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

研究成果: ジャーナルへの寄稿学術誌査読

16 被引用数 (Scopus)

抄録

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.

本文言語英語
ページ(範囲)8699-8705
ページ数7
ジャーナルPhysical Chemistry Chemical Physics
17
14
DOI
出版ステータス出版済み - 4月 14 2015

!!!All Science Journal Classification (ASJC) codes

  • 物理学および天文学一般
  • 物理化学および理論化学

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