Intramolecular NH/pi complexes of 2-allylaniline derivatives in the ground and excited states.
The photochemical and photophysical properties of three 8-allyl-1,2,3,4-tetrahydroquinolines (1a-c) have been studied. These compounds exhibit a 2-allylaniline-like photochemical behavior, undergoing photocyclization to lilolidines (3a-c). The absorption, emission, and excitation spectra of 1a-c, employing convenient model compounds for comparison, demonstrate the formation of a NH/pi intramolecular ground-state complex (AB). This species can absorb light at long wavelengths (330-340 nm), giving rise to the corresponding excited complex AB*. Emission from AB* is red-shifted (420 nm) with respect to that observed when the monomer A is excited (lambda(exc) = 300 nm). These experimental results have been rationalized by means of density-functional theory calculations.
Leo
Edgar A
EA
Departamento de Química-Instituto de Tecnología Química UPV-CSIC, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain.
Tormos
Rosa
R
Monti
Sandra
S
Domingo
Luis R
LR
Miranda
Miguel A
MA