Multistep Photochemical Reactions of Polypyridine-Based Ruthenium Nitrosyl Complexes in Dimethylsulfoxide
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The photorelease of nitric oxide (NO·) has been investigated in dimethylsulfoxide (DMSO) on two compounds of formula [Ru(R-tpy)(bpy)(NO)](PF), in which bpy stands for 2,2'-bipyridine and R-tpy for the 4'--2,2':6',2″-terpyridine with R = H and MeOPh. It is observed that both complexes are extremely sensitive to traces of water, leading to an equilibrium between [Ru(NO)] and [Ru(NO)]. The photoproducts of formula [Ru(R-tpy)(bpy)(DMSO)](PF) are further subjected to a photoreaction leading to a reversible linkage isomerization between the stable Ru-DMSO (sulfur linked) and the metastable Ru-DMSO (oxygen linked) species. A set of 4 [Ru(R-tpy)(bpy)(DMSO)] complexes (R = H, MeOPh, BrPh, NOPh) is investigated to characterize the ratio and mechanism of the isomerization which is tentatively related to the difference in absorbance between the Ru-DMSO and Ru-DMSO forms. In addition, the X-ray crystal structures of [Ru(tpy)(bpy)(NO)](PF) and [Ru(MeOPh-tpy)(bpy)(DMSO)](PF) are presented.
Song L, Bai H, Liu C, Gong W, Wang A, Wang L Molecules. 2021; 26(9).
PMID: 33925453 PMC: 8123785. DOI: 10.3390/molecules26092545.