Theoretical study on rotation of pyrrole rings in porphyrin and N-confused porphyrin

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Rotation of pyrrole rings in regular porphyrins and N-confused porphyrins is theoretically investigated by DFT calculations. While the inversion of the pyrrole rings in the regular porphyrins requires high activation energies (36.5-49.1 kcal/mol), the inversion of the confused pyrrole rings in the N-confused porphyrins requires much lower activation energies (18.1-24.5 kcal/mol). This marked difference can be explained by the intramolecular hydrogen bondings and aromatic stabilization due to the [18]annulenic substructures, where confusion and NH tautomerism play an important role. In both of the macrocycles, 360° rotation of their pyrrole rings would be difficult possibly due to the small cavity. Alternatively, a reaction pathway for the production of N-fused porphyrin from. N-confused porphyrin is obtained, which is consistent with the experimental, observation.

Original languageEnglish
Pages (from-to)13953-13963
Number of pages11
JournalJournal of Physical Chemistry A
Issue number50
Publication statusPublished - Dec 17 2009

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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