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Counterion-Dependent Excitonic Spectra of Tetra(p-carboxyphenyl)porphyrin Aggregates in Acidic Aqueous Solution.

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Title: Counterion-Dependent Excitonic Spectra of Tetra(p-carboxyphenyl)porphyrin Aggregates in Acidic Aqueous Solution.
Authors: Myong Yong Choi, Pollard, Jennifer A., Webb, M. Adam, McHale, Jeanne L.
Source: Journal of the American Chemical Society. 1/22/2003, Vol. 125 Issue 3, p810. 11p. 5 Diagrams, 2 Charts, 16 Graphs.
Subjects: Acids, Polyvinyl alcohol
Abstract: Aggregates of the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP) are found to be stabilized in aqueous solution at low pH in the presence of poly(vinyl alcohol). At pH values in the range from about 1 to 4, a split Sorer band is observed which is independent of counterion and tentatively assigned to a dimer species. As the pH is made lower than 1, the spectra evolve to reveal the presence of porphyrin aggregates. As in the case of the well-known aggregates of the related tetra(p-sulfonatophenyl)porphyrin (TSPP) diacid, the concentration of spectroscopically distinguishable aggregates increases with increasing ionic strength or decreasing pH. Unlike aggregates of TSPP, however, TCPP aggregates below pH 1 have visible absorption spectra which depend on the counterion, which is Cl[sup -] or NO[sub 3, sup -] in this study. In this work, we present visible absorption, light-scattering, and resonance Raman spectra of TCPP diacid in its monomer, dimer, and aggregated forms and attempt to understand the structural basis for counterion-dependent structure and excitonic coupling in the aggregates. Evidence is presented for intercalation of inorganic counterions between porphyrin molecules in the aggregate, an effect which to our knowledge has not been previously reported. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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An: 8993254
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  Data: Counterion-Dependent Excitonic Spectra of Tetra(p-carboxyphenyl)porphyrin Aggregates in Acidic Aqueous Solution.
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  Data: <searchLink fieldCode="AR" term="%22Myong+Yong+Choi%22">Myong Yong Choi</searchLink><br /><searchLink fieldCode="AR" term="%22Pollard%2C+Jennifer+A%2E%22">Pollard, Jennifer A.</searchLink><br /><searchLink fieldCode="AR" term="%22Webb%2C+M%2E+Adam%22">Webb, M. Adam</searchLink><br /><searchLink fieldCode="AR" term="%22McHale%2C+Jeanne+L%2E%22">McHale, Jeanne L.</searchLink>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 1/22/2003, Vol. 125 Issue 3, p810. 11p. 5 Diagrams, 2 Charts, 16 Graphs.
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  Data: <searchLink fieldCode="DE" term="%22Acids%22">Acids</searchLink><br /><searchLink fieldCode="DE" term="%22Polyvinyl+alcohol%22">Polyvinyl alcohol</searchLink>
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  Label: Abstract
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  Data: Aggregates of the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP) are found to be stabilized in aqueous solution at low pH in the presence of poly(vinyl alcohol). At pH values in the range from about 1 to 4, a split Sorer band is observed which is independent of counterion and tentatively assigned to a dimer species. As the pH is made lower than 1, the spectra evolve to reveal the presence of porphyrin aggregates. As in the case of the well-known aggregates of the related tetra(p-sulfonatophenyl)porphyrin (TSPP) diacid, the concentration of spectroscopically distinguishable aggregates increases with increasing ionic strength or decreasing pH. Unlike aggregates of TSPP, however, TCPP aggregates below pH 1 have visible absorption spectra which depend on the counterion, which is Cl[sup -] or NO[sub 3, sup -] in this study. In this work, we present visible absorption, light-scattering, and resonance Raman spectra of TCPP diacid in its monomer, dimer, and aggregated forms and attempt to understand the structural basis for counterion-dependent structure and excitonic coupling in the aggregates. Evidence is presented for intercalation of inorganic counterions between porphyrin molecules in the aggregate, an effect which to our knowledge has not been previously reported. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/ja0274397
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      – Code: eng
        Text: English
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        Type: general
      – SubjectFull: Polyvinyl alcohol
        Type: general
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      – TitleFull: Counterion-Dependent Excitonic Spectra of Tetra(p-carboxyphenyl)porphyrin Aggregates in Acidic Aqueous Solution.
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            NameFull: Pollard, Jennifer A.
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              Text: 1/22/2003
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              Y: 2003
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