Trans - cis isomerisation of a, � unsaturated alkenes can be used to design photoswitches. We investigated the photoreactivity of trans alkenes 1a  -c . We used laser flash photolysis (LFP, ?=308 nm, 17 ns; ?=266 nm, 5 ns; ?=355 nm, 5 ns), product studies, time resolved IR (TRIR, ? = 266 nm), matrix isolation studies (? > 300 nm), phosphorescence and theoretical DFT calculations to identify the intermediates formed by irradiating 1a-c . Solutions photolysis (? > 300 nm) of 1a  -c  yields TK of 1a  -c  which then decays to form biradicals (TBR) of 1a  -c . TBR of 1a  -c  can rotate around C � C bond and form 2a  -c  or rearrange back to form 1a-c  again. The lifetime of TBR of 1a-c  is significantly longer than that for the TK of 1a-c .

Efficient trans-cis isomerization via triplet 1,2-biradical: A study using time-resolved UV/visible, time-resolved IR, matrix isolation, and DFT calculations

244th National Meeting (2012)

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