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Calculations were performed on [Ru(tpy)(bpy)(dmso)] 2+ (tpy = 2,2′:6′,2′′-terpyridine; bpy = 2,2′-bipyridine, dmso = dimethylsulfoxide, 1 ), cis -[Ru(tpy)(Me-pic)(dmso)] + (Me-pic = 6-methylpicolinate, 2 ), trans -[Ru(tpy)(Me-pic)(dmso)] + ( 3 ), and trans -[Ru(tpy)(pic)(dmso)] + (pic = picolinate, 4 ) to gain an understanding of the differences in their photoisomerization behavior. The results do not support a promoting role for the σ* ligand field (LF) states during excited-state S→O isomerization. Instead, the calculations show that the Ru−S bonding, the identity of the highest occupied molecular orbital, and steric interactions are important factors in dmso photoisomerization. Furthermore, the atom positioned trans to the S atom plays a critical role in promoting enhanced photoisomerizataion yields.
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Lutterman et al. (2010) studied this question.
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