In the cation formed by photoinduced C-F bond cleavage in fleroxacin, intramolecular reaction with the N-ethyl chain is prevented by the electron-withdrawing effect of fluorine and intermolecular attack by nucleophiles is facilitated.

The morpholinofluorophenyloxazolidinone 1 (the antibacterial drug linezolid) is found to undergo reductive defluorination upon irradiation in water (Phi 0.33), in some of the products accompanied by the simultaneous oxidative degradation of the morpholine side chain. In the presence of chloride, iodide and pyrrole, the fluorine is substituted by these groups (with pyrrole, in position 2). The defluorination is less efficient in methanol and mainly leads to reduction (Phi 0.053). These data can be accommodated through two different mechanisms, viz. either C-F bond heterolysis to give a phenyl cation [S(N)1(Ar*)], or ionization to give a radical cation [S(R(+)N)1(Ar*)]. Steady-state and time resolved data have been gathered for clarifying this issue. It is found that, indeed, ionization of 1 is efficient and proceeds from the singlet, but leads to no irreversible change. On the contrary, triplet (3)1 (lifetime 0.5 micros in MeOH, <0.1 micros in water) fragments and gives the corresponding triplet phenyl cation. The last intermediate explains well the observed hydrogen abstraction both inter- (from the solvent, when this is reducing) and intramolecularly (from the morpholine group), as well as addition to a charged anion or to a neutral pi nucleophile such as pyrrole. The rationalization is supported by the study of some related molecules. Thus, the only photochemical reaction from the non fluorinated analogue of linezolid (that ionizes just as 1) is an inefficient degradation of the morpholine chain (Phi 0.001), while a simple model such as N-(2-fluorophenyl)morpholine undergoes photosolvolysis in water and is not trapped by pyrrole.

Hydrogen abstraction from the C-7 position of cholesterol (Ch) by triplet excited benzophenone (BZP) exhibits remarkable solvent-dependence in product studies. Kinetic measurements on the intramolecular version of the process in dyads containing covalently linked Ch and BZP units reveal important solvent effects and significant stereodifferentiation.