The photophysics of thioxanthone (TX) dissolved in methanol (MeOH) and 2,2,2,-trifluoroethanol (TFE) was studied by time-resolved fluorescence and absorption spectroscopy. The spectrally integrated stimulated emission is seen to lose amplitude within ∼5-10 ps. This is much shorter than the fluorescence lifetimes of the compound (2.7 ns for MeOH and 7.6 ns for TFE). The initial reduction in amplitude is attributed to reversible intersystem crossing between the primarily excited (1)ππ* and a triplet (3)nπ* state. The latter one is energetically slightly (∼0.02 eV) above the former one. Addition of the quencher 1-methylnaphthalene (1-MN) reduces the fluorescence lifetime and yields triplet excited 1-MN, giving further evidence for the equilibrium of singlet and triplet excitations. The depopulation of these two states on the nanosecond time scale results in the rise of the lowest triplet state, a (3)ππ* state. Temperature dependencies attribute this to an activated internal conversion process between the two triplet states. Kinetic and energetic parameters derived from the experimental data will be compared with quantum chemical results in the accompanying paper [Rai-Constapel , V. , Villnow , T. , Ryseck , G. , Gilch , P. , and Marian , C. M. J. Phys. Chem. A 2014 , DOI: 10.1021/jp5099415].

The photophysics of thioxanthone dissolved in cyclohexane was studied by femtosecond fluorescence and transient absorption spectroscopy. From these experiments two time constants of ∼400 fs and ∼4 ps were retrieved. With the aid of quantum chemically computed spectral signatures and rate constants for intersystem crossing, the time constants were assigned to the underlying processes. Ultrafast internal conversion depletes the primarily excited (1)ππ* state within ∼400 fs. The (1)nπ* state populated thereby undergoes fast intersystem crossing (∼4 ps) yielding the lowest triplet state of (3)ππ* character.

The chimeric behavior of thioxanthone in protic solvents has been investigated employing computational chemistry methods. In particular, methanol and 2,2,2-trifluoroethanol have been chosen in this study. The solvent environment has been modeled using microsolvation in combination with a conductor-like screening model. The vertical excitation spectrum within the same solvent is seen to depend on the number of specific bonds formed between the chromophore and the solvent molecules. Two different models have been discussed in this work, namely, one and two H-bond models. In particular, the formation of the second H-bond causes the energy gap between the πHπL* and nOπL* states to increase further. Excited-state absorption spectra for the photophysically relevant electronic states have been theoretically determined for comparison with the time-resolved spectra recorded experimentally [Villnow, T.; Ryseck, G.; Rai-Constapel, V.; Marian, C. M.; Gilch, P. J. Phys. Chem. A 2014]. The equilibration of the 1(πHπL*) and 3(nOπL*) states holds responsible for the chimeric behavior. This equilibrium sets in with a calculated time constant of 23 ps in methanol and 14 ps in TFE (5 and 10 ps in experiment, respectively). The radiative decay from the optically bright 1(πHπL*) state is computed to occur with a time constant of 25 ns in both solvents (14–25 ns in experiment).

The photo-isomerization of o-acetylbenzaldehyde (oABA) in acetonitrile was studied by femto- and nanosecond transient absorption spectroscopy. Spectroscopic signatures are assigned with the aid of TD-DFT, TD-CAM-DFT and DFT-MRCI computations. The isomerization yields a lactone, 3-methylphthalide (3MP), with a quantum yield of 0.3 (30%). As evidenced by femtosecond stimulated Raman spectroscopy (FSRS), the isomerization proceeds via a ketene intermediate. It is formed within ∼2-3 ps after photo-excitation. Intersystem crossing (ISC) populating the triplet state of oABA seems to compete with the ketene formation. Experiments on the non-reactive meta- and para-derivatives, which undergo efficient ISC with time constants of 5 ps, support this statement. The triplet state of oABA also contributes to the ketene formation, presumably involving a biradical intermediate. The ketene exhibits a lifetime of 1.4 μs and generates an additional intermediate in the cascade towards the lactone.

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