Conjugated electron transfer

To extend the quinone chemistry, polyanilines and quinonediimines as 3t-conjugated polymers or molecules are studied to serve as organic catalysts for proton-conjugated electron transfer. Dimension of t-conjugated systems is controlled by use of a porphyrin or its zinc complex as a molecular scaffold to permit photorefractive electron transfer. 

Pd(II) was shown to be separated from Ni(II), Cr(III) and Co(III) by ACs completely, and only up to 3 % of Cu(II) and Fe(II) evaluate from solution together with Pd(II), this way practically pure palladium may be obtained by it s sorption from multi-component solutions. The selectivity of Pd(II) evaluation by ACs was explained by soi ption mechanism, the main part of which consists in direct interaction of Pd(II) with 7t-conjugate electron system of carbon matrix and electrons transfer from carbon to Pd(II), last one can be reduced right up to Pd in dependence on reducing capability of AC. 

One suggested mechanism is that the reaction may take place by a conjugate hydride-transfer mechanism, analogous to what occurs during alcohol oxidations with NAD+. Electrons on the enolate ion might expel a (3 hydride ion, which could add to the doubly bonded NS nitrogen on FAD. Protonation of the intermediate at N1 would give the product. 

The first realization of a conjugated polymer/fullerene diode [89] was achieved only recently after the detection of the ultrafasl phoioinduced electron transfer for an lTO/MEH-PPV/CW)/Au system. The device is shown in Figure 15-18. Figure 15-19 shows the current-voltage characteristics of such a bilayer in the dark at room temperature. The devices discussed in the following section typically had a thickness of 100 nm for the MEH-PPV as well as the fullerene layer. Positive bias is defined as positive voltage applied to the 1TO contact. The exponential current tum-on at 0.5 V in forward bias is clearly observable. The rectification ratio at 2 V is approximately l()4. 

At this point, special mention37 should be made of the behaviour of highly conjugated ethylenic sulphones in weakly acidic media. For example, in the case when R1 =Ph (Z isomer), a fairly stable anion radical was obtained in dry DMF. However, either in aprotic (consecutive two one-electron transfer) or in protic media (ECE process, occurrence of the protonation step on anion radical), C—S bond cleavage is observed. The formation of the corresponding olefins by C—S bond cleavage may occur in high yield, and is nearly quantitative when R1 = H and R2 = Ph for an electrolysis conducted in... 

Scheme 36). Interestingly, the higher order cuprate 206 underwent conjugate addition with only moderate selectivity. This is likely due to the intervention of an electron transfer pathway. Competing electron transfer reactions involving a-alkoxymetal reagents of this type have also been reported by Cohen [81]. 

Proton-coupled intramolecular electron transfer has been investigated for the quinonoid compounds linked to the ferrocene moiety by a 7r-conjugated spacer, 72 (171) and 75 (172). The complex 72 undergoes 2e oxidation in methanol to afford 74, which consists of an unusual allene and a quinonoid structure, with the loss of two hydrogen atoms from 72 (Scheme 2). The addition of CF3SO3H to an acetonitrile solution of 74 results in two intense bands around 450 nm, characteristic of a semi-quinone radical, and a weak broad band at lOOOnm in the electronic... 

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