Non-emissive Ru^II Polypyridyl Complexes as Efficient and Selective Photosensitizers for the Photooxidation of Benzylamines

Five new Ru^II polypyridyl complexes bearing N-(arylsulfonyl)-8-amidoquinolate ligands and three of their biscyclometalated Ir^III congeners have been prepared and employed as photocatalysts (PCs) in the photooxidation of benzylamines with O₂. In particular, the new Ru^II complexes do not exhibit photoluminescence, rather they harvest visible light efficiently and are very stable in solution under irradiation with blue light. Their non-emissive behavior has been related to the low electrochemical energy gaps and rationalized on the basis of theoretical calculations (DFT analysis) that predict low S₀←T₁ energy values. Moreover, the Ru^II complexes, despite being non-emissive, display excellent activities in the selective photocatalytic transformation of benzylamines into the corresponding imines. The presence of an electron-withdrawing group (-CF3) on the arene ring of the N-(arylsulfonyl)-8-amidoquinolate ligand improves the photocatalytic activity of the corresponding photocatalyst. Furthermore, all the experimental evidence, including transient absorption spectroscopy measurements suggest that singlet oxygen is the actual oxidant. The Ir^III analogues are considerably more photosensitive and consequently less efficient photosensitizers (PSs).