The doubly deprotonated bridging ligand L12- 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 (L12- → L22-) 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 [1n+]/[2n+] and [3n+] systems were found regarding variable but mostly metal centred oxidation, the two processes separated much more for [3n+]. 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.