Poly redox properties

PMo220 4q, is analytically usehil, being formed in the molybdenum test for phosphate ion. Poly- and heteropolymolybdate ions are used in the precipitation of dyes. The protonated forms of the ions are strongly acidic and many poly- and heteropolymolybdate compounds have catalytic activity that is attributable to their acid—base or redox properties. 

There is one report of the redox properties of poly(ferrocenylene) by Oyama et al. noting that the cyclic voltammetry of low molecular weight poly(ferrocenylene) (Mw 900) dissolved in CH2C12 or electrodeposited on Pt gives a broad redox wave with two (or three) peaks between 0.2 and 0.8 V vs. SSCE (70). 

Poly(dithiafulvene)s toward intelligent functional materials have been synthesized [76-78]. An alternating -conjugated copolymer (13) of ferrocene with dithiafulvene showed a unique redox property [76]. Although 13... 

The example considered is the redox polymer, [Os(bpy)2(PVP)ioCl]Cl, where PVP is poly(4-vinylpyridine) and 10 signifies the ratio of pyridine monomer units to metal centers. Figure 5.66 illustrates the structure of this metallopolymer. As discussed previously in Chapter 4, thin films of this material on electrode surfaces can be prepared by solvent evaporation or spin-coating. The voltammetric properties of the polymer-modified electrodes made by using this material are well-defined and are consistent with electrochemically reversible processes [90,91]. The redox properties of these polymers are based on the presence of the pendent redox-active groups, typically those associated with the Os(n/m) couple, since the polymer backbone is not redox-active. In sensing applications, the redox-active site, the osmium complex in this present example, acts as a mediator between a redox-active substrate in solution and the electrode. In this way, such redox-active layers can be used as electrocatalysts, thus giving them widespread use in biosensors. 

The redox properties of the ferrocene unit were also used to control the liquid-crystalline organization of side-chain liquid-crystalline poly(methacrylates) the reduced polymer gave rise to smectic C and smectic A phases whereas the oxidized polymer showed a nematic phase. ... 

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