Bond-coupled electron transfer reactions

Photoisomerization of norbornadiene to quadricyclane

A. Cuppoletti, J. P. Dinnocenzo, J. L. Goodman, Ian Gould

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)11255-11256
Number of pages2
JournalJournal of Physical Chemistry A
Volume103
Issue number51
StatePublished - Dec 23 1999

Fingerprint

Photoisomerization
electron transfer
Electrons
Ions
isomerization
Isomerization
ions
Chloranil
quinones
Quantum yield
Energy transfer
energy transfer
quenching
Ground state
Quenching
valence
ground state
quadricyclane
energy
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Bond-coupled electron transfer reactions : Photoisomerization of norbornadiene to quadricyclane. / Cuppoletti, A.; Dinnocenzo, J. P.; Goodman, J. L.; Gould, Ian.

In: Journal of Physical Chemistry A, Vol. 103, No. 51, 23.12.1999, p. 11255-11256.

Research output: Contribution to journalArticle

Cuppoletti, A. ; Dinnocenzo, J. P. ; Goodman, J. L. ; Gould, Ian. / Bond-coupled electron transfer reactions : Photoisomerization of norbornadiene to quadricyclane. In: Journal of Physical Chemistry A. 1999 ; Vol. 103, No. 51. pp. 11255-11256.
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