Deprotonation-induced aromaticity enhancement and new conjugated networks in meso-hexakis(pentafluorophenyl)[26]hexaphyrin

Won Young Cha, Jong Min Lim, Min Chul Yoon, Young Mo Sung, Byung Sun Lee, Sho Katsumata, Masaaki Suzuki, Hirotaka Mori, Yoshiya Ikawa, Hiroyuki Furuta, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26π-electronic circuit can be regarded as a real homolog of porphyrin with an 18π-electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso-hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner N-H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono- and dianions of [26]hexaphyrin display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π-electronic circuit and cause enhanced aromaticity. Circuit tuning: Deprotonation causes significant structural deformations, which give rise to different and more effective π-conjugated circuits that have been found to be responsible for enhanced aromaticity (see figure). This work highlights the potential of the deprotonation strategy for tuning the electronic properties of expanded porphyrins.

Original languageEnglish
Pages (from-to)15838-15844
Number of pages7
JournalChemistry - A European Journal
Volume18
Issue number49
DOIs
Publication statusPublished - 2012 Dec 3

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Deprotonation
Networks (circuits)
Porphyrins
Tuning
Excited states
Electronic properties
Molecular structure
Fluorescence

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Cha, Won Young ; Lim, Jong Min ; Yoon, Min Chul ; Sung, Young Mo ; Lee, Byung Sun ; Katsumata, Sho ; Suzuki, Masaaki ; Mori, Hirotaka ; Ikawa, Yoshiya ; Furuta, Hiroyuki ; Osuka, Atsuhiro ; Kim, Dongho. / Deprotonation-induced aromaticity enhancement and new conjugated networks in meso-hexakis(pentafluorophenyl)[26]hexaphyrin. In: Chemistry - A European Journal. 2012 ; Vol. 18, No. 49. pp. 15838-15844.
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abstract = "meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26π-electronic circuit can be regarded as a real homolog of porphyrin with an 18π-electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso-hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner N-H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono- and dianions of [26]hexaphyrin display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π-electronic circuit and cause enhanced aromaticity. Circuit tuning: Deprotonation causes significant structural deformations, which give rise to different and more effective π-conjugated circuits that have been found to be responsible for enhanced aromaticity (see figure). This work highlights the potential of the deprotonation strategy for tuning the electronic properties of expanded porphyrins.",
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Cha, WY, Lim, JM, Yoon, MC, Sung, YM, Lee, BS, Katsumata, S, Suzuki, M, Mori, H, Ikawa, Y, Furuta, H, Osuka, A & Kim, D 2012, 'Deprotonation-induced aromaticity enhancement and new conjugated networks in meso-hexakis(pentafluorophenyl)[26]hexaphyrin', Chemistry - A European Journal, vol. 18, no. 49, pp. 15838-15844. https://doi.org/10.1002/chem.201200991

Deprotonation-induced aromaticity enhancement and new conjugated networks in meso-hexakis(pentafluorophenyl)[26]hexaphyrin. / Cha, Won Young; Lim, Jong Min; Yoon, Min Chul; Sung, Young Mo; Lee, Byung Sun; Katsumata, Sho; Suzuki, Masaaki; Mori, Hirotaka; Ikawa, Yoshiya; Furuta, Hiroyuki; Osuka, Atsuhiro; Kim, Dongho.

In: Chemistry - A European Journal, Vol. 18, No. 49, 03.12.2012, p. 15838-15844.

Research output: Contribution to journalArticle

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T1 - Deprotonation-induced aromaticity enhancement and new conjugated networks in meso-hexakis(pentafluorophenyl)[26]hexaphyrin

AU - Cha, Won Young

AU - Lim, Jong Min

AU - Yoon, Min Chul

AU - Sung, Young Mo

AU - Lee, Byung Sun

AU - Katsumata, Sho

AU - Suzuki, Masaaki

AU - Mori, Hirotaka

AU - Ikawa, Yoshiya

AU - Furuta, Hiroyuki

AU - Osuka, Atsuhiro

AU - Kim, Dongho

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