A hexagonal prismatic porphyrin array: Synthesis, STM detection, and efficient energy hopping in near-infrared region

Min Chul Yoon, Zin Seok Yoon, Sung Cho, Dongho Kim, Akihiko Takagi, Takuya Matsumoto, Tomoji Kawai, Takaaki Hori, Xiaobin Peng, Naoki Aratani, Atsuhiro Osuka

Research output: Contribution to journalArticle

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Abstract

A belt-shaped hexagonal cyclic porphyrin array 2 that comprises of six meso-meso, β-β, β-β triply linked diporphyrins 3 bridged by 1,3-phenylene spacers is prepared by oxidation from cyclic dodecameric array 1 consisting of six meso-meso directly linked diporphyrins 4 with DDQ and Sc(OTf)3. The absorption spectrum of 2 is similar to that of the constituent subunit 3 but shows a slight red-shift for the Q-bands in near-infrared (NIR) region, indicating the exciton coupling between the neighboring diporphyrin chromophores. Observed total exciton coupling energies in the absorption spectra were largely matched with the calculated values based on point-dipole exciton coupling approximation. It was found that the experimental exciton coupling strength (292 cm-1) of the Q-band in 2 is slightly larger than the calculated one (99 cm-1), indicating that the electronic communications are enhanced through 1,3-phenylene linkers in hexameric macromolecule. A rate of the excitation energy hopping (EEH) that occurs in 2 at the lowest excited singlet state in the near-infrared region has been determined to be (1.8 ps)-1 on the basis of the pump-power dependent femtosecond transient absorption (TA) and the transient absorption anisotropy (TAA) decay measurements. The 2 times faster EEH rate of 2 than that of 1 (4.0 ps)-1 mainly comes from involving through-bond energy transfer among diporphyrin subunits via 1,3-phenylene bridges as well as Förster-type through-space EEH processes. STM measurement of 2 in the Cu(100) surface revealed that it takes several discrete conformations with respect to the relative orientation of neighboring diporphyrins. Collectively, an effective EEH in the NIR region is realized in 2 due largely to the intensified oscillator strength in the S1 state (Q-band) and the close proximity held by 1,3-phenylene spacers.

Original languageEnglish
Pages (from-to)9233-9239
Number of pages7
JournalJournal of Physical Chemistry A
Volume111
Issue number38
DOIs
Publication statusPublished - 2007 Sep 27

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Excitation energy
Porphyrins
porphyrins
Infrared radiation
excitons
synthesis
excitation
Absorption spectra
spacers
energy
absorption spectra
Chromophores
Macromolecules
Excited states
Crystal orientation
Energy transfer
Conformations
Anisotropy
macromolecules
red shift

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Yoon, Min Chul ; Yoon, Zin Seok ; Cho, Sung ; Kim, Dongho ; Takagi, Akihiko ; Matsumoto, Takuya ; Kawai, Tomoji ; Hori, Takaaki ; Peng, Xiaobin ; Aratani, Naoki ; Osuka, Atsuhiro. / A hexagonal prismatic porphyrin array : Synthesis, STM detection, and efficient energy hopping in near-infrared region. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 38. pp. 9233-9239.
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abstract = "A belt-shaped hexagonal cyclic porphyrin array 2 that comprises of six meso-meso, β-β, β-β triply linked diporphyrins 3 bridged by 1,3-phenylene spacers is prepared by oxidation from cyclic dodecameric array 1 consisting of six meso-meso directly linked diporphyrins 4 with DDQ and Sc(OTf)3. The absorption spectrum of 2 is similar to that of the constituent subunit 3 but shows a slight red-shift for the Q-bands in near-infrared (NIR) region, indicating the exciton coupling between the neighboring diporphyrin chromophores. Observed total exciton coupling energies in the absorption spectra were largely matched with the calculated values based on point-dipole exciton coupling approximation. It was found that the experimental exciton coupling strength (292 cm-1) of the Q-band in 2 is slightly larger than the calculated one (99 cm-1), indicating that the electronic communications are enhanced through 1,3-phenylene linkers in hexameric macromolecule. A rate of the excitation energy hopping (EEH) that occurs in 2 at the lowest excited singlet state in the near-infrared region has been determined to be (1.8 ps)-1 on the basis of the pump-power dependent femtosecond transient absorption (TA) and the transient absorption anisotropy (TAA) decay measurements. The 2 times faster EEH rate of 2 than that of 1 (4.0 ps)-1 mainly comes from involving through-bond energy transfer among diporphyrin subunits via 1,3-phenylene bridges as well as F{\"o}rster-type through-space EEH processes. STM measurement of 2 in the Cu(100) surface revealed that it takes several discrete conformations with respect to the relative orientation of neighboring diporphyrins. Collectively, an effective EEH in the NIR region is realized in 2 due largely to the intensified oscillator strength in the S1 state (Q-band) and the close proximity held by 1,3-phenylene spacers.",
author = "Yoon, {Min Chul} and Yoon, {Zin Seok} and Sung Cho and Dongho Kim and Akihiko Takagi and Takuya Matsumoto and Tomoji Kawai and Takaaki Hori and Xiaobin Peng and Naoki Aratani and Atsuhiro Osuka",
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Yoon, MC, Yoon, ZS, Cho, S, Kim, D, Takagi, A, Matsumoto, T, Kawai, T, Hori, T, Peng, X, Aratani, N & Osuka, A 2007, 'A hexagonal prismatic porphyrin array: Synthesis, STM detection, and efficient energy hopping in near-infrared region', Journal of Physical Chemistry A, vol. 111, no. 38, pp. 9233-9239. https://doi.org/10.1021/jp0723923

