title: Valence-state alternatives in diastereoisomeric complexes [(acac)2Ru(mu-QL)Ru(acac)2]n (QL2- = 1,4-dioxido-9,10-anthraquinone,n = +2, +1, 0, -1, -2).
abstract: The title complexes were obtained in neutral form (n = 0) as rac (1) and meso isomers (2). 2 was crystallized for X-ray diffraction and its temperature-dependent magnetism studied. It contains two antiferromagnetically coupled ruthenium(III) ions, bridged by the quinizarine dianion QL(2-) (quinizarine = 1,4-dihydroxy-9,10-anthraquinone). The potential of both the ligand (QLo --> QL4-) and the metal complex fragment combination [(acac)2RuII]2 --> ([(acac)2RuIV]2)4+ to exist in five different redox states creates a large variety of combinations, which was assessed for the electrochemically reversibly accessible 2+, 1+, 0, 1-, 2- forms using cyclic voltammetry as well as EPR and UV-vis-NIR spectroelectrochemistry. The results for the two isomers are similar: Oxidation to 1+ or 2+ causes the emergence of a near-infrared band (1390 nm), without revealing an EPR response even at 4 K. Reduction to 1- or 2- produces an EPR signal, signifying metal-centered spin but no near-infrared absorption. Tentatively, we assume metal-based oxidation of [(acac)2RuIII(mu-QL2-)RuIII(acac)2] to a mixed-valent intermediate [(acac)2RuIII(mu-QL2-)RuIV(acac)2]+ and ligand-centered reduction to a radical complex [(acac)2RuIII(mu-QL.3-)RuIII(acac)2 (-) with antiferromagnetic three-spin interaction.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai-400076, India.
authors.forename: Somnath
authors.initials: S
authors.lastname: Maji
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Shaikh M
authors.initials: SM
authors.lastname: Mobin
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler
authors.forename: Francisco A
authors.initials: FA
authors.lastname: Urbanos
authors.forename: Reyes
authors.initials: R
authors.lastname: Jimenez-Aparicio
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Lahiri