Surface-Enhanced Infrared Spectra of Manganese (III) Tetraphenylporphine Chloride Physisorbed on Gold Island Films

Vongsvivut, Jitraporn, Itoh, Tamitake, Ikehata, Akifumi, Ekgasit, Sanong and Ozaki, Yukihiro 2006, Surface-Enhanced Infrared Spectra of Manganese (III) Tetraphenylporphine Chloride Physisorbed on Gold Island Films, ScienceAsia, vol. 32, no. 3, pp. 261-269, doi: 10.2306/scienceasia1513-1874.2006.32.261.

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Title Surface-Enhanced Infrared Spectra of Manganese (III) Tetraphenylporphine Chloride Physisorbed on Gold Island Films
Author(s) Vongsvivut, Jitraporn
Itoh, Tamitake
Ikehata, Akifumi
Ekgasit, Sanong
Ozaki, Yukihiro
Journal name ScienceAsia
Volume number 32
Issue number 3
Start page 261
End page 269
Publisher Science Society of Thailand under the Patronage of His Majesty the King
Place of publication Bangkok, Thailand
Publication date 2006
ISSN 1513-1874
Keyword(s) tetraphenylporphine
surface-enhanced infrared absorption
metal island film
atomic force microscopy
Summary Surface-enhanced infrared absorption (SEIRA) spectra of manganese (III) tetraphenylporphine chloride (Mn(TPP)Cl) on metal island films were measured in transmission mode. Dependences of the enhancement factor of SEIRA on both the sample quantity and the type of evaporated metal were investigated by subsequently increasing the amount of Mn(TPP)Cl on gold and silver substrates. The enhancement increases nonlinearly with the amount of sample and varies slightly with the thickness of metal islands. In particular, the SEIRA transmission method presents an anomalous spectral enhancement by a factor of 579, with substantial spectral shifts, observed only for the physisorbed Mn(TPP)Cl that remained on a 3-nm-thick gold film after immersion of the substrates into acetone. A charge-transfer (CT) interaction between the porphyrinic Mn and gold islands is therefore proposed as an additional factor in the SEIRA mechanism of the porphyrin system. The number of remaining porphyrin molecules was estimated by calibration-based fluorescence spectroscopy to be 2.36×1013 molecules (i.e., ~2.910-11 mol/cm2) for a 3-nm-thick gold film, suggesting that the physisorbed molecules distributed very loosely on the metal island surface as a result of the weak van der Waals interactions. Fluorescence microscopy revealed the formation of microcrystalline porphyrin aggregates during the consecutive increase in sample solution. However, the immersion likely redistributed the porphyrin to be directly attached on the gold surface, as evidenced by an absence of porphyrinic microcrystals and the observed SEIRA enhancement. The distinctive red shift in the UV-visible spectra and the SEIRA-enhanced peaks indicate the presence of a preferred orientation in the form of the porphyrin ring inclined with respect to the gold surface.
Language eng
DOI 10.2306/scienceasia1513-1874.2006.32.261
Field of Research 030101 Analytical Spectrometry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2005, ScienceAsia. All Rights Reserved
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Document type: Journal Article
Collection: School of Life and Environmental Sciences
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