Journal of Chemical Sciences

, Volume 120, Issue 1, pp 115–129

Cyclic porphyrin dimers as hosts for coordinating ligands

Article

Abstract

Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H4A) and adjacent (cisoid, H4B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H8A4+/H8A4+ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H4A/H4B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1: I complex. The Zn2A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 Å. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 Å. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.

Keywords

Crystal structure cyclic porphyrin dimmers host-guest complexes solution conformation 

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Copyright information

© Indian Academy of Sciences 2008

Authors and Affiliations

  • G. Vaijayanthimala
    • 1
  • V. Krishnan
    • 1
  • S. K. Mandal
    • 1
  1. 1.Department of Inorganic and Physical Chemistry Indian Institute of ScienceBangaloreIndia
  2. 2.Chemical Biology Unit of the Jawaharlal Nehru Centre for Advanced Scientific ResearchIndian Institute of Science CampusBangaloreIndia

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