TY - JOUR
T1 - Bond-coupled electron transfer reactions
T2 - Photoisomerization of norbornadiene to quadricyclane
AU - Cuppoletti, A.
AU - Dinnocenzo, J. P.
AU - Goodman, J. L.
AU - Gould, Ian
PY - 1999/12/23
Y1 - 1999/12/23
N2 - In this paper, we report on the bond coupled electron transfer (BCET) isomerization reaction of norbornadiene (NB) to quadricyclane (Q). We have used several triplet sensitizers to examine electron and energy quenching by NB. In the case of acetophenone, energy transfer generates the detectable 3NB, which rearranges to give 3Q which relaxes to Q. Using chloranil, benzoquinone, and 2,5-dichlorobenzoquinone as triplet sensitizers, the triplet ion pairs are generated, but cannot access either 3NB or 3Q, 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 3Q efficiently, which then relaxes to Q. To our knowledge, this is the first example of an efficient electron-transfer mechanism to photoisomerize NB to Q without the intermediacy of 3NB. Consequently, in the valence isomerization of NB 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.
AB - In this paper, we report on the bond coupled electron transfer (BCET) isomerization reaction of norbornadiene (NB) to quadricyclane (Q). We have used several triplet sensitizers to examine electron and energy quenching by NB. In the case of acetophenone, energy transfer generates the detectable 3NB, which rearranges to give 3Q which relaxes to Q. Using chloranil, benzoquinone, and 2,5-dichlorobenzoquinone as triplet sensitizers, the triplet ion pairs are generated, but cannot access either 3NB or 3Q, 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 3Q efficiently, which then relaxes to Q. To our knowledge, this is the first example of an efficient electron-transfer mechanism to photoisomerize NB to Q without the intermediacy of 3NB. Consequently, in the valence isomerization of NB 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.
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U2 - 10.1021/jp992884i
DO - 10.1021/jp992884i
M3 - Article
AN - SCOPUS:17344384257
SN - 1089-5639
VL - 103
SP - 11255
EP - 11256
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 51
ER -