title: Biradical intermediates in the photoisomerization of dibenzodihydropentalenofurans to dibenzosemibullvalenes.
abstract: The photoisomerization of a few substituted dibenzodihydropentalenofurans to the corresponding dibenzosemibullvalenes is reported. Steady-state photolysis of the dibenzodihydropentalenofurans 3a--d gave the corresponding dibenzosemibullvalenes 2a--d in nearly quantitative yields. The quantum yields of this photoisomerization were found to be in the range 0.17--0.26. Laser flash photolysis studies of the dibenzodihydropentalenofurans 3a-e showed transients, with absorption maxima around 410 nm and decaying by first-order kinetics. The lifetimes were in the range 14--30 micros in degassed benzene at 25 degrees C. These transients were readily quenched (trapped) by molecular oxygen, and the Stern-Völmer quenching constants were found to be in the range (2.45--3.17) x 10(9) M(-1) s(-1). As a representative example, the 1,3-biradical intermediate from 3e was trapped by molecular oxygen to give the corresponding endoperoxide 11e. The transients were weakly quenched by triplet/radical quenchers such as 2,2,6,6-tetramethylpiperinyl-1-oxy (TEMPO) and 4-hydroxy-2,2,6,6-tetramethylpiperinyl-1-oxy (HTEMPO), and the quenching constants are found to be in the range (1.09--3.19) x 10(6) M(-1) s(-1). The decay rates of the transients were found to be temperature dependent and obeyed the Arrhenius equation. For example, the activation energy of the transient from 3a was approximately 4.5 kcal mol(-1) and the Arrhenius preexponential factor log(A/s(-1)) for the decay of the transients was approximately 7.5. On the basis of our studies, these transients were assigned as the ground-state triplet biradicals, generated by the cleavage of the C--O bond of the starting dibenzodihydropentalenofurans.
authors.affiliation: Photochemistry Research Unit, Regional Research Laboratory (CSIR), Trivandrum 695 019, India.
authors.forename: M C
authors.initials: MC
authors.lastname: Sajimon
authors.forename: D
authors.initials: D
authors.lastname: Ramaiah
authors.forename: K G
authors.initials: KG
authors.lastname: Thomas
authors.forename: M V
authors.initials: MV
authors.lastname: George