6392-96-7Relevant articles and documents
Variable noninnocence of substituted azobis(phenylcyanamido)diruthenium complexes
Choudhuri, Mohommad M. R.,Behzad, Mahdi,Al-Noaimi, Mousa,Yap, Glenn P. A.,Kaim, Wolfgang,Sarkar, Biprajit,Crutchley, Robert J.
, p. 1508 - 1517 (2015)
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.
