Bond-coupled electron transfer reactions: Photoisomerization of norbornadiene to quadricyclane

In this paper, we report on the bond coupled electron transfer (BCET) isomerization reaction of norbornadiene (NB) to quadricyclane (Q). We have used several tripler sensitizers to examine electron and energy quenching by NE. In the case of acetophenone, energy transfer generates the detectable (NB)-N-3, which rearranges to give (3)Q which relaxes to Q. Using chloranil, benzoquinone, and 2,5-dichlorobenzoquinone as triplet sensitizers, the triplet ion pairs are generated, but cannot access either (NB)-N-3 or (3)Q, and so the ion pair undergoes return electron transfer to the ground state. However, with 3,3',4,4'-benzophenonetetracarboxylic dianhydride as the triplet sensitizer, the triplet ion pair is generated, but can undergo BCET to (3)Q efficiently, which then relaxes to Q. To our knowledge, this is the first example of an efficient electron-transfer mechanism to photoisomerize NE to Q without the intermediacy of (NB)-N-3. Consequently, in the valence isomerization of NE to Q, it is possible to directly access the NB-Q triplet surface by controlling the energy of the triplet ion pair photogenerated, and in effect, the quantum yield can be modulated.