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Titre du document / Document title

Ground-and excited-state tautomerism in porphycenes

Auteur(s) / Author(s)

WALUK Jacek ;

Résumé / Abstract

Owing to short distances between the inner nitrogen atoms and, therefore, strong intramolecular hydrogen bonds, porphycenes display completely different tautomeric properties than porphyrins, their constitutional isomers. Tunneling splitting caused by delocalization of two inner hydrogen atoms is observed for porphycenes isolated in supersonic jets. The barrier to tautomerization is higher in the lowest excited singlet state than in the ground state. Still, rapid exchange of inner hydrogen atoms is detected in S1. The mechanism of tautomerization involves synchronous double hydrogen tunneling, activated by excitation of a low-frequency mode, which modulates the NH···N separation. This separation can also be strongly altered by peripheral substitution. In porphycenes with alkyl substituents on the ethylene bridges, the NH···N distances become extremely small. For these derivatives, both trans and cis tautomeric forms are detected. Tautomerism in porphycenes was also monitored on a single-molecule level.

Revue / Journal Title

Accounts of chemical research    ISSN  0001-4842 

Source / Source

2006, vol. 39, no12, pp. 945-952 [8 page(s) (article)]

Langue / Language

Anglais

Editeur / Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1968) (Revue)

Localisation / Location

INIST-CNRS, Cote INIST : 13765, 35400014517412.0080

Nº notice refdoc (ud4) : 18362380



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