DMSO Solvent Induced Photochemistry in Highly Photostable Compounds. The Role of Intermolecular Hydrogen Bonding

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Abstract

2-(2‘-Hydroxy-5‘-methylphenyl)benzotriazole, 1, Tinuvin P, and o-hydroxybenzophenone, 2, are thought to achieve exceptional photostability through highly reversible deactivation associated with their intramolecular hydrogen bonds. Excimer laser excitation (10 mJ, 20 ns at 308 nm) of these molecules in argon-bubbled hexane solution at room temperature affords no discernible transient signals (absorption or emission) between 320 and 800 nm. In DMSO solution under the same conditions, however, strong transient absorptions in the visible (λmax 410 and 425 nm for 1 and 2, respectively) are observed. The transients responsible for the absorptions are quenched by oxygen and acid, and the spectra match well with the ground state difference spectra generated from the corresponding phenolate ions. When a bulky group is incorporated ortho to the hydroxyl function such as in 2-(2‘-hydroxy-3‘-cumyl-5‘-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 3, Tinuvin 928, no appreciable transient absorption is observed even in DMSO solution. These results are consistent with the disruption of the intramolecular hydrogen bond of 1 and 2 (but not 3) as the result of intermolecular hydrogen bond formation with DMSO. The “dramatic” ortho effect implies that the bulky group adjacent to the hydroxyl function sterically shields the intramolecular hydrogen bond from disruption by polar basic environments.

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