Conformational preference of 2-(4-methoxyphenyl)ethanol studied by supersonic jet spectroscopy: Intramolecular OH/ interaction

A pi-type hydrogen bonding between the OH group and the pi electron is a crucial factor for the conformational preference of the molecular structure with a flexible group. However, the information on the effect of the substituent on the OH/pi interaction is insufficient. The laser-induced fluorescence (LIF) excitation, the dispersed fluorescence (DF), the IR-UV hole-burning, and the IR dip spectra of jet-cooled 2-(4-methoxyphenyl)ethanol were measured for the first time. Almost all bands observed in the spectral region of 35 550-36 500 cm(-1) in the LIF excitation spectrum were successfully assigned with the DF and the IR-UV hole-burning spectra coupled with the quantum chemical calculation at M06-2x/6-311G and MP2/6-311G levels. Five conformers were found in the LIF excitation spectrum. The most stable conformer was Gg pi, and the second most stable conformer was Gg pi ' (the trans rotamer of the methoxy group for Gg pi). Gg pi and Gg pi ' had the OH group directed toward the pi electron system of the benzene ring. The OH stretching frequency of Gg pi/Gg pi ' of MPE in the IR dip spectra was red-shifted against that of Gg pi of phenylethanol, indicating that the introduction of the methoxy group would enhance the intramolecular OH/pi interaction. In addition, the torsional vibration between the benzene ring and the side chain (-CH2CH2OH) (mode 63) was observed in the DF spectra of the Gg pi-0(0) and Gg pi '-0(0) band excitation, but their intensities were rather different, resulting from the different orientation of the OH group for each conformer toward the pi electron system. The methoxy group would increase the negative charge on the benzene ring and would enhance the intramolecular OH/pi interaction through the electrostatic interaction.