Bonded exciplexes. A new concept in photochemical reactions

Yingsheng Wang, Olesya Haze, Joseph P. Dinnocenzo, Samir Farid, Ramy S. Farid, Ian Gould

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

(Graph Presented) Charge-transfer quenching of the singlet excited states of cyanoaromatic electron acceptors by pyridine is characterized by a driving force dependence that resembles those of conventional electron-transfer reactions, except that a plot of the log of the quenching rate constants versus the free energy of electron transfer is displaced toward the endothermic region by 0.5-0.8 eV. Specifically, the reactions with pyridine display rapid quenching when conventional electron transfer is highly endothermic. As an example, the rate constant for quenching of the excited dicyanoanthracene is 3.5 × 109 M-1 s-1, even though formation of a conventional radical ion pair, A•-D•+, is endothermic by ∼0.6 eV. No long-lived radical ions or exciplex intermediates can be detected on the picosecond to microsecond time scale. Instead, the reactions are proposed to proceed via formation of a previously undescribed, short-lived charge-transfer intermediate we call a "bonded exciplex", A--D+. The bonded exciplex can be formally thought of as resulting from bond formation between the unpaired electrons of the radical ions A•- and D•+. The covalent bonding interaction significantly lowers the energy of the charge-transfer state. As a result of this interaction, the energy decreases with decreasing separation distance, and near van der Waals contact, the A--D+ bonded state mixes with the repulsive excited state of the acceptor, allowing efficient reaction to form A--D+ even when formation of a radical ion pair A•-D•- is thermodynamically forbidden. Evidence for the bonded exciplex intermediate comes from studies of steric and Coulombic effects on the quenching rate constants and from extensive DFT computations that clearly show a curve crossing between the ground state and the low-energy bonded exciplex state.

Original languageEnglish (US)
Pages (from-to)6970-6981
Number of pages12
JournalJournal of Organic Chemistry
Volume72
Issue number18
DOIs
StatePublished - Aug 31 2007

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Photochemical reactions
Quenching
Electrons
Ions
Charge transfer
Rate constants
Excited states
Rapid quenching
Discrete Fourier transforms
Ground state
Free energy
pyridine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Wang, Y., Haze, O., Dinnocenzo, J. P., Farid, S., Farid, R. S., & Gould, I. (2007). Bonded exciplexes. A new concept in photochemical reactions. Journal of Organic Chemistry, 72(18), 6970-6981. https://doi.org/10.1021/jo071157d

Bonded exciplexes. A new concept in photochemical reactions. / Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P.; Farid, Samir; Farid, Ramy S.; Gould, Ian.

In: Journal of Organic Chemistry, Vol. 72, No. 18, 31.08.2007, p. 6970-6981.

Research output: Contribution to journalArticle

Wang, Y, Haze, O, Dinnocenzo, JP, Farid, S, Farid, RS & Gould, I 2007, 'Bonded exciplexes. A new concept in photochemical reactions', Journal of Organic Chemistry, vol. 72, no. 18, pp. 6970-6981. https://doi.org/10.1021/jo071157d
Wang, Yingsheng ; Haze, Olesya ; Dinnocenzo, Joseph P. ; Farid, Samir ; Farid, Ramy S. ; Gould, Ian. / Bonded exciplexes. A new concept in photochemical reactions. In: Journal of Organic Chemistry. 2007 ; Vol. 72, No. 18. pp. 6970-6981.
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AB - (Graph Presented) Charge-transfer quenching of the singlet excited states of cyanoaromatic electron acceptors by pyridine is characterized by a driving force dependence that resembles those of conventional electron-transfer reactions, except that a plot of the log of the quenching rate constants versus the free energy of electron transfer is displaced toward the endothermic region by 0.5-0.8 eV. Specifically, the reactions with pyridine display rapid quenching when conventional electron transfer is highly endothermic. As an example, the rate constant for quenching of the excited dicyanoanthracene is 3.5 × 109 M-1 s-1, even though formation of a conventional radical ion pair, A•-D•+, is endothermic by ∼0.6 eV. No long-lived radical ions or exciplex intermediates can be detected on the picosecond to microsecond time scale. Instead, the reactions are proposed to proceed via formation of a previously undescribed, short-lived charge-transfer intermediate we call a "bonded exciplex", A--D+. The bonded exciplex can be formally thought of as resulting from bond formation between the unpaired electrons of the radical ions A•- and D•+. The covalent bonding interaction significantly lowers the energy of the charge-transfer state. As a result of this interaction, the energy decreases with decreasing separation distance, and near van der Waals contact, the A--D+ bonded state mixes with the repulsive excited state of the acceptor, allowing efficient reaction to form A--D+ even when formation of a radical ion pair A•-D•- is thermodynamically forbidden. Evidence for the bonded exciplex intermediate comes from studies of steric and Coulombic effects on the quenching rate constants and from extensive DFT computations that clearly show a curve crossing between the ground state and the low-energy bonded exciplex state.

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