EXCITED-STATE PROPERTIES OF THE INDOLE CHROMOPHORE - ELECTRONIC-TRANSITION MOMENT DIRECTIONS FROM LINEAR DICHROISM MEASUREMENTS - EFFECT OF METHYL AND METHOXY SUBSTITUENTS

From measurements of UV and IR linear dichroism on molecules partially oriented in stretched polyethylene host the transition moment directions for the first four pi-pi* transitions of indole and some indole derivatives were determined. Relative to the pseudosymmetry long axis of indole, the transitions were normally found to be polarized at (angles counted away from the ring nitrogen): +42 +/- 50-degrees (1A1 --> 1L(by) at 287 nm), -46 +/- 5-degrees (1A1 --> 1L(a) at 265 nm), 0 +/- 15-degrees (1A1 --> 1B(by) at 220 nm), and for the 1A1 --> 1B(a) transition occurring around 200 nm, at least at +/- 30-degrees away from this axis. In addition, indication for a weak, essentially short axis polarized transition was found at 235 nm, possibly due to the 1A1 --> 1C transition. An ambiguity problem regarding the sign of the angles was resolved by exploiting the change of orientation properties upon introduction of substituents. Orientation parameters (including diagonalizing angle) were determined by consideration of a large number of in-plane as well as out-of-plane polarized vibrational transitions. The question regarding effects on the excited states by the presence of methyl and methoxy substituents, at varied positions in the indole chromophore, was addressed in terms of the perturbations they caused on the transition moments. Whereas none of the four transitions was found to be very sensitive in this respect to methyl or methoxy groups introduced in 2-, 3-, 5-, or 7-position of indole, the directions of the weak 1A1 --> 1L(by) but also the strong 1A1 --> 1B(by) transition were found to become significantly altered by a methoxy group in 4- as well as 6-position. The conclusions are consistent with recent fluorescence anisotropy data and semiempirical calculations.