Primary donor quenching

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 fluorescence of 3-t (113-117) and 3-7 (118) is quenched by secondary and tertiary amines. Rate constants for quenching of It by tertiary amines increase with decreasing amine ionization or oxidation potential (Table 11), as expected for the formation of a charge-transfer stabilized exciplex in which the amine serves as the electron donor. Electron transfer quenching in nonpolar solvent is calculated to be exothermic for amines with E 2 < 1 34 V. Thus, it is not surprising that secondary and tertiary amines quench 3-t with rate constants which approach or even exceed the rate of diffusion. The inefficient quenching of It and 3-7 by primary amines is consistent with their higher oxidation potentials. 

Quenching the triplet-excited states of the fullerenes by the electron donors occurs efficiently in polar solvents like benzonitrile. The mechanism is a primary electron transfer [Eq. (1) [120,125,133,139,148,154-162],... 

As follows from the data from Sect. 2, the primary photochemical stage in the majority of the membrane systems studied is the redox quenching of the excited photosensitizer by an electron acceptor or donor leading to electron transfer across the membrane // water interface. For electron transfer to occur from the membrane-embedded photosensitizer to the water soluble acceptor, it is necessary for the former to be located sufficiently close to the membrane surface, though the direct contact of the photosensitizer with the aqueous phase is not obligatory. For example, Tsuchida et al. [147] have shown that electron transfer to MV2 + from photoexcited Zn-porphyrin inserted into the lecithin membrane, is observed only until the distance from the porphyrin ring to the membrane surface does not exceed about 12 A. 

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. 

Many reactions mediated by Sml2 require the presence of a proton donor. The primary role of the proton donor is to quench alkoxides and carbanions produced as intermediates upon reduction or reductive coupling. The most commonly utilised proton donors are alcohols, glycols and water. It is now very clear, however, that proton donors can have a considerable impact on the efficiency of Sml2-mediated reactions and their regiochemical and stereochemical outcome. Often, even a modest change in the proton donor or its concentration can have a profound impact on product distributions. Two important examples of this phenomenon are discussed below. 

---