Ternary iron(III) complex showing photocleavage of DNA in the photodynamic therapy window

Abstract

A new ternary iron(III) complex [FeL(dpq)] containing dipyridoquinoxaline (dpq) and 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (H₃L) is prepared and structurally characterized by X-ray crystallography. The high-spin complex with a FeN₃O₃ core shows a quasi-reversible iron(III)/iron(II) redox couple at -0.62 V (vs SCE) in DMF/0.1 M TBAP and a broad visible band at 470 nm in DMF/Tris buffer. Laser photoexcitation of this phenolate (L)-to-iron(III) charge-transfer band at visible wavelengths including red light of ≥630 nm leads to cleavage of supercoiled pUC19 DNA to its nicked circular form via a photoredox pathway forming hydroxyl radicals.