Hydrogen-bond Formation between isoindolo[2,1-a]indol-6-one and aliphatic alcohols in n-hexane

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The spectroscopic, kinetic, and equilibrium properties of isoindolo[2,1-a]indol-6-one (I) were studied in n-hexane in the presence and absence of alcohols (X). Hydrogen-bonded-complex formation was found to occur between the alcohol and the ground state as well as the excited state of the I molecule. The spectra of I and its singly complexed derivative (IX) are similar; however, that of IX is red shifted. The extent of red shift increases with the hydrogen-bonding ability of the alcohol. Equilibrium constant measurements were made to determine the hydrogen-bond basicity (β2H) for I and the singlet excited 1I. The β2H value for 1I is found to be about twice that of the ground-state I. Time-resolved fluorescence decay measurements indicate that the reaction of singlet excited I with fluorinated alcohols is diffusion controlled, while the rate of complexation with nonfluorinated (weaker hydrogen bonding) aliphatic alcohols depends on the Gibbs energy change in the complexation reaction. The quantitative correlation between the rate coefficient of complexation of 1I with alcohols and the Gibbs energy change in the complexation process allowed us to estimate the rate coefficient for the complexation of the ground-state I with alcohols. The formation of the singlet excited hydrogen-bonded complex is irreversible; 1IX disappears in a first order and an alcohol induced second order reaction. The first order decay is predominantly due to internal conversion to the ground state, the rate of which depends on the ionization energy of the complexing alcohol.

Original languageEnglish
Pages (from-to)2043-2049
Number of pages7
JournalJournal of Physical Chemistry A
Issue number10
Publication statusPublished - Mar 17 2005


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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