Diosmium compounds containing bis(imidazole)-p-quinone bridging ligands

The doubly deprotonated bridging ligand L₁^2- derived from 2,6-bis(2-pyridyl)-1,5-dihydro-1',4'-benzoquinono[2',3'-d:5',6'-d']diimidazole H₂L₁ forms coordination compounds with two bis(2,2'-bipyridine)osmium(II) complex fragments in anti ([1](ClO₄)₂) and syn configurations ([2](ClO₄)₂) of {(μ-L₁)[Os(bpy)₂]₂}(ClO₄)₂, as evident from crystal structure analyses. Exchange of the metal-coordinating 2-pyridyl functions in the bridge through non-coordinating 4-tolyl substituents (L₁^2- → L₂^2-) leads to [3](ClO₄)₂ which involves chelation of the [Os(bpy)₂]²⁺ groups through imidazole-N and carbonyl-O atoms of the central p-quinone function. In addition to identification, the compounds were subjected to electrochemical (CV, DPV) and spectroelectrochemical (UV-vis-NIR, EPR) analyses of electron transfer, the results being supported by results from TD-DFT calculations. Essential differences between [1]/[2] and [3] systems were found regarding variable but mostly metal centred oxidation, the two processes separated much more for [3]. The first reduction is bpy ([1⁺], [2⁺]) or quinone ligand centred ([3⁺]). Electronic structures and electron transfer behaviour are thus highly sensitive to differences of configuration and coordination.