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