ABSTRACT
Reactions of [{Ru(tmpa)}2(µ-Cl)2][ClO4]2, (2[ClO4]2, tmpa=tris(2-pyridylmethyl)amine) with 2,5-dihydroxy-1,4-benzoquinone (L1), 2,5-di-[2,6-(dimethyl)-anilino]-1,4-benzoquinone (L2), or 2,5-di-[2,4,6-(trimethyl)-anilino)]-1,4-benzoquinone (L3) in the presence of a base led to the formation of the dinuclear complexes [{Ru(tmpa)}2(µ-L1-2H)][ClO4]2 (3[ClO4]2), [{Ru(tmpa)}2(µ-L2-2H)][ClO4]2 (4[ClO4]2), and [{Ru(tmpa)}2(µ-L3-2H)][ClO4]2 (5[ClO4]2). Structural characterization of 5[ClO4]2 showed the localization of the double bonds within the quinonoid ring and a twisting of the mesityl substituents with respect to the quinonoid plane. Cyclic voltammetry of the complexes show two reversible oxidation and quinonoid-based reduction processes. Results obtained from UV/Vis/NIR and EPR spectroelectrochemistry are invoked to discuss ruthenium- versus quinonoid-ligand-centered redox activity. The complex 3[ClO4]2 is compared to the reported complex [{Ru(bpy)}2(µ-L1-2 H)]2+ (12+, bpy=2,2'-bipyridine). The effects of substituting the bidentate and better π-accepting bpy co-ligands with tetradentate tmpa ligands [pure σ-donating (amine) as well as σ-donating and π-accepting (pyridines)] on the redox and electronic properties of the complexes are discussed. Comparisons are also made between complexes containing the dianionic forms of the all-oxygen-donating L1 ligand with the L2 and L3 ligands containing an [O,N,O,N] donor set. The one-electron oxidized forms of the complexes show absorption in the NIR region. The position as well as the intensity of this band can be tuned by the substituents on the quinonoid bridge. In addition, this band can be switched on and off by using tunable redox potentials, making such systems attractive candidates for NIR electrochromism.
ABSTRACT
Reactions of [(az(-H))Pd(µ-Cl)(2)Pd(az(-H))] (az = azobenzene) with the zwitterionic, p-benzoquinonemonoimine-type ligands 4-(n-butylamino)-6(n-butylimino)-3-oxocyclohexa-1,4-dien-1-olate (Q(1)) or 4-(isopropylamino)-6(isopropylimino)-3-oxocyclohexa-1,4-dien-1-olate) (Q(2)) in the presence of a base leads to the formation of the mononuclear complexes [(az(-H))Pd(Q(1)(-H))] (1) and [(az(-H))Pd(Q(2)(-H))] (2) respectively. Structural characterization of 2 shows an almost square planar coordination geometry around the Pd(II) centre, a short Pd-C bond, a slight elongation of the N=N double bond of the az(-H) ligand and localization of the double bonds within the Q(2)(-H) ligand. Additionally, intermolecular N-H-O interactions exist between the uncoordinated N-H and O groups of two different molecules. Cyclic voltammetry of the complexes reveals an irreversible oxidation and two reversible reduction processes. A combination of electrochemical and UV-vis-NIR and EPR spectroelectrochemical studies are used to show that both coordinated ligands participate successively in the redox processes, thus revealing their non-innocent character.
ABSTRACT
An unprecedented quinonoid-bridged dicopper(I) complex is described together with its redox, EPR and structural properties, which indicate a non-innocent role of the zwitterion-derived bridging ligand.
