The photo- and electrochemically induced linkage isomerism of six new complexes [Ru(bpy)2(L)(dmso-S)]+, where dmso is dimethylsulfoxide, bpy is 2,2′-bipyridine, and L- is pentachloro-, 2,3,5,6-tetrachloro-, 2,4,5-trichloro-, 2,4-dichloro-, 4-chloro-, and unsubstituted phenylcyanamide anion, were investigated. The quantum yields of linkage isomerism forming the metastable [Ru(bpy)2(L)(dmso-O)] + complexes are shown to decrease with increasing donor properties of the phenylcyanamide ligand, and it is suggested that the donor properties of the cyanamide ligand stabilize the [Ru(bpy)2(L)(dmso-S)]+ complexes in the 3MLCT excited state. The cyclic voltammetry of these complexes showed two oxidation processes: a phenylcyanamide L(0/-) couple (an assignment supported by density functional theory (DFT) calculations) and a Ru(III/II) couple at more positive potential. Upon oxidation to Ru(III), the complexes rearranged to form Ru-O linkage isomers, and the scan rate dependent voltammograms permitted estimates of the rates of linkage isomerism.

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Persistent URL dx.doi.org/10.1021/ic402600h
Journal Inorganic Chemistry
Citation
Choudhuri, M.M.R. (Mohommad M. R.), & Crutchley, R. (2013). Phenylcyanamide ligand control of photo-induced linkage isomerism. Inorganic Chemistry, 52(24), 14404–14410. doi:10.1021/ic402600h