Switching of the triplet excited state of styryl 2,6-diiodo-bodipy and its application in acid-activatable singlet oxygen photosensitizing

J Org Chem. 2014 Nov 7;79(21):10240-55. doi: 10.1021/jo5019014. Epub 2014 Oct 17.

Abstract

IodoBodipy-styrylBodipy dyads triplet photosensitizers were prepared (B-1 and B-2) which contain acid-responsive moiety. Both compounds show broadband visible light absorption, due to the resonance energy transfer (RET) between the two different visible light-harvesting Bodipy units. The photophysical properties of the dyads were studied with steady-state and nanosecond time-resolved transient absorption spectroscopy. The production of triplet excited state is switched ON or OFF by protonation/deprotonation of the amino group in the dyads. In the neutral form, the excited state is short-lived (<10 ns) and no singlet oxygen ((1)O2) photosensitizing was observed. Upon protonation, a long-lived triplet excited state was observed (τT = 3.1 μs) and the (1)O2 quantum yield (ΦΔ) is up to 73.8%. The energy levels of the components of the dyads were changed upon protonation and this energy level tuning exerts significant influence on the triplet state property of the dyad. Acid-activated shuffling of the localization of the triplet excited state between two components of a dyad was observed. Furthermore, we observed a rare example that a chromophore giving shorter absorption wavelength is acting as the singlet energy acceptor in RET. The experimental results were rationalized by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Boron Compounds / chemistry*
  • Iodides / chemistry*
  • Light
  • Molecular Structure
  • Photochemical Processes
  • Photosensitizing Agents / chemistry
  • Quantum Theory
  • Singlet Oxygen / chemistry*
  • Spectrophotometry, Ultraviolet
  • Styrenes / chemistry*

Substances

  • 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  • Boron Compounds
  • Iodides
  • Photosensitizing Agents
  • Styrenes
  • Singlet Oxygen