Probing the Endo/Exo Isomeric Variants of a Binary Complex of Cyclopropylamine with p-Fluorophenol by LIF Spectroscopy: A Comparative Study with Ammonia Complex.

Abstract

Conformational isomers of an O-H···N hydrogen-bonded binary complex between para-fluorophenol (pFP) and a nonrigid primary amine base, cyclopropylamine (CPA), have been probed by means of laser-induced fluorescence (LIF) spectroscopy in a supersonic jet expansion. Two closely spaced electronic origin bands have been identified in the measured LIF excitation spectrum, and their assignments have been corroborated by making comparisons with the spectra of the parent pFP-NH3 complex recorded under the same expansion condition. The observation is consistent with the presence of endo and exo isomeric variants of the complex predicted by electronic structure theory methods, and the endo isomer is stabilized by ∼2 kcal/mol additionally owing to the formation of a C-H···O and a C-H···π type of weak hydrogen bonds between the two moieties. In the fluorescence excitation (FE) spectrum, the low-frequency bands for different intermolecular modes gain substantial intensity, and this spectral feature is in contrast to that of the pFP-NH3 complex. The Franck-Condon intensity of the bands has been simulated invoking Duschinsky rotation scheme, taking into consideration the ground- and excited-state geometries.