Triplet photochemistry within zeolites through heavy atom effect, sensitization and light atom effect

Abstract

Methods to generate triplets of organic molecules within zeolites have been established by employing the Zimmerman rearrangement of barrelenes, oxa-di-π-methane rearrangement of β,γ-unsaturated ketones and photodimerization of acenaphthylene as probe reactions. The two methods, heavy cation effect and triplet sensitization, are well established solution techniques and these work well within zeolites. The Zimmerman rearrangement of dibenzobarrelene is enhanced even within Li⁺ and Na⁺ exchanged zeolites and these are believed to be the result of slowing of the rearrangement to dibenzocyclooctatetraene from S₁ through cation-π interaction. The methods described here provide an opportunity to explore the control afforded by the zeolite environment on triplet reactions.