Intramolecular charge transfer character in tetrathiafulvalene-annulated porphyrinoids: effects of core modification and protonation

Ramababu Bolligarla, Masatoshi Ishida, Vijayendra S. Shetti, Kazuhisa Yamasumi, Hiroyuki Furuta, Chang Hee Lee

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

The synthesis, characterization, and photophysical and electrochemical properties of a novel tetrathiafulvalene (TTF)-annulated core-modified porphyrin (1) and its expanded rubyrin analogue (2) are described. The sulfur core modifications in 1 and 2 allow a feasible intramolecular charge transfer from the TTF fragments to the central conjugated core as inferred from comparative spectroscopic and electrochemical measurements. DFT calculations also support the intramolecular charge transfer nature of 1 and 2 upon excitation. Further the electronic perturbation of the TTF-annulated porphyrins was achieved by protonation, giving rise to a drastic change in the optical features with an extremely low energy band in the NIR region. The pronounced electron accepting ability of the macrocyclic core of the dicationic species (H212+ and H222+) resulted in the thermally excited electron transfer occurring at room temperature as elucidated by EPR spectroscopy. This journal is

Original languageEnglish
Pages (from-to)8699-8705
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume17
Issue number14
DOIs
Publication statusPublished - Apr 14 2015

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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