Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium-Tin Oxide Electrode

Hiroshi Imahori, Kohei Hosomizu, Yukie Mori, Tomoo Sato, Tae Kyu Ahn, Seong Keun Kim, Dongho Kim, Yoshinobu Nishimura, Iwao Yamazaki, Hirotake Ishii, Hiroki Hotta, Yoshihiro Matano

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)-visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes remain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir-Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.

Original languageEnglish
Pages (from-to)5018-5025
Number of pages8
JournalJournal of Physical Chemistry B
Volume108
Issue number16
Publication statusPublished - 2004 Apr 22

Fingerprint

Porphyrins
Self assembled monolayers
Tin oxides
porphyrins
indium oxides
Indium
tin oxides
Monolayers
Electrodes
electrodes
ITO (semiconductors)
Excited states
Fluorescence
Photosystem I Protein Complex
Triethanolamine
fluorescence
indium tin oxide
Langmuir Blodgett films
Quantum yield
Langmuir-Blodgett films

All Science Journal Classification (ASJC) codes

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

Cite this

Imahori, Hiroshi ; Hosomizu, Kohei ; Mori, Yukie ; Sato, Tomoo ; Ahn, Tae Kyu ; Kim, Seong Keun ; Kim, Dongho ; Nishimura, Yoshinobu ; Yamazaki, Iwao ; Ishii, Hirotake ; Hotta, Hiroki ; Matano, Yoshihiro. / Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium-Tin Oxide Electrode. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 16. pp. 5018-5025.
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abstract = "Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)-visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes remain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir-Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.",
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Imahori, H, Hosomizu, K, Mori, Y, Sato, T, Ahn, TK, Kim, SK, Kim, D, Nishimura, Y, Yamazaki, I, Ishii, H, Hotta, H & Matano, Y 2004, 'Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium-Tin Oxide Electrode', Journal of Physical Chemistry B, vol. 108, no. 16, pp. 5018-5025.

Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium-Tin Oxide Electrode. / Imahori, Hiroshi; Hosomizu, Kohei; Mori, Yukie; Sato, Tomoo; Ahn, Tae Kyu; Kim, Seong Keun; Kim, Dongho; Nishimura, Yoshinobu; Yamazaki, Iwao; Ishii, Hirotake; Hotta, Hiroki; Matano, Yoshihiro.

In: Journal of Physical Chemistry B, Vol. 108, No. 16, 22.04.2004, p. 5018-5025.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium-Tin Oxide Electrode

AU - Imahori, Hiroshi

AU - Hosomizu, Kohei

AU - Mori, Yukie

AU - Sato, Tomoo

AU - Ahn, Tae Kyu

AU - Kim, Seong Keun

AU - Kim, Dongho

AU - Nishimura, Yoshinobu

AU - Yamazaki, Iwao

AU - Ishii, Hirotake

AU - Hotta, Hiroki

AU - Matano, Yoshihiro

PY - 2004/4/22

Y1 - 2004/4/22

N2 - Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)-visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes remain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir-Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.

AB - Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)-visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes remain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir-Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.

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