Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins

Masaru Kon-No, John MacK, Nagao Kobayashi, Masahiko Suenaga, Kenji Yoza, Teruo Shinmyozu

Research output: Contribution to journalArticle

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Abstract

The synthesis, structures, optical properties, and electronic structures of the tetraphenyltetrathiaporphyrin dication (S 4TPP 2+, 6) and tetrakis(pentafluorophenyl)tetrathiaisophlorin (S 4F 20TPP, 7) are reported. S 4TPP 2+ (6) and S 4F 20TPP (7) were synthesized by acid-catalyzed condensation of the corresponding hydroxylmethylthiophene, followed by oxidation. The electronic structures of S 4TPP 2+ (6) and S 4F 20TPP (7) were analyzed by using UV/Vis-absorption spectroscopy and by magnetic /ular dichroism (MCD) spectroscopy and the bands were assigned by using time-dependent density functional theory (TD-DFT) and ZINDO/s calculations. A red-shift of the Q bands of S 4TPP 2+ (6) is observed relative to the spectra of tetraphenylporphyrins because a destabilization of the HOMO leads to a narrower HOMO-LUMO band-gap. Michl's perimeter model was used to assign the absorption bands and MCD spectra of S 4F 20TPP (7). Current-density maps and nucleus-independent chemical-shift (NICS) calculations of S 4TPP 2+ (6) and of a model compound predict marked modification to the diamagnetic ring current, whilst nonaromatic character is predicted for S 4F 20TPP (7).

Original languageEnglish
Pages (from-to)13361-13371
Number of pages11
JournalChemistry - A European Journal
Volume18
Issue number42
DOIs
Publication statusPublished - Oct 15 2012

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Porphyrins
Dichroism
Electronic structure
Optical properties
Chemical shift
Ultraviolet spectroscopy
Absorption spectroscopy
Density functional theory
Absorption spectra
Condensation
Energy gap
Current density
Spectroscopy
Oxidation
Acids
tetraphenylporphyrin

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins. / Kon-No, Masaru; MacK, John; Kobayashi, Nagao; Suenaga, Masahiko; Yoza, Kenji; Shinmyozu, Teruo.

In: Chemistry - A European Journal, Vol. 18, No. 42, 15.10.2012, p. 13361-13371.

Research output: Contribution to journalArticle

Kon-No, Masaru ; MacK, John ; Kobayashi, Nagao ; Suenaga, Masahiko ; Yoza, Kenji ; Shinmyozu, Teruo. / Synthesis, optical properties, and electronic structures of fully core-modified porphyrin dications and isophlorins. In: Chemistry - A European Journal. 2012 ; Vol. 18, No. 42. pp. 13361-13371.
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