The tandem process
of phenol addition to a cyclic α,β-unsaturated
ester followed by intramolecular transesterification and [1,5] sigmatropic
rearrangement affords a series of helical coumarins based upon a previously
unknown 3-amino-7-hydroxybenzo[3,4]cyclohepta[1,2-
c
]chromen-6-one core. These novel polarized coumarins, possessing
a β-ketoester moiety, have been employed to synthesize more
rigid and helical coumarin–pyrazolones, which display green
fluorescence. The enhanced emission of coumarin–pyrazolones
in polar solvents depends on the nature of the
S
1
state. The coumarin–pyrazolones are predicted to have
two vertical states close in energy: a weakly absorbing
S
1
(
1
LE) followed by a bright
S
2
state (
1
CT). In polar solvents, the
1
CT can be stabilized below the
1
LE and may become
the fluorescent state. Solvatochromism of the fluorescence spectra
confirms this theoretical prediction. The presence of an N—H···O=C
intramolecular hydrogen bond in these coumarin–pyrazolone hybrids
facilitates excited-state intramolecular proton transfer (ESIPT).
This process leads to a barrierless conical intersection with the
ground electronic state and opens a radiationless deactivation channel
effectively competing with fluorescence. Solvent stabilization of
the CT state increases the barrier for ESIPT and decreases the efficiency
of the nonradiative channel. This results in the observed correlation
between solvatochromism and an increase of fluorescence intensity
in polar solvents.