Sensitivity of the valence structure in diruthenium complexes as a function of terminal and bridging ligands

The compounds [(acac)2Ru(III)(μ-H2L(2-))Ru(III)(acac)2] (rac, 1, and meso, 1') and [(bpy)2Ru(II)(μ-H2L(•-))Ru(II)(bpy)2](ClO4)3 (meso, [2](ClO4)3) have been structurally, magnetically, spectroelectrochemically, and computationally characterized (acac(-) = acetylacetonate, bpy = 2,2'-bipyridine, and H4L = 1,4-diamino-9,10-anthraquinone). The N,O;N',O'-coordinated μ-H2L(n-) forms two β-ketiminato-type chelate rings, and 1 or 1' are connected via NH···O hydrogen bridges in the crystals. 1 exhibits a complex magnetic behavior, while [2](ClO4)3 is a radical species with mixed ligand/metal-based spin. The combination of redox noninnocent bridge (H2L(0) → → → →H2L(4-)) and {(acac)2Ru(II)} → →{(acac)2Ru(IV)} or {(bpy)2Ru(II)} → {(bpy)2Ru(III)} in 1/1' or 2 generates alternatives regarding the oxidation state formulations for the accessible redox states (1(n) and 2(n)), which have been assessed by UV-vis-NIR, EPR, and DFT/TD-DFT calculations. The experimental and theoretical studies suggest variable mixing of the frontier orbitals of the metals and the bridge, leading to the following most appropriate oxidation state combinations: [(acac)2Ru(III)(μ-H2L(•-))Ru(III)(acac)2](+) (1(+)) → [(acac)2Ru(III)(μ-H2L(2-))Ru(III)(acac)2] (1) → [(acac)2Ru(III)(μ-H2L(•3-))Ru(III)(acac)2](-)/[(acac)2Ru(III)(μ-H2L(2-))Ru(II)(acac)2](-) (1(-)) → [(acac)2Ru(III)(μ-H2L(4-))Ru(III)(acac)2](2-)/[(acac)2Ru(II)(μ-H2L(2-))Ru(II)(acac)2](2-) (1(2-)) and [(bpy)2Ru(III)(μ-H2L(•-))Ru(II)(bpy)2](4+) (2(4+)) → [(bpy)2Ru(II)(μ-H2L(•-))Ru(II)(bpy)2](3+)/[(bpy)2Ru(II)(μ-H2L(2-))Ru(III)(bpy)2](3+) (2(3+)) → [(bpy)2Ru(II)(μ-H2L(2-))Ru(II)(bpy)2](2+) (2(2+)). The favoring of Ru(III) by σ-donating acac(-) and of Ru(II) by the π-accepting bpy coligands shifts the conceivable valence alternatives accordingly. Similarly, the introduction of the NH donor function in H2L(n) as compared to O causes a cathodic shift of redox potentials with corresponding consequences for the valence structure.