Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution

Laurent Ruhlmann, Asao Nakamura, Johannes G. Vos, Jürgen Hinrich Fuhrhop

Research output: Contribution to journalArticle

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Abstract

Noncovalent face-to-face heterodimers and -trimers between β-tetracationic and meso-tetraanionic manganese(III) porphyrins have been prepared in bulk water at pH 12. They are held together by Coulomb interactions between four β-methylpyridinium and meso-phenylsulfonate or meso-phenylcarboxylate ion pairs in eclipsed orientations. Spectroelectrochemistry has been used to characterize the redox products and to establish reversibility. UV-visible titrations indicate quantitative trimerization at concentrations > 10-5 M. Cyclic voltammetry shows that all three Mn(III) ions were oxidized simultaneously to Mn(IV) at potentials close to 300 mV at pH 12. Electroreduction to Mn(II) was often not observed in the trimers, although the monomers reacted readily under the same conditions. Quantitative chemical reduction of Mn(III) to Mn(II) porphyrin trimers was, however, achieved with dithionite. Trimers containing three paramagnetic Mn(II) or Mn(IV) ions are thus easily accessible. The heterodimers and -trimers and homodimers also catalyzed the formation of dioxygen by electrooxidation of Mn(III) to Mn(IV) between 0.6 and 2.0 V while at pH 12.

Original languageEnglish
Pages (from-to)6052-6059
Number of pages8
JournalInorganic Chemistry
Volume37
Issue number23
Publication statusPublished - 1998
Externally publishedYes

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Porphyrins
Manganese
trimers
porphyrins
manganese
Ions
aqueous solutions
Spectroelectrochemistry
Dithionite
Electrooxidation
Coulomb interactions
Titration
Cyclic voltammetry
Monomers
ions
Oxygen
Water
titration
monomers
products

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ruhlmann, L., Nakamura, A., Vos, J. G., & Fuhrhop, J. H. (1998). Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution. Inorganic Chemistry, 37(23), 6052-6059.

Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution. / Ruhlmann, Laurent; Nakamura, Asao; Vos, Johannes G.; Fuhrhop, Jürgen Hinrich.

In: Inorganic Chemistry, Vol. 37, No. 23, 1998, p. 6052-6059.

Research output: Contribution to journalArticle

Ruhlmann, L, Nakamura, A, Vos, JG & Fuhrhop, JH 1998, 'Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution', Inorganic Chemistry, vol. 37, no. 23, pp. 6052-6059.
Ruhlmann, Laurent ; Nakamura, Asao ; Vos, Johannes G. ; Fuhrhop, Jürgen Hinrich. / Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution. In: Inorganic Chemistry. 1998 ; Vol. 37, No. 23. pp. 6052-6059.
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