Photoswitched singlet energy transfer in a porphyrin-spiropyran dyad

J Am Chem Soc. 2001 Jul 25;123(29):7124-33. doi: 10.1021/ja010058t.

Abstract

A photochromic nitrospiropyran moiety (Sp) has been covalently linked to a zinc (PZn) and to a free-base (P(H2)) porphyrin. In the resulting dyads (P(Zn)-Sp(c) and P(H2)-Sp(c)), 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-Sp(o)) 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-Sp(o). 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-1Sp(o). The quantum yield of energy transfer is 0.93. Quenching is also observed in the free base dyad, where 1P(H2)-Sp(o) and P(H2)-1Sp(o) 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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Benzopyrans / chemical synthesis
  • Benzopyrans / chemistry*
  • Benzopyrans / radiation effects
  • Energy Transfer / radiation effects*
  • Indoles
  • Light
  • Models, Molecular
  • Nitro Compounds
  • Photosynthesis
  • Porphyrins / chemical synthesis
  • Porphyrins / chemistry*
  • Porphyrins / radiation effects
  • Spectrum Analysis
  • Zinc / chemistry

Substances

  • Benzopyrans
  • Indoles
  • Nitro Compounds
  • Porphyrins
  • spiropyran
  • Zinc