PUB - Publikationen an der Universität Bielefeld

We have developed a family of dinuclear complexes using 2,7-disubstituted 1,8-naphthalenediol ligands that bind by molecular recognition to two neighboring phosphate diesters of the DNA backbone with the dinuclear CuII and NiII complexes exhibiting a severe cytotoxicity for human cancer cells. To increase the binding affinity, we intended to synthesize the corresponding dinuclear FeIII complex. Surprisingly, we obtained a tetranuclear FeIII perylene-based complex instead of the expected dinuclear FeIII naphthalene-based complex. In order to establish a rational and reproducible synthesis, we carefully analyzed this reaction. This revealed a multistep oxidative cascade reaction including the pre-coordination of FeII ions in the N3-binding pockets, the Lewis-acid assisted MOM-deprotection of the pre-ligand by the pre-oriented FeII ions, two oxidative aromatic C-C coupling reactions, oxidation of the perylene-based backbone and of FeII to FeIII. The careful analysis of bond lengths, HOMA indices (harmonic oscillation model of aromaticity), FTIR and UV-Vis-NIR spectra supported by DFT calculations reveals the presence of an aromatic 18-electron oxidized perylenequinone ligand backbone. In summary, a multistep cascade reaction involving in total a 10-electron oxidation has been established for the straight-forward synthesis of an unprecedented perylenequinone-based ligand system. © 2024 Wiley‐VCH GmbH.