Variable electronic structure and spin distribution in bis(2,2′-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- and 4,5-diimido-pyrene

Abstract

The odd-electron compounds [M(bpy)₂(L¹)](ClO₄) M = Ru ([1](ClO₄)) or Os ([2](ClO₄)), and the even-electron species [M(bpy)₂(H₂L²)](ClO₄)₂, M = Ru ([3](ClO₄)₂) or Os ([4](ClO₄)₂) were obtained from pyrene-4,5-dione, L¹, or 4,5-diaminopyrene, H₄L², and were characterised structurally, electrochemically and spectroscopically. Experimental and computational analysis (TD-DFT) revealed rather different electronic structures and spin distributions of the paramagnetic monocations 1⁺–4⁺. EPR investigations and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series 1⁺ < 3⁺ < 4⁺ < 2⁺, illustrated by g value and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the π system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations.