Solvent- and temperature-dependent conformational changes between hückel antiaromatic and möbius aromatic species in meso-trifluoromethyl substituted [28]hexaphyrins

Min Chul Yoon, Pyosang Kim, Hyejin Yoo, Soji Shimizu, Taro Koide, Sumito Tokuji, Shohei Saito, Atsuhiro Osuka, Dongho Kim

研究成果: ジャーナルへの寄稿記事

37 引用 (Scopus)

抄録

We investigated the photophysical properties of figureeight- like meso-hexakis(trifluoromethyl) [26]- and [28]hexaphyrins- (1.1.1.1.1.1) denoted as TFM26H and TFM28H, respectively, using steady-state and time-resolved spectroscopy along with theoretical calculations to explore their electronic and magnetic natures depending on their molecular aromaticity. TFM26H exhibited a well-resolved absorption feature and intense fluorescence, both of which were neither solvent- nor temperature-dependent. These optical properties were in agreement with its Hückel's [4n + 2] aromaticity as observed in typical aromatic porphyrinoids. The S1-state lifetime of ̃50 ps for TFM26H in solution was shorter than those in planar aromatic hexaphyrins (>100 ps) presumably due to nonplanar figure-eight geometry of TFM26H. However, TFM28H exhibited remarkable changes in solvent- and temperature-dependent absorption spectra as well as excited-state lifetimes indicating that a dynamic equilibrium occurs between the two conformational species. With the help of quantum mechanical geometry optimization and vertical excitation energy calculations, we found that the figure-eight double-sided conformer observed in the solid-state and single-sided distorted one could be the best candidates for the two conformers, which should be Hückel antiaromatic and Möbius aromatic species, respectively, based on their optical characteristics, molecular orbital structures, and excited-state lifetimes. Conformational dynamics between these two conformers of TFM28H was scrutinized in detail by temperature-dependent 1H NMR spectra in various solvents, which showed that the conformational equilibrium was quite sensitive to solvents and that a conformational change faster than the NMR time-scale occurs even at 173 K.

元の言語英語
ページ(範囲)14928-14937
ページ数10
ジャーナルJournal of Physical Chemistry B
115
発行部数50
DOI
出版物ステータス出版済み - 12 22 2011
外部発表Yes

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Temperature
Excited states
life (durability)
Nuclear magnetic resonance
excitation
nuclear magnetic resonance
temperature
Geometry
Excitation energy
Molecular orbitals
geometry
Molecular Structure
Absorption spectra
Spectrum Analysis
molecular orbitals
Optical properties
Fluorescence
Spectroscopy
solid state
absorption spectra

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

これを引用

Solvent- and temperature-dependent conformational changes between hückel antiaromatic and möbius aromatic species in meso-trifluoromethyl substituted [28]hexaphyrins. / Yoon, Min Chul; Kim, Pyosang; Yoo, Hyejin; Shimizu, Soji; Koide, Taro; Tokuji, Sumito; Saito, Shohei; Osuka, Atsuhiro; Kim, Dongho.

:: Journal of Physical Chemistry B, 巻 115, 番号 50, 22.12.2011, p. 14928-14937.

研究成果: ジャーナルへの寄稿記事

Yoon, Min Chul ; Kim, Pyosang ; Yoo, Hyejin ; Shimizu, Soji ; Koide, Taro ; Tokuji, Sumito ; Saito, Shohei ; Osuka, Atsuhiro ; Kim, Dongho. / Solvent- and temperature-dependent conformational changes between hückel antiaromatic and möbius aromatic species in meso-trifluoromethyl substituted [28]hexaphyrins. :: Journal of Physical Chemistry B. 2011 ; 巻 115, 番号 50. pp. 14928-14937.
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title = "Solvent- and temperature-dependent conformational changes between h{\"u}ckel antiaromatic and m{\"o}bius aromatic species in meso-trifluoromethyl substituted [28]hexaphyrins",
abstract = "We investigated the photophysical properties of figureeight- like meso-hexakis(trifluoromethyl) [26]- and [28]hexaphyrins- (1.1.1.1.1.1) denoted as TFM26H and TFM28H, respectively, using steady-state and time-resolved spectroscopy along with theoretical calculations to explore their electronic and magnetic natures depending on their molecular aromaticity. TFM26H exhibited a well-resolved absorption feature and intense fluorescence, both of which were neither solvent- nor temperature-dependent. These optical properties were in agreement with its H{\"u}ckel's [4n + 2] aromaticity as observed in typical aromatic porphyrinoids. The S1-state lifetime of ̃50 ps for TFM26H in solution was shorter than those in planar aromatic hexaphyrins (>100 ps) presumably due to nonplanar figure-eight geometry of TFM26H. However, TFM28H exhibited remarkable changes in solvent- and temperature-dependent absorption spectra as well as excited-state lifetimes indicating that a dynamic equilibrium occurs between the two conformational species. With the help of quantum mechanical geometry optimization and vertical excitation energy calculations, we found that the figure-eight double-sided conformer observed in the solid-state and single-sided distorted one could be the best candidates for the two conformers, which should be H{\"u}ckel antiaromatic and M{\"o}bius aromatic species, respectively, based on their optical characteristics, molecular orbital structures, and excited-state lifetimes. Conformational dynamics between these two conformers of TFM28H was scrutinized in detail by temperature-dependent 1H NMR spectra in various solvents, which showed that the conformational equilibrium was quite sensitive to solvents and that a conformational change faster than the NMR time-scale occurs even at 173 K.",
author = "Yoon, {Min Chul} and Pyosang Kim and Hyejin Yoo and Soji Shimizu and Taro Koide and Sumito Tokuji and Shohei Saito and Atsuhiro Osuka and Dongho Kim",
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T1 - Solvent- and temperature-dependent conformational changes between hückel antiaromatic and möbius aromatic species in meso-trifluoromethyl substituted [28]hexaphyrins

