Quenching Radical pairs

Fig. 3 Transient spectra obtained upon the application of a 200-fs laser pulse to a solution of stilbene (S) and chloranil (Q) in dioxane. (a) The fast decay ( 20 ps) of the contact ion-radical pair S+ , Q generated by direct charge-transfer excitation (CT path), (b) The slow growth ( 1.6 ns) of the ion pair S+ Q due to the diffusional quenching of triplet chloranil (A path) as described in Scheme 13. Reproduced with permission from Ref. 55.

However, the short lifetimes ( 50 ps) of the ion-radical pair ArMe"1", CA- owing to rapid back electron transfer ( bet) does not allow other reactions to compete effectively.203 In contrast, the diffusional quenching of the photoex-cited chloranil with methylbenzenes leads to (spectrally) indistinguishable ion-radical pairs with greatly enhanced lifetimes,204 i.e.,... 

The mechanism for the photoreaction between 133 and cyclohexene can be summarized as in Scheme 8. The initiating electron transfer fluorescence quenching of 133 by cyclohexene resulted in the formation of an w-amino radical-radical cation pair 136. Proton transfer from the 2-position of the cyclohexene radical cation to the nitrogen atom of the a-amino radical leads to another radical cation-radical pair 137. Recombination of 137 at the radical site affords the adduct 134, while nucleophilic attack at the cation radical of 136 leads to another radical pair 138 which is the precursor for the adduct 135. 

The Patterno-Buchi coupling of various stilbenes (S) with chloroanil (Q) to yield fran -oxetanes is achieved by the specific charge-transfer photo-activation of the electron donor-acceptor complexes (SQ). Time-resolved spectroscopy revealed the (singlet) ion-radical pair[S+% Q" ] to be the primary reaction intermediate and established the electron-transfer pathway for this Patterno-Buchi transformation. Carbonyl quinone activation leads to the same oxetane products with identical isomer ratios. Thus, an analogous mechanism is applied which includes an initial transfer quenching of the photo-activated (triplet) quinone acceptor by the stilbene donors resulting in triplet ion-radical pairs. ... 

The photochemical reduction of 1-methylquinolinium ions by (TMS)3SiH proceeds regioselectively to afford the corresponding 1,4-dihydroquinones in a water-acetonitrile solvent system (Reaction 4.47) [83]. Mechanistic studies demonstrated that the reactions are initiated by photoinduced electron transfer from the silane to the singlet excited states of 1-methylquinolinium ions to give the silane radical cation-quinolinyl radical pairs, followed by hydrogen transfer in the cage to yield 1,4-dihydroquinones and silicenium ion. Silyl cations are quenched by water. 

Kochi and co-workers studied photoinduced Diels-Alder cycloadditions via direct photoexcitation of anthracene as a diene with maleic anhydride and various maleimides as dienophiles. Here, fluorescence-quenching experiments, time-resolved absorption measurements, and the effect of solvent polarity provide striking evidence for an ion-radical pair to be the decisive intermediate [83],... 

Some other covalently bound porphyrin-acceptor complexes such as por-phyrin-viologen [68-73] and pyromellitimide-bridged porphyrins [74, 75] have been synthesized and studied. As in the case of P-Q complexes, strong fluorescence quenching and ion radical pair formation were observed in these systems under irradiation of complexes in porphyrin absorption bands. 

Quantum yields for adduct 63 and total product (63-65) formation from the reaction of - -t with several tertiary amines are summarized in Table 12. Quantum yields measured at 1.0 M amine concentration are lower than the values extrapolated to infinite amine concentration due to incomplete quenching of It. Extrapolated total quantum yields range from 0.07 to 0.33, providing a lower limit for the efficiency of the proton transfer step, kh> in Fig. 11. The other reaction products, 1,2-diphenylethane (64) and 1,2,3,4-tetraphenylbenzene (65), are formed mainly via in-cage radical pair disproportionation and out of cage combination, respectively. The relative importance of radical pair combination, disproportionation, and cage escape is dependent... 

Hydrogen atom transfer from anthracene, excited into its lowest excited singlet state, to anthraquinone impurity molecules creates a radical pair that strongly quenches the fluorescence from anthracene crystals. The reverse transfer rate constant, found from measurements of fluorescence intensity and its characteristic lifetime at different moments after the creation of the radical pair, varies from 106 to 10s s 1 in the range 110-65 K, kc = 4 x 104 s 1, TC = 60K. The kc values drops to 102 s 1 in the deuteroanthracene crystal [Lavrushko and Benderskii, 1978]. 

The high value for the quenching of 3,4-dimethoxyacetophenone by phenol suggests that it is probable that within the lignin structure hydroxyl groups are able to quench carbonyls by a static mechanism to yield phenoxy-ketyl radical pairs which decay on a timescales faster than the time resolution of our laser flash photolysis apparatus. Intersystem crossing rate constants for triplet radical pairs in the restricted environments of micelles have been demonstrated to be of the order of 2 -5 x 106 s-1 (25, 24). However, in the lignin matrix where diffusional processes are likely to be... 

Time-resolved (fs/ps) spectroscopy revealed that the (singlet) ion-radical pair is the primary reaction intermediate and established the electron-transfer pathway for this Paterno-Buchi transformation. The alternative pathway via direct electronic activation of the carbonyl component led to the same oxetane regioisomers in identical ratios. Thus, a common electron-transfer mechanism applies involving quenching of the excited quinone acceptor by the stilbene donor to afford a triplet ion-radical intermediate which appear on the ns/ps time scale. The spin multiplicities of the critical ion-pair intermediates in the two photoactivation paths determine the time scale of the reaction sequences and also the efficiency of the relatively slow ion-pair collapse ( c=108/s) to the 1,4-biradical that ultimately leads to the oxetane product 54. 

Careful study of (S)- (+) -2-phenylpropiophenone reveals that approximately half of the radical pairs recombine before diffusing out of the initial solvent cage 50>. This conclusion follows from the 44% quantum weld of scavengable benzoyl radicals and the 33% quantum yield for racemization. Alkyl thiols are excellent radical scavengers in carbonyl photochemistry because they quench triplet ketones fairly slowly 51>. Lewis has shown that concentrations of thiol above 0.03 M generally trap all free benzoyl radicals as benzaldehyde 50>. Of course, the minimum concentration for complete scavenging depends on conversion. 

The kinetics of combination of radical pairs formed by quenching of the triplet excited state of B by 2,4,6-trimethylphenol (HR) in films of rigid and plasticized polyvinylchloride (PVC) were studied by the method of laser flash photolysis by Levin et al. At high concentrations of the phenol quencher ( 15 wt%), most of the triplet excited state of the ketone is quenched and the formation and disappearance of the ketyl and phenoxyl radicals can be followed from changes in their characteristic transient absorptions at 540 and 390 nm, respectively. 

Since the cage effect is less than 100 % in most cases (Table 1), some of the radical pairs exit the micelle and become water solubilized free radicals. At some later time, the free radicals recombine to form DPE. This has been verified by Cu2+ quenching experiments (Fig. 6)13,19). The disappearance of DBK is not dependent upon the concentration of Cu2+. However, the yield of DPE drops very rapidly with increasing copper concentration and then levels off. The leveling off region is directly related to the amount of cage reaction. The products formed by reaction with copper are benzyl chloride (4), and benzyl alcohol (5) (Scheme V)20). 

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