Abstract
AbstractThe impact of metal‐to‐ligand charge transfer towards the redox noninnocence of 2,2′‐azobis(benzothiazole) (abbt) has been highlighted on coordination to {RuII(acac)2} (acac=2,4‐pentanedionato). It led to the authentication of a series of mononuclear and dinuclear complexes incorporating variable oxidation states of abbt (abbt0/.−/2−). Mononuclear 1 was identified as [RuIII(abbt.−)], a MLCT excited state of [RuII(abbt)]. Dinuclear 2 was however recognized as two discrete redox isomers: (i) radical bridged mixed‐valent meso‐[Ru2.5(μ‐abbt.−)Ru2.5] (2a) and (ii) dianionic ligand bridged isovalent meso‐[RuIII(μ‐abbt2−)RuIII] (2b), demonstrating unprecedented structural confirmation of valence tautomerism in azo‐based ligand systems. A crystal structure of [2]ClO4 validated the formation of [RuIII(μ‐abbt.−) RuIII]ClO4. Analysis of electronic structural forms of 1 and 2 in accessible redox states via spectroelectrochemistry and DFT revealed their electron reservoir feature.
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