Resonance Raman spectroscopic investigation of directly linked zinc(II) porphyrin linear arrays

Dae Hong Jeong, Min Chul Yoon, Sung Moon Jang, Dongho Kim, Dae Won Cho, Naoya Yoshida, Naoki Aratani, Atsuhiro Osuka

Research output: Contribution to journalArticle

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Abstract

We have investigated the resonance Raman (RR) spectra of the directly linked porphyrin arrays in order to elucidate the relationship between excitonic interactions and molecular geometry depending on the number of pigments in the arrays. The RR spectra obtained by photoexcitation at the high-energy exciton Soret bands in the arrays are mainly composed of Raman modes localized on the constituent porphyrin monomers. In contrast, the RR spectra of the arrays with photoexcitation at the low-energy exciton split Soret bands reveal some characteristic Raman bands arising from strong excitonic interactions between the adjacent porphyrins in the arrays. Based on the RR measurements of the isotope labeled analogues and the normal-mode analysis of the dimer, it is suggested that the photoexcitation at the high-energy Soret band produces an electronically excited state largely localized within a monomer unit and that at the low-energy exciton split Soret band the excited state is in a way delocalized throughout the array. Normal mode calculation revealed that some of the RR bands of Z2 arise from vibrational splitting by dimeric interactions. Phonon-like behaviors were observed for some Cm-Cm stretching modes of the arrays, which is ascribed to enhanced polarizability induced by phenyl group movement. Collectively, our data from RR spectroscopic measurements as well as the normal-mode analysis provide a picture of the exciton coupling in relation to the molecular structure of the directly linked linear porphyrin arrays.

Original languageEnglish
Pages (from-to)2359-2368
Number of pages10
JournalJournal of Physical Chemistry A
Volume106
Issue number10
DOIs
Publication statusPublished - 2002 Mar 14

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Porphyrins
linear arrays
porphyrins
Zinc
zinc
Photoexcitation
Raman scattering
photoexcitation
excitons
Excited states
Raman spectra
Monomers
monomers
Pigments
Isotopes
Dimers
Band structure
Molecular structure
Stretching
energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Jeong, Dae Hong ; Yoon, Min Chul ; Jang, Sung Moon ; Kim, Dongho ; Cho, Dae Won ; Yoshida, Naoya ; Aratani, Naoki ; Osuka, Atsuhiro. / Resonance Raman spectroscopic investigation of directly linked zinc(II) porphyrin linear arrays. In: Journal of Physical Chemistry A. 2002 ; Vol. 106, No. 10. pp. 2359-2368.
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abstract = "We have investigated the resonance Raman (RR) spectra of the directly linked porphyrin arrays in order to elucidate the relationship between excitonic interactions and molecular geometry depending on the number of pigments in the arrays. The RR spectra obtained by photoexcitation at the high-energy exciton Soret bands in the arrays are mainly composed of Raman modes localized on the constituent porphyrin monomers. In contrast, the RR spectra of the arrays with photoexcitation at the low-energy exciton split Soret bands reveal some characteristic Raman bands arising from strong excitonic interactions between the adjacent porphyrins in the arrays. Based on the RR measurements of the isotope labeled analogues and the normal-mode analysis of the dimer, it is suggested that the photoexcitation at the high-energy Soret band produces an electronically excited state largely localized within a monomer unit and that at the low-energy exciton split Soret band the excited state is in a way delocalized throughout the array. Normal mode calculation revealed that some of the RR bands of Z2 arise from vibrational splitting by dimeric interactions. Phonon-like behaviors were observed for some Cm-Cm stretching modes of the arrays, which is ascribed to enhanced polarizability induced by phenyl group movement. Collectively, our data from RR spectroscopic measurements as well as the normal-mode analysis provide a picture of the exciton coupling in relation to the molecular structure of the directly linked linear porphyrin arrays.",
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Jeong, DH, Yoon, MC, Jang, SM, Kim, D, Cho, DW, Yoshida, N, Aratani, N & Osuka, A 2002, 'Resonance Raman spectroscopic investigation of directly linked zinc(II) porphyrin linear arrays', Journal of Physical Chemistry A, vol. 106, no. 10, pp. 2359-2368. https://doi.org/10.1021/jp0132331

Resonance Raman spectroscopic investigation of directly linked zinc(II) porphyrin linear arrays. / Jeong, Dae Hong; Yoon, Min Chul; Jang, Sung Moon; Kim, Dongho; Cho, Dae Won; Yoshida, Naoya; Aratani, Naoki; Osuka, Atsuhiro.

In: Journal of Physical Chemistry A, Vol. 106, No. 10, 14.03.2002, p. 2359-2368.

Research output: Contribution to journalArticle

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T1 - Resonance Raman spectroscopic investigation of directly linked zinc(II) porphyrin linear arrays

AU - Jeong, Dae Hong

AU - Yoon, Min Chul

AU - Jang, Sung Moon

AU - Kim, Dongho

AU - Cho, Dae Won

AU - Yoshida, Naoya

AU - Aratani, Naoki

AU - Osuka, Atsuhiro

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N2 - We have investigated the resonance Raman (RR) spectra of the directly linked porphyrin arrays in order to elucidate the relationship between excitonic interactions and molecular geometry depending on the number of pigments in the arrays. The RR spectra obtained by photoexcitation at the high-energy exciton Soret bands in the arrays are mainly composed of Raman modes localized on the constituent porphyrin monomers. In contrast, the RR spectra of the arrays with photoexcitation at the low-energy exciton split Soret bands reveal some characteristic Raman bands arising from strong excitonic interactions between the adjacent porphyrins in the arrays. Based on the RR measurements of the isotope labeled analogues and the normal-mode analysis of the dimer, it is suggested that the photoexcitation at the high-energy Soret band produces an electronically excited state largely localized within a monomer unit and that at the low-energy exciton split Soret band the excited state is in a way delocalized throughout the array. Normal mode calculation revealed that some of the RR bands of Z2 arise from vibrational splitting by dimeric interactions. Phonon-like behaviors were observed for some Cm-Cm stretching modes of the arrays, which is ascribed to enhanced polarizability induced by phenyl group movement. Collectively, our data from RR spectroscopic measurements as well as the normal-mode analysis provide a picture of the exciton coupling in relation to the molecular structure of the directly linked linear porphyrin arrays.

AB - We have investigated the resonance Raman (RR) spectra of the directly linked porphyrin arrays in order to elucidate the relationship between excitonic interactions and molecular geometry depending on the number of pigments in the arrays. The RR spectra obtained by photoexcitation at the high-energy exciton Soret bands in the arrays are mainly composed of Raman modes localized on the constituent porphyrin monomers. In contrast, the RR spectra of the arrays with photoexcitation at the low-energy exciton split Soret bands reveal some characteristic Raman bands arising from strong excitonic interactions between the adjacent porphyrins in the arrays. Based on the RR measurements of the isotope labeled analogues and the normal-mode analysis of the dimer, it is suggested that the photoexcitation at the high-energy Soret band produces an electronically excited state largely localized within a monomer unit and that at the low-energy exciton split Soret band the excited state is in a way delocalized throughout the array. Normal mode calculation revealed that some of the RR bands of Z2 arise from vibrational splitting by dimeric interactions. Phonon-like behaviors were observed for some Cm-Cm stretching modes of the arrays, which is ascribed to enhanced polarizability induced by phenyl group movement. Collectively, our data from RR spectroscopic measurements as well as the normal-mode analysis provide a picture of the exciton coupling in relation to the molecular structure of the directly linked linear porphyrin arrays.

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