Abstract
The photochemistry of 4-methylpentan-2-one, heptan-2-one, 5-methyl-heptan-3-one and 5-methylhexan-2-one has been investigated in several solvents. A treatment of the data is given that allows a differentiation of the solvent effect from the quenching by the solvent. Cyclohexane, cyclohexene and benzene, when employed as solvents, quench excited triplet states with pseudo first-order constants of 4 × 10 6, 2 × 10 8 and 7 × 10 7 s −1 respectively. On the other hand, cyclohexene is the only solvent investigated that is able to partly quench the excited singlet state. By considering the effect of the different solvents upon the photochemistry of ketones having widely different mean lives, it is concluded that the change in behaviour with solvent is due almost entirely to quenching of the excited states and not to a “solvent effect”. The behaviour of both singlet and triplet biradicals is similar in n-hexane, cyclohexane, cyclohexene and benzene.
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