Cation-radicals definition

An important point is that the electrochemically driven charge transport in these polymeric materials is not dependent on the presence of mixed valence interactions which are well known to give rise to electronic conductivity — in a number of cation radical crystalline salts. This is clearly seen from the absorption spectrum of the electrochemically oxidized pyrazoline films (Figure 8) which show no evidence for the mixed valence states that are the structural electronic prerequisites for electrical conductivity in the crystalline salts. A more definitive confirmation of this point is provided by the absorption spectrum (Figure 10) of electrochemically oxidized TTF polymer films which shows... 

Other reactions of aromatic hydrocarbon anion radicals and amine cation radicals lead to exciplex emission, particularly in nonpolar solvents [15], Luminescence from exciplexes is most definitively observed in systems for which the redox reaction is energetically unable to yield a localized excited state. The free energy of exciplex formation, jE exc, is associated with solvation and geometry optimization in the encounter complex of and A+. 

Russell and co-workers have obtained cation-radicals in the 1,2-dithiete system. Such radicals are cyclic, conjugated within the heterocycle, and possess (4 -P 1) electrons, with = 1 they are consequently heteroaromatic witliin the definition given in the introduction to Part I. 3,4-Dimethyl-l,2-dithiete cation radical 89 (R = R = Me) was obtained by treatment of acetoin in sulfuric acid with sulfide ion. The radical is persistent at ambient temperature and unaffected by oxygen. This evident stability, and its formation from open-chain precursors to the exclusion of acyclic possibilities such as 90, whose oxygen equivalent exists, implies that aromatic stabilization of 89 and similar radicals is a matter of fact and not merely definition. 

Thioxanthenes cannot give radicals which are aromatic by the definition adopted here, by simple gain or loss of electrons, as conjugation within the heterocycle is incomplete the cation-radical has been suggested to occur in... 

Because of thermodynamic and electrochemical conventions, standard potentials are defined in the direction of reduction, independently of the respective chemical stabilities of the molecules involved. Thus for the oxidation of toluene to its cation radical, E° refers to the reduction of the highly unstable cation radical into the highly stable toluene. To overcome such a priori chemical nonsence, E is frequently designated as the standard oxidation potential of toluene for example. However, such a term should not be accepted according to canonical rules because it formally implies that the cell now operates in a driven mode, that is, is connected to an external power supply [19]. Thus in this chapter we prefer to use the denomination standard reduction potentials, rather than the usual temi standard potential, as a reminder of the E° definition, although such as expression is basically a pleonasm. 

Knowledge of how aluminum chloride oxidizes aromatics to cation radicals is practically non-existent. At one time it seemed that a nitro compound was a necessary co-acceptor (Buck et al., 1960) and that, whereas with mononuclear alkylaromatics, the Lewis acid-nitro compound pair formed only charge transfer complexes (Brown and Grayson, 1953), complete electron transfer occurred with more easily oxidized aromatics. But, cation-radical formation from perylene, anthracene, and chrysene was found to occur in carbon disulfide, chloroform, and benzene solutions, too (Rooney and Pink, 1961) and even occurs on warming anthracene and naphthacene with solid aluminum chloride (Sato and Aoyama, 1973). There is no doubt that a nitro compound enhances electron transfer, however (Sullivan and Norman, 1972). Cation radical formation in AlCl3-nitromethane has been estimated as approximately 100% as compared with 1% in sulfuric acid oxidation of dialkoxybenzenes (Forbes and Sullivan, 1966). Unfortunately, aluminum halide salts have not been isolated and, therefore, even the beginnings of analytical data have yet to be collected. There is no definite knowledge of either the nature of the counter ion or the fate of the electrons in these cation-radical formations. 

The understanding of the mechanisms involved in the polymer synthesis with natural precursors is definitively a key factor for their appropriate exploitation. Taking into account this need, Ronda et al. explained recently different pathways to modify natural resources. These authors proposed three routes to modify vegetable oils to transform them into polymers (1) direct polymerization (cationic, radical, or thermal polymerization) (2) functionalization and polymerization and (3) monomer synthesized, chemical modification and polymerization [32]. 

According to our definitions, the well studied valence isomerization of quadricyclane to norbomadiene in the presence of appropriate transition metal complexes is also regarded as a photoinduced catalytic reaction. This reaction was recently discussed by Kutal[35], [36] as photo-generated catalysis. The observed quantum yield exceeds unity (( )s = 1.6) because a chain reaction is involved. Photochemically formed [Ru(bpy)3] , e.g., initiates the chain reaction by oxidation of quadricyclane to the corresponding cation radical which acts as chain carrier. The quadricyclane cation radical undergoes an isomerization to the more stable norbomadiene cation radical. The oxidation of quadricyclane by the latter one leads to the formation of norbomadiene as the product upon regeneration of the chain carrier. 

Whereas the above strategies tend to confer a two-dimensional character on the conjugated PT backbone, the possibility of building up three-dimensional conjugated systems has been envisioned very recently. In a first attempt in this direction, tetrahedral PT precursors in which four polymerizable monomers are linked to a central silicon atom have been synthesized. While the insolubility of 69 did not allow any polymerization (A. Guy and J. Roncali, unpublished), electrooxidation of 70 leads to the deposition of a tetrakis cation radical salt that can be subsequently converted into a material containing sexithienyl units by further electrooxidation [128]. Although reported electrochemical, spectroscopic, and EDX data are in accord with the expected 3D structure, further physical characterizations are needed to definitively confirm this conclusion. 

Such a mechanism is open to serious objections both on theoretical and experimental grounds. Cationic polymerizations usually are conducted in media of low dielectric constant in which the indicated separation of charge, and its subsequent increase as monomer adds to the chain, would require a considerable energy. Moreover, termination of chains growing in this manner would be a second-order process involving two independent centers such as occurs in free radical polymerizations. Experimental evidence indicates a termination process of lower order (see below). Finally, it appears doubtful that a halide catalyst is effective without a co-catalyst such as water, alcohol, or acetic acid. This is quite definitely true for isobutylene, and it may hold also for other monomers as well. 

Besides the numerous examples of anionic/anionic processes, anionic/pericydic domino reactions have become increasingly important and present the second largest group of anionically induced sequences. In contrast, there are only a few examples of anionic/radical, anionic/transition metal-mediated, as well as anionic/re-ductive or anionic/oxidative domino reactions. Anionic/photochemically induced and anionic/enzyme-mediated domino sequences have not been found in the literature during the past few decades. It should be noted that, as a consequence of our definition, anionic/cationic domino processes are not listed, as already stated for cationic/anionic domino processes. Thus, these reactions would require an oxidative and reductive step, respectively, which would be discussed under oxidative or reductive processes. 

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