Synthesis, X-structure and solvent induced electronic states tuning of meso-tris(4-nitrophenyl)corrolato-copper complex

Copper(II) ion insertion into the coordination core of meso-tris(p-nitrophenyl)corrole (1), in air showed the formation of meso-tris(p-nitrophenyl)corrolatoCu(III) (2), with the generation of superoxide radical as the side product of the reaction. Single-crystal X-ray diffraction analysis revealed that 2 exhibits weak π–π stacking interaction. Among the two electronic states, diamagnetic Cu(III)–corrole3− exits in DCM solution and in contrast is paramagnetic Cu(II)–corrole2− cationic radical in DMF solution. This difference in electronic behavior in solution is due to the small energy gap between HOMO and LUMO that is readily influenced by solvent interaction.

Graphical abstractCu(II) ion insertion into the coordination core of meso-tris(p-nitrophenyl)corrole (1), in air showed the formation of meso-tris(p-nitrophenyl)corrolatoCu(III) (2) and superoxide radical as the side product of the reaction.Figure optionsDownload full-size imageDownload as PowerPoint slide