactive part and a passive fraction.67-71 However, ifwe control the variables acting on the kinetics of the different simultaneous reactions, the complexity also provides flexibility, allowing us to obtain materials tailored for specific applications. 

In 1979, Diaz et al. produced the first flexible, stable polypyrrole (PPy) film with high conductivity (1(X) Scm ). The substance was polymerized on a Pt-electrode by anodic oxidation in acetonitrile. The then known chemical methods of synthesis " usually produced low conductivity powders from the monomers. By contrast, electropolymerization in organic solvents formed smooth and manageable films of good conductivity. Thus, this technique soon gained general currency, stimulating further electropolymerization experiments with other monomers. In 1982, Tourillon... 

Meanwhile, the R-R coupling (see Sect. 2.2) has evidently found general acceptance as the main reaction path for the electropolymerization of conducting polymers The ionic character of the coupling species explains why polar additives such as anions or solvents with high permittivity accelerate the rate of polymerization and function as catalysts. Thus, electropolymerization of pyrrole is catalyzed in CHjCN by bromide ions or in aqueous solution by 4,5-dihydro-1,3-benzenedisulfonic acid The electrocatalytic influence of water has been known since the work... 

Vinyl substituted bipyridine complexes of ruthenium 9 and osmium 10 can be electropolymerized directly onto electrode surfaces The polymerization is initiated and controlled by stepping or cycling the electrode potential between positive and negative values and it is more successful when the number of vinyl groups in the complexes is increased, as in 77 A series of new vinyl substituted terpyridinyl ligands have recently been synthesized whose iron, cobalt and ruthenium complexes 72 are also susceptible to electropolymerization... 

The ideal electropolymerization scheme (Eq. (5.5.39)) is further complicated by the fact that lower oligomers can react with nucleophilic substances (impurities, electrolyte anions, and solvent) and are thus deactivated for subsequent polymerization. The rate of these undesired side reactions apparently increases with increasing oxidation potential of the monomer, for example, in the series ... 

Dloxygen reduction electrocatalysis by metal macrocycles adsorbed on or bound to electrodes has been an Important area of Investigation (23 ) and has achieved a substantial molecular sophistication in terms of structured design of the macrocyclic catalysts (2A). Since there have been few other electrochemical studies of polymeric porphyrin films, we elected to inspect the dloxygen electrocatalytic efficacy of films of electropolymerized cobalt tetraphenylporphyrins. All the films exhibited some activity, to differing extents, with films of the cobalt tetra(o-aminophenylporphyrin) being the most active (2-4). Curiously, this compound, both as a monomer In solution and as an electropolymerized film, also exhibited two electrochemical waves... 

The development of polypyrroles bearing supported diphosphine ligands protected from oxidation by borane groups has been reported.86 The polymer was produced by the electropolymerization of l-(7V-but-4-yl-pyrrol)-l,2-bis(diphenylphosphinoborane) (62) (Fig. 40). These preformed polymeric films lend themselves to the incorporation... 

Polymeric films of [(//5-C s Me5)M(L)Cl]+complexes (M = Ir, Rh L = pyrrole-substituted bpy or phen) have been coated on an electrode by oxidative electropolymerization. The buildup of hydrido complexes in films is well known 27,28,30 the high electrocatalytic activity of these molecular electrode materials towards dihydrogen evolution in organic and aqueous electrolytes is also well known.25,31 For example, H2 is evolved at —0.55 V vs. SCE at a poly [(j75-C5Me5)-Rh(bpy)Cl]+ film in pH 1 aqueous solution.31... 

Asymmetric ECH with [Rh(L)2(Cl)2]+ complexes containing chiral polypyridyl ligands has been attempted, in homogeneous media (L = (7)-(12)) and at carbon electrodes coated with polymer films prepared by electropolymerization of [Rh(13)2(Cl)2]+ -61 62 The latter catalytic system gave the best results in terms of turnover number (up to 4,750) and enantiomeric excess, (ee) when applied to the hydrogenation of acetophenone (ee 18%) and 2-butanone (ee 10%).62 Polymeric materials derived from the complexes [RhI(bpy)(COD)]+ 36 and [Pd(bpy)2]2+33have also been applied to the ECH reaction. 

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