Photonic modulation of electron transfer with switchable phase inversion

Julien Frey, Gerdenis Kodis, Stephen D. Straight, Thomas A Moore, Ana L Moore, John Devens Gust

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Photochromes may be reversibly photoisomerized between two metastable states and their properties can influence, and be influenced by, other chromophores in the same molecule through energy or electron transfer. In the photochemically active molecular tetrad described here, a porphyrin has been covalently linked to a fullerene electron acceptor, a quinoline-derived dihydroindolizine photochrome, and a dithienylethene photochrome. The porphyrin first excited singlet state undergoes photoinduced electron transfer to the fullerene to generate a charge-separated state. The quantum yield of charge separation is modulated by the two photochromes: one isomer of each quenches the porphyrin excited state, reducing the quantum yield of electron transfer to near zero. Interestingly, when the molecule is illuminated with white light, the quantum yield decreases as the white light intensity is increased, generating an out-of-phase response of the quantum yield to white light. However, when the same experiment is performed in the presence of additional, steady-state UV illumination, a phase inversion occurs. The quantum yield of electron transfer now increases with increasing white light intensity. Such effects illustrate emergent complexity in a relatively simple system and could find applications in molecular logic, photochemical labeling and drug delivery, and photoprotection for artificial photosynthetic molecules. The photochemistry leading to this behavior is discussed.

Original languageEnglish
Pages (from-to)607-615
Number of pages9
JournalJournal of Physical Chemistry A
Volume117
Issue number3
DOIs
Publication statusPublished - Jan 24 2013

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Quantum yield
Photonics
electron transfer
Modulation
photonics
inversions
Porphyrins
modulation
Electrons
porphyrins
Fullerenes
Excited states
luminous intensity
Molecules
fullerenes
molecules
phase response
Photochemical reactions
quinoline
polarization (charge separation)

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Photonic modulation of electron transfer with switchable phase inversion. / Frey, Julien; Kodis, Gerdenis; Straight, Stephen D.; Moore, Thomas A; Moore, Ana L; Gust, John Devens.

In: Journal of Physical Chemistry A, Vol. 117, No. 3, 24.01.2013, p. 607-615.

Research output: Contribution to journalArticle

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