Photoenhanced oxidative DNA cleavage with non-heme iron(II) complexes

The DNA cleavage activity of iron(II) complexes of a series of monotopic pentadentate N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine (N4Py)-derived ligands (1-5) was investigated under laser irradiation at 473, 400.8, and 355 nm in the absence of a reducing agent and compared to that under ambient lighting. A significant increase in activity was observed under laser irradiation, which is dependent on the structural characteristics of the complexes and the wavelength and power of irradiation. Under photoirradiation at 355 nm, direct double-stand DNA cleavage activity was observed with Fe(II)-1 and Fe(II)-3-5, and a 56-fold increase in the single-strand cleavage activity was observed with Fe(II)-2. Mechanistic investigations revealed that O(2)(?-), (1)O(2), and OH(?) contribute to the photoenhanced DNA cleavage activity, and that their relative contribution is dependent on the wavelength. It is proposed that the origin of the increase in activity is the photoenhanced formation of an Fe(III)OOH intermediate as the active species or precursor.