Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit

Juwon Oh, Hirotaka Mori, Young Mo Sung, Woojae Kim, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The switching phenomena of conformation with π-electronic network through deprotonation-protonation processes were investigated by employing a series of 5,20-bis(α-oligothienyl) substituted hexaphyrins(1.1.1.1.1.1). They showed significant changes in the absorption and emission spectra with deprotonation, and returned to the initial state with protonation. Through NMR measurements and single crystal X-ray diffraction analysis, we found that the 5,20-bis(α-oligothienyl) substituted hexaphyrins, which possess acyclic, helical electronic networks involving oligothienyl chains in dumbbell conformations (type-I) in a neutral form, underwent effective deprotonation upon treatment with tetrabutylammonium fluoride (TBAF) to generate the corresponding dianions, which display cyclic electronic networks with enhanced aromaticity in rectangular conformations (type-II). Our quantum calculation results provide an unambiguous description for the switchable conformation and π-conjugation, which revealed that a deprotonation-induced enhanced aromatic conjugation pathway is involved in the switchable π-electronic network.

Original languageEnglish
Pages (from-to)2239-2245
Number of pages7
JournalChemical Science
Volume7
Issue number3
DOIs
Publication statusPublished - 2016 Mar 1

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Deprotonation
Conformations
Networks (circuits)
Protonation
X ray diffraction analysis
Nuclear magnetic resonance
Single crystals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Oh, Juwon ; Mori, Hirotaka ; Sung, Young Mo ; Kim, Woojae ; Osuka, Atsuhiro ; Kim, Dongho. / Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit. In: Chemical Science. 2016 ; Vol. 7, No. 3. pp. 2239-2245.
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Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit. / Oh, Juwon; Mori, Hirotaka; Sung, Young Mo; Kim, Woojae; Osuka, Atsuhiro; Kim, Dongho.

In: Chemical Science, Vol. 7, No. 3, 01.03.2016, p. 2239-2245.

Research output: Contribution to journalArticle

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