Variable Noninnocence of Substituted Azobis(phenylcyanamido)diruthenium Complexes
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https://figshare.com/articles/dataset/Variable_Noninnocence_of_Substituted_Azobis_phenylcyanamido_diruthenium_Complexes/2195962
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资源简介：
The synthetic chemistry of substituted
4,4′-azobis(phenylcyanamide) ligands was investigated, and
the complexes [{Ru(tpy)(bpy)}2(μ-L)][PF6]2, where L = 2,2′:5,5′-tetramethyl-4,4′-azobis(phenylcyanamido)
(Me4adpc2–), 2,2′-dimethyl-4,4′-azobis(phenylcyanamido)
(Me2adpc2–), unsubstituted (adpc2–), 3,3′-dichloro-4,4′-azobis(phenylcyanamido)
(Cl2adpc2–), and 2,2′:5,5′-tetrachloro-4,4′-azobis(phenylcyanamido)
(Cl4adpc2–), were prepared and characterized
by cyclic voltammetry and vis–near-IR (NIR) and IR spectroelectrochemistry.
The room temperature electron paramagnetic resonance spectrum of [{Ru(tpy)(bpy)}2(μ-Me4adpc)]3+ showed an organic
radical signal and is consistent with an oxidation-state description
[RuII, Me4adpc•–, RuII]3+, while that of [{Ru(tpy)(bpy)}2(μ-Cl2adpc)]3+ at 10 K showed a low-symmetry
RuIII signal, which is consistent with the description
[RuIII, Cl2adpc2–, RuII]3+. IR spectroelectrochemistry data suggest that
[{Ru(tpy)(bpy)}2(μ-adpc)]3+ is delocalized
and [{Ru(tpy)(bpy)}2(μ-Cl2adpc)]3+ and [{Ru(tpy)(bpy)}2(μ-Cl4adpc)]3+ are valence-trapped mixed-valence systems. A NIR absorption
band that is unique to all [{Ru(tpy)(bpy)}2(μ-L)]3+ complexes is observed; however, its energy and intensity
vary depending on the nature of the bridging ligand and, hence, the
complexes’ oxidation-state description.
创建时间：
2016-02-14
