Polarized Helical Coumarins: [1,5] Sigmatropic Rearrangement and Excited-State Intramolecular Proton Transfer

[Image: see text] 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.