D'Alessandro Deanna M, Davies Murray S, Keene F Richard
School of Pharmacy and Molecular Sciences, James Cook University, Townsville, Queensland, Australia.
Inorg Chem. 2006 Feb 20;45(4):1656-66. doi: 10.1021/ic051699i.
The intervalence charge transfer (IVCT) properties of the mixed-valence forms of the diastereoisomers of the dinuclear [Ru(bpy)2[M(bpy)2]]5+ (M = Ru or Os) complexes and the trinuclear heterochiral [[Ru(bpy)2]2Os(bpy)2]n+ (n = 7, 8; HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2'-bipyridine) species display a marked dependence on the nuclearity and extent of oxidation of the assemblies, while small differences are also observed for the diastereoisomers of the same complex in the dinuclear cases. The mixed-valence heterochiral [[Ru(bpy)2]2Os(bpy)2]n+ (n = 7, 8) forms exhibit IVCT properties that are intermediate between those of the diastereoisomeric forms of the localized hetero-dinuclear complex [Ru(bpy)2[Os(bpy)2]]5+ and the borderline localized-to-delocalized homo-trinuclear complex [[Ru(bpy)2]3(mu-HAT)]n+ (n = 7, 8). The near-infrared (NIR) spectrum of the +7 mixed-valence species exhibits both interconfigurational (IC) and IVCT transitions which are quantitatively similar to those in [Ru(bpy)2[Os(bpy)2]]5+ and are indicative of the localized mixed-valence formulation [[Ru(II)(bpy)2]2Os(III)(bpy)2]7+. The +8 state exhibits a new band attributable to an IVCT transition in the near-infrared region.
双核[[Ru(bpy)₂](μ - HAT)[M(bpy)₂]]⁵⁺（M = Ru或Os）非对映异构体的混合价态形式以及三核杂手性[[Ru(bpy)₂]₂[Os(bpy)₂](μ - HAT)]ⁿ⁺（n = 7, 8；HAT = 1,4,5,8,9,12 - 六氮杂三亚苯；bpy = 2,2'-联吡啶）物种的价间电荷转移（IVCT）性质对组装体的核数和氧化程度表现出显著依赖性，而在双核情况下，同一配合物的非对映异构体之间也观察到了微小差异。混合价态杂手性[[Ru(bpy)₂]₂[Os(bpy)₂](μ - HAT)]ⁿ⁺（n = 7, 8）形式表现出的IVCT性质介于局域化杂双核配合物[[Ru(bpy)₂](μ - HAT)[Os(bpy)₂]]⁵⁺的非对映异构形式和边界局域化到离域化的同三核配合物[[Ru(bpy)₂]₃(μ - HAT)]ⁿ⁺（n = 7, 8）之间。+7混合价态物种的近红外（NIR）光谱同时呈现出构型间（IC）和IVCT跃迁，这些跃迁在数量上与[[Ru(bpy)₂](μ - HAT)[Os(bpy)₂]]⁵⁺中的跃迁相似，表明其为局域化混合价态结构[[Ru(II)(bpy)₂]₂[Os(III)(bpy)₂](μ - HAT)]⁷⁺。+8态在近红外区域呈现出一条归因于IVCT跃迁的新谱带。
