Photoswitched singlet energy transfer in a porphyrin-spiropyran dyad

J. L. Bahr, G. Kodis, L. De la Garza, S. Lin, Ana L Moore, Thomas A Moore, John Devens Gust

Research output: Contribution to journalArticle

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Abstract

A photochromic nitrospiropyran moiety (Sp) has been covalently linked to a zinc (PZn) and to a free-base (PH2) porphyrin. In the resulting dyads (PZn-Spc and PH2-Spc), the porphyrin first excited singlet states are unperturbed by the closed form of the attached spiropyran. Excitation of the spiropyran moiety of either dyad in the near-UV region results in ring opening to a merocyanine form (P-Spo) that absorbs at 600 nm. The open form re-closes thermally in 2-methyltetrahydrofuran with a time constant of 20 s, or following irradiation into the 600 nm band. Excitation of the zinc porphyrin moiety in the merocyanine form of the dyad yields 1PZn-Spo. The lifetime of the zinc porphyrin excited state is reduced from its usual value of 1.8 ns to 130 ps by singlet-singlet energy transfer to the merocyanine moiety to give PZn-1Spo. The quantum yield of energy transfer is 0.93. Quenching is also observed in the free base dyad, where 1PH2-Spo and PH2-1Spo exchange singlet excitation energy. This photoswitchable quenching phenomenon provides light-activated control of the porphyrin excited states, and consequently control of any subsequent energy or electron-transfer processes that might be initiated by these excited states in more complex molecular photonic or optoelectronic devices.

Original languageEnglish
Pages (from-to)7124-7133
Number of pages10
JournalJournal of the American Chemical Society
Volume123
Issue number29
DOIs
Publication statusPublished - 2001

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Energy Transfer
Porphyrins
Excited states
Energy transfer
Zinc
Optics and Photonics
Quenching
Photonic devices
Excitation energy
Quantum yield
Optoelectronic devices
Electrons
Light
Equipment and Supplies
Irradiation
spiropyran
merocyanine
zinc hematoporphyrin

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Photoswitched singlet energy transfer in a porphyrin-spiropyran dyad. / Bahr, J. L.; Kodis, G.; De la Garza, L.; Lin, S.; Moore, Ana L; Moore, Thomas A; Gust, John Devens.

In: Journal of the American Chemical Society, Vol. 123, No. 29, 2001, p. 7124-7133.

Research output: Contribution to journalArticle

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