Near-Infrared S 2 Fluorescence from Deprotonated Möbius Aromatic [32]Heptaphyrin

Jun Oh Kim, Yongseok Hong, Taeyeon Kim, Won Young Cha, Tomoki Yoneda, Takanori Soya, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

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Abstract

This study revealed S 2 fluorescence from deprotonated meso-pentafluorophenyl-substituted Möbius aromatic [32]heptaphyrin(1.1.1.1.1.1.1) that was formed upon treatment of neutral antiaromatic [32]heptephyrin with tetrabutylammonium fluoride. Higher excited-state dynamics and emission were studied by fs-transient absorption spectroscopy and a broad-band fluorescence upconversion technique. This is the first S 2 fluorescence from chromophores with twisted Möbius topology, and the observation of S 2 fluorescence in the near-infrared region has been unprecedented. The higher excited-state dynamics of neutral and deprotonated [32]heptaphyrins were compared by ultrafast transient absorption spectroscopy to understand the S 2 fluorescence origin. In the antiaromatic [32]heptaphyrin, a fast time component of 65 fs was assigned as an internal conversion process from the S B state to the S Q state, which occurs prior to relaxation to the optically dark, lowest electronic state (S D ). Therefore, the S Q state of the antiaromatic [32]heptaphyrin acts as a trap state intervening radiative transitions from the S B state to the S 0 state. In deprotonated [32]heptaphyrin, the internal conversion from the S B state to the S Q state proceeds with a slower time constant of 150 fs for owing to its rigid structure, helping the observation of its S 2 fluorescence.

Original languageEnglish
Pages (from-to)4527-4531
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume9
Issue number16
DOIs
Publication statusPublished - 2018 Aug 16

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Fluorescence
Infrared radiation
fluorescence
internal conversion
Absorption spectroscopy
Excited states
absorption spectroscopy
Rigid structures
Electronic states
Chromophores
rigid structures
chromophores
time constant
excitation
fluorides
topology
Topology
traps
broadband
electronics

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Kim, Jun Oh ; Hong, Yongseok ; Kim, Taeyeon ; Cha, Won Young ; Yoneda, Tomoki ; Soya, Takanori ; Osuka, Atsuhiro ; Kim, Dongho. / Near-Infrared S 2 Fluorescence from Deprotonated Möbius Aromatic [32]Heptaphyrin In: Journal of Physical Chemistry Letters. 2018 ; Vol. 9, No. 16. pp. 4527-4531.
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abstract = "This study revealed S 2 fluorescence from deprotonated meso-pentafluorophenyl-substituted M{\"o}bius aromatic [32]heptaphyrin(1.1.1.1.1.1.1) that was formed upon treatment of neutral antiaromatic [32]heptephyrin with tetrabutylammonium fluoride. Higher excited-state dynamics and emission were studied by fs-transient absorption spectroscopy and a broad-band fluorescence upconversion technique. This is the first S 2 fluorescence from chromophores with twisted M{\"o}bius topology, and the observation of S 2 fluorescence in the near-infrared region has been unprecedented. The higher excited-state dynamics of neutral and deprotonated [32]heptaphyrins were compared by ultrafast transient absorption spectroscopy to understand the S 2 fluorescence origin. In the antiaromatic [32]heptaphyrin, a fast time component of 65 fs was assigned as an internal conversion process from the S B state to the S Q state, which occurs prior to relaxation to the optically dark, lowest electronic state (S D ). Therefore, the S Q state of the antiaromatic [32]heptaphyrin acts as a trap state intervening radiative transitions from the S B state to the S 0 state. In deprotonated [32]heptaphyrin, the internal conversion from the S B state to the S Q state proceeds with a slower time constant of 150 fs for owing to its rigid structure, helping the observation of its S 2 fluorescence.",
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Near-Infrared S 2 Fluorescence from Deprotonated Möbius Aromatic [32]Heptaphyrin . / Kim, Jun Oh; Hong, Yongseok; Kim, Taeyeon; Cha, Won Young; Yoneda, Tomoki; Soya, Takanori; Osuka, Atsuhiro; Kim, Dongho.

In: Journal of Physical Chemistry Letters, Vol. 9, No. 16, 16.08.2018, p. 4527-4531.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Near-Infrared S 2 Fluorescence from Deprotonated Möbius Aromatic [32]Heptaphyrin

AU - Kim, Jun Oh

AU - Hong, Yongseok

AU - Kim, Taeyeon

AU - Cha, Won Young

AU - Yoneda, Tomoki

AU - Soya, Takanori

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2018/8/16

Y1 - 2018/8/16

N2 - This study revealed S 2 fluorescence from deprotonated meso-pentafluorophenyl-substituted Möbius aromatic [32]heptaphyrin(1.1.1.1.1.1.1) that was formed upon treatment of neutral antiaromatic [32]heptephyrin with tetrabutylammonium fluoride. Higher excited-state dynamics and emission were studied by fs-transient absorption spectroscopy and a broad-band fluorescence upconversion technique. This is the first S 2 fluorescence from chromophores with twisted Möbius topology, and the observation of S 2 fluorescence in the near-infrared region has been unprecedented. The higher excited-state dynamics of neutral and deprotonated [32]heptaphyrins were compared by ultrafast transient absorption spectroscopy to understand the S 2 fluorescence origin. In the antiaromatic [32]heptaphyrin, a fast time component of 65 fs was assigned as an internal conversion process from the S B state to the S Q state, which occurs prior to relaxation to the optically dark, lowest electronic state (S D ). Therefore, the S Q state of the antiaromatic [32]heptaphyrin acts as a trap state intervening radiative transitions from the S B state to the S 0 state. In deprotonated [32]heptaphyrin, the internal conversion from the S B state to the S Q state proceeds with a slower time constant of 150 fs for owing to its rigid structure, helping the observation of its S 2 fluorescence.

AB - This study revealed S 2 fluorescence from deprotonated meso-pentafluorophenyl-substituted Möbius aromatic [32]heptaphyrin(1.1.1.1.1.1.1) that was formed upon treatment of neutral antiaromatic [32]heptephyrin with tetrabutylammonium fluoride. Higher excited-state dynamics and emission were studied by fs-transient absorption spectroscopy and a broad-band fluorescence upconversion technique. This is the first S 2 fluorescence from chromophores with twisted Möbius topology, and the observation of S 2 fluorescence in the near-infrared region has been unprecedented. The higher excited-state dynamics of neutral and deprotonated [32]heptaphyrins were compared by ultrafast transient absorption spectroscopy to understand the S 2 fluorescence origin. In the antiaromatic [32]heptaphyrin, a fast time component of 65 fs was assigned as an internal conversion process from the S B state to the S Q state, which occurs prior to relaxation to the optically dark, lowest electronic state (S D ). Therefore, the S Q state of the antiaromatic [32]heptaphyrin acts as a trap state intervening radiative transitions from the S B state to the S 0 state. In deprotonated [32]heptaphyrin, the internal conversion from the S B state to the S Q state proceeds with a slower time constant of 150 fs for owing to its rigid structure, helping the observation of its S 2 fluorescence.

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DO - 10.1021/acs.jpclett.8b01829

M3 - Article

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SP - 4527

EP - 4531

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

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