Radical non-radical states of the [Ru(PIQ)] core in complexes (PIQ = 9,10-phenanthreneiminoquinone)

9,10-Phenanthreneiminosemiquinonate anion radical (PIQ˙(-)) complexes of ruthenium of types trans-[Ru(II)(PIQ˙(-))(PPh3)2(CO)Cl] () and trans-[Ru(III)(PIQ˙(-))(PPh3)2Cl2] () are reported. Reactions of and with I2 afford trans-[Ru(III)(PIQ˙(-))(PPh3)2(CO)Cl](+)I3(-)·½CH2Cl2 ((+)I3(-)·½CH2Cl2) and trans-[Ru(PIQ˙(-))2(PPh3)2(μ-Cl)3](+)I3(-)·¼I2·¼toluene) ((+)I3(-)·¼I2·¼toluene), while the reaction of with Br2 yields a 9,10-phenanthreneiminoquinone (PIQ) complex of the type mer-[Ru(III)(PIQ)(PPh3)Br3]·½CH2Cl2 (·½CH2Cl2). In comparison, the reaction of trans-[Ru(III)(PQ˙(-))(PPh3)2Cl2] (PQ), a 9,10-phenanthrenequinone (PQ) analogue of affords only trans-[Ru(III)(PQ)(PPh3)2Cl2](+)Br3(-) ((+)Br3(-)). Considering the X-ray bond parameters, EPR spectra and the atomic spin densities obtained from the density functional theory (DFT) calculations, is defined as a PIQ˙(-) (average C-O/N and C-C lengths, 1.280(2) and 1.453(3) Å) complex of ruthenium(ii) while is a neutral PIQ (average C-O, C-N, C-C and C-O/N lengths, 1.248(7), 1.284(7), 1.485(8) and 1.266(7) Å) complex of the ruthenium(iii) ion. The single crystal X-ray bond parameters proposed that (+)I3(-) (average C-O/N and C-C lengths, 1.294(8) and 1.449(9) Å) and (average C-O/N and C-C lengths, 1.289(2) and 1.447(4) Å) are PIQ˙(-) complexes of ruthenium(iii), while the (+) ion (average C-O/N and C-C lengths, 1.288 ± 0.004 and 1.450 ± 0.017 Å) is a co-facial bi-octahedral complex of ruthenium(iii). In contrast, the (+) ion is a PQ complex of the ruthenium(iii) ion. EPR spectra and the calculated atomic spin densities authenticated that the (+) ion obtained after constant potential coulometric oxidation of is a PIQ complex of ruthenium(iii), while the (-) ion is a hybrid state of [Ru(II)(PIQ˙(-))] and [Ru(III)(PIQ(2-))] states. It is observed that the PIQ˙(-) state in which spin is more localized on the nitrogen (∼38% in and ∼35% in (-) ion) is stable and the coordination of the PIQ(2-) state is not observed in this study. Redox activities, UV-vis/NIR absorption spectra and their origins and the spectroelectrochemical measurements for → (+), → (-) and (+) → (2+) conversions are analyzed.