N-Alkoxyheterocycles As Irreversible Photooxidants (pages 313–328)
Zofia M. Wosinska, Faye L. Stump, Rajeev Ranjan, Edward D. Lorance, GeNita N. Finley, Priya P. Patel, Muzamil A. Khawaja, Katie L. Odom, Wolfgang H. Kramer and Ian R. Gould
Article first published online: 16 JAN 2014 | DOI: 10.1111/php.12227
The return or reverse electron transfer that occurs in the primary charge-separated pair that is a feature of all photoinduced electron transfer reactions wastes energy and competes with useful chemistry in the charge-separated species. Here, we describe photoinduced electron transfer schemes that made irreversible by using fragmentable sensitizers. The fragmentable sensitizers are N-methoxyheterocycles that cleave a relatively weak N–O bond in either their reduced or excited forms. Sensitization mechanisms in both the singlet and the triplet manifolds are described. Irreversible oxidation of guanosine is demonstrated as an illustrative example.