A hexagonal prismatic porphyrin array : Synthesis, STM detection, and efficient energy hopping in near-infrared region. / Yoon, Min Chul; Yoon, Zin Seok; Cho, Sung; Kim, Dongho; Takagi, Akihiko; Matsumoto, Takuya; Kawai, Tomoji; Hori, Takaaki; Peng, Xiaobin; Aratani, Naoki; Osuka, Atsuhiro.

In: Journal of Physical Chemistry A, Vol. 111, No. 38, 27.09.2007, p. 9233-9239.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A hexagonal prismatic porphyrin array

T2 - Synthesis, STM detection, and efficient energy hopping in near-infrared region

AU - Yoon, Min Chul

AU - Yoon, Zin Seok

AU - Cho, Sung

AU - Kim, Dongho

AU - Takagi, Akihiko

AU - Matsumoto, Takuya

AU - Kawai, Tomoji

AU - Hori, Takaaki

AU - Peng, Xiaobin

AU - Aratani, Naoki

AU - Osuka, Atsuhiro

PY - 2007/9/27

Y1 - 2007/9/27

N2 - A belt-shaped hexagonal cyclic porphyrin array 2 that comprises of six meso-meso, β-β, β-β triply linked diporphyrins 3 bridged by 1,3-phenylene spacers is prepared by oxidation from cyclic dodecameric array 1 consisting of six meso-meso directly linked diporphyrins 4 with DDQ and Sc(OTf)3. The absorption spectrum of 2 is similar to that of the constituent subunit 3 but shows a slight red-shift for the Q-bands in near-infrared (NIR) region, indicating the exciton coupling between the neighboring diporphyrin chromophores. Observed total exciton coupling energies in the absorption spectra were largely matched with the calculated values based on point-dipole exciton coupling approximation. It was found that the experimental exciton coupling strength (292 cm-1) of the Q-band in 2 is slightly larger than the calculated one (99 cm-1), indicating that the electronic communications are enhanced through 1,3-phenylene linkers in hexameric macromolecule. A rate of the excitation energy hopping (EEH) that occurs in 2 at the lowest excited singlet state in the near-infrared region has been determined to be (1.8 ps)-1 on the basis of the pump-power dependent femtosecond transient absorption (TA) and the transient absorption anisotropy (TAA) decay measurements. The 2 times faster EEH rate of 2 than that of 1 (4.0 ps)-1 mainly comes from involving through-bond energy transfer among diporphyrin subunits via 1,3-phenylene bridges as well as Förster-type through-space EEH processes. STM measurement of 2 in the Cu(100) surface revealed that it takes several discrete conformations with respect to the relative orientation of neighboring diporphyrins. Collectively, an effective EEH in the NIR region is realized in 2 due largely to the intensified oscillator strength in the S1 state (Q-band) and the close proximity held by 1,3-phenylene spacers.

AB - A belt-shaped hexagonal cyclic porphyrin array 2 that comprises of six meso-meso, β-β, β-β triply linked diporphyrins 3 bridged by 1,3-phenylene spacers is prepared by oxidation from cyclic dodecameric array 1 consisting of six meso-meso directly linked diporphyrins 4 with DDQ and Sc(OTf)3. The absorption spectrum of 2 is similar to that of the constituent subunit 3 but shows a slight red-shift for the Q-bands in near-infrared (NIR) region, indicating the exciton coupling between the neighboring diporphyrin chromophores. Observed total exciton coupling energies in the absorption spectra were largely matched with the calculated values based on point-dipole exciton coupling approximation. It was found that the experimental exciton coupling strength (292 cm-1) of the Q-band in 2 is slightly larger than the calculated one (99 cm-1), indicating that the electronic communications are enhanced through 1,3-phenylene linkers in hexameric macromolecule. A rate of the excitation energy hopping (EEH) that occurs in 2 at the lowest excited singlet state in the near-infrared region has been determined to be (1.8 ps)-1 on the basis of the pump-power dependent femtosecond transient absorption (TA) and the transient absorption anisotropy (TAA) decay measurements. The 2 times faster EEH rate of 2 than that of 1 (4.0 ps)-1 mainly comes from involving through-bond energy transfer among diporphyrin subunits via 1,3-phenylene bridges as well as Förster-type through-space EEH processes. STM measurement of 2 in the Cu(100) surface revealed that it takes several discrete conformations with respect to the relative orientation of neighboring diporphyrins. Collectively, an effective EEH in the NIR region is realized in 2 due largely to the intensified oscillator strength in the S1 state (Q-band) and the close proximity held by 1,3-phenylene spacers.

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