Polymer charge state

A Structural characteristic of conducting organic polymers is the conjugation of the chain-linked electroactive monomeric units, i.e. the monomers interact via a 7t-electron system. In this respect they are fundamentally different from redox polymers. Although redox polymers also contain electroactive groups, the polymer backbone is not conjugated. Consequently, and irrespective of their charge state, redox polymers are nonconductors. Their importance for electrochemistry lies mainly in their use as materials for modified el trodes. Redox polymers have been discussed in depth in the literature and will not be included in this review. 

Although these examples demonstrate the feasibility of using calculated values as estimates, several constraints and assumptions must be kept in mind. First, the diffusant molecules are assumed to be in the dilute range where Henry s law applies. Thus, the diffusant molecules are presumed to be in the unassociated form. Furthermore, it is assumed that other materials, such as surfactants, are not present. Self-association or interaction with other molecules will tend to lower the diffusion coefficient. There may be differences in the diffusion coefficient for molecules in the neutral or charged state, which these equations do not account for. Finally, these equations only relate diffusion to the bulk viscosity. Therefore, they do not apply to polymer solutions where microenvironmental viscosity plays a role in diffusion. 

It should also be noted that comparison of quenching efficiency of conjugated polymers with small-molecule fluorophores is complicated and oversimplification can lead to misleading claims of exceptional sensitivity enhancements. In their 2007 review, Swager and co-workers discuss cases where the charge state of the small molecule used for comparison differed fundamentally from the polymer and exceptional quenching efficiencies were inappropriately attributed to super-quenching alone [3], In addition, a polymer will create a different local... 

We mentioned the main models for generation, transfer, and recombination of the charge carriers in polymers. Very often, these models are interwoven. For example, the photogeneration can be considered in the frame of the exciton model and transport in the frame of the hopping one. The concrete nature of the impurity centers, deep and shallow traps, intermediate neutral and charged states are specific for different types of polymers. We will try to take into account these perculiarities for different classes of the macro-molecules materials in the next sections. 

Polaronic and bipolaronic charge states are well known in electroactive polymers, and can be observed in model oligomers with overall delocalization lengths as small as 16 atoms. It has been suggested that localized charge states may be involved in oligomers and polymers having enhanced proper-... 

Originally, the effect of charge state of nanostructures on their catalytic activity was recognized from analysis of the experimental data on the catalytic properties of metallic nanoparticles immobilized in the matrix of a poly-paraxylylene polymer [13-15,24]. It was found that the dependence of the catalytic activity (and, in some cases, of the selectivity) of copper, palladium, and iron nanoparticles on the metal content of these structures has a maximum. This maximum exists not only for the specific (related to unit weight) activity, but also for the absolute activity. More specifically, for copper and... 

In bulk heterojunction solar cells, the metal/semiconductor interface is even more complex. Now the metal comes into contact with two semiconductors, one p-type (typically the polymer) and one n-type (typically the fullerene) semiconductor. A classical electrical characterization technique for studying the occurrence of charged states in the bulk or at the interface of a solar cell is admittance spectroscopy. If a solar cell is considered as a capacitor with capacitance C, the complex admittance Y is given by... 

Bipolaron — Bipolarons are double-charged, spinless quasiparticles introduced in solid state physics [i]. A bipolaron is formed from two -> polarons (charged defects in the solid). For chemists the double-charged states mean dications or dianions, however, bipolarons are not localized sites, they alter and move together with their environment. By the help of the polaron-bipolaron model the high conductivity of -> conducting polymers can be explained. 

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