Desaktivierungsverhalten von Arenen und Heteroarenen. XXXI [11]. Ein Modell für die reversible Photodimerisierung von Anthracen und 9‐Methylanthracen

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Abstract
Deactivation Behaviour of Arenes and Heteroarenes. XXXI. A Model of the Reversible Photodimerization of Anthracene and 9‐MethylanthraceneStarting from the Woodward‐Hoffmann state diagram of the reversible photodimerization of anthracene and 9‐methyl‐anthracene the potential correlation diagram is shown due to an excimer formation. This qualitative diagram is fixed by ten values of the state potential, which are determined directly or indirectly, respectively, by variation of the influence of environment. The mechanism and the kinetics of the photoreaction are discussed on the basis of the given potential correlation diagram and for the reversible photodimerization a common pericyclic transition state is assumed. The photochemical dimerization is a pure diabatic reaction. The photochemical decomposition of the dimer occurs mainly diabatic, and the quantum yield of the adiabatic excimer formation is only about the twentieth part of those of the diabatic reaction.