AU - Yoon, Min Chul

AU - Kim, Pyosang

AU - Yoo, Hyejin

AU - Shimizu, Soji

AU - Koide, Taro

AU - Tokuji, Sumito

AU - Saito, Shohei

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2011/12/22

Y1 - 2011/12/22

N2 - We investigated the photophysical properties of figureeight- like meso-hexakis(trifluoromethyl) [26]- and [28]hexaphyrins- (1.1.1.1.1.1) denoted as TFM26H and TFM28H, respectively, using steady-state and time-resolved spectroscopy along with theoretical calculations to explore their electronic and magnetic natures depending on their molecular aromaticity. TFM26H exhibited a well-resolved absorption feature and intense fluorescence, both of which were neither solvent- nor temperature-dependent. These optical properties were in agreement with its Hückel's [4n + 2] aromaticity as observed in typical aromatic porphyrinoids. The S1-state lifetime of ̃50 ps for TFM26H in solution was shorter than those in planar aromatic hexaphyrins (>100 ps) presumably due to nonplanar figure-eight geometry of TFM26H. However, TFM28H exhibited remarkable changes in solvent- and temperature-dependent absorption spectra as well as excited-state lifetimes indicating that a dynamic equilibrium occurs between the two conformational species. With the help of quantum mechanical geometry optimization and vertical excitation energy calculations, we found that the figure-eight double-sided conformer observed in the solid-state and single-sided distorted one could be the best candidates for the two conformers, which should be Hückel antiaromatic and Möbius aromatic species, respectively, based on their optical characteristics, molecular orbital structures, and excited-state lifetimes. Conformational dynamics between these two conformers of TFM28H was scrutinized in detail by temperature-dependent 1H NMR spectra in various solvents, which showed that the conformational equilibrium was quite sensitive to solvents and that a conformational change faster than the NMR time-scale occurs even at 173 K.

AB - We investigated the photophysical properties of figureeight- like meso-hexakis(trifluoromethyl) [26]- and [28]hexaphyrins- (1.1.1.1.1.1) denoted as TFM26H and TFM28H, respectively, using steady-state and time-resolved spectroscopy along with theoretical calculations to explore their electronic and magnetic natures depending on their molecular aromaticity. TFM26H exhibited a well-resolved absorption feature and intense fluorescence, both of which were neither solvent- nor temperature-dependent. These optical properties were in agreement with its Hückel's [4n + 2] aromaticity as observed in typical aromatic porphyrinoids. The S1-state lifetime of ̃50 ps for TFM26H in solution was shorter than those in planar aromatic hexaphyrins (>100 ps) presumably due to nonplanar figure-eight geometry of TFM26H. However, TFM28H exhibited remarkable changes in solvent- and temperature-dependent absorption spectra as well as excited-state lifetimes indicating that a dynamic equilibrium occurs between the two conformational species. With the help of quantum mechanical geometry optimization and vertical excitation energy calculations, we found that the figure-eight double-sided conformer observed in the solid-state and single-sided distorted one could be the best candidates for the two conformers, which should be Hückel antiaromatic and Möbius aromatic species, respectively, based on their optical characteristics, molecular orbital structures, and excited-state lifetimes. Conformational dynamics between these two conformers of TFM28H was scrutinized in detail by temperature-dependent 1H NMR spectra in various solvents, which showed that the conformational equilibrium was quite sensitive to solvents and that a conformational change faster than the NMR time-scale occurs even at 173 K.

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