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Removal of an electron from a bonding orbital or addition of an electron to an antibonding orbital of a diamagnetic molecule activates the resulting radical ion for fragmentation. Such reactive radical ions may be generated by photoinduced electron transfer (PET). There are two alternative ways to accomplish the transfer of an electron: (1) the local excitation of a donor or an acceptor which is well...
Recent work on the mechanisms of the photohydrodehalogenation of haloarenes, with an emphasis on polyhaloarenes, and the related mechanisms of phototransformations of aliphatic halocompounds are reviewed. Attention is focused on the nature of the excimer in the photochemical transformations of haloarenes without additional electron transfer reagent and on the nature of the exciplex formed in phototransformations...
Reductive properties of excited state organic anions are discussed, starting from the preliminary presentation of other related properties: spectral characteristics, ion pair associations and photoejection ability. Electron transfer reactions may be correlated by the Marcus treatment and some peculiarities of the use of this model, in the case of oxyanions, are pinpointed. Photoreactions...
The primary aim of this chapter is to provide a review of the chemistry of PET generated aromatic radical ions in solution. Extensive delocalization of the unpaired electron makes these species relatively stable. Thus it is possible to exploit both aspects of their reactivity (as radicals and as ions) and to intercept them both with electrophiles (or respectively with nucleophiles) and with radicals...
PET processes between ground and excited states of donor-acceptor pairs lead to the formation of radical ion pairs which upon disproportionation gives neutral radicals and/or ions required for synthetic purposes. A host of new reactions has been uncovered, the nature of which is governed by the chemical properties and reactivity profiles of these reactive intermediates. Our objective in this chapter...
Fluorescent PET (photoinduced electron transfer) sensors are considered to be those molecular systems where the binding of ions and other species leads to the perturbation of the competition between the de-excitation pathways of fluorescence and electron transfer. The early developments in this field are traced and the design logic of these sensors is detailed. A variety of examples drawn from different...
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