Low-Temperature Infrared Spectra and Ultraviolet-Induced Rotamerization of 5-Chlorosalicylaldehyde.

Abstract

5-Chlorosalicylaldehyde (abbreviated as 5CSA) is an important chemical used in the synthesis of fragrances, dyes, and pharmaceuticals. In this investigation, 5CSA isolated in solid N2, at 10 K, and in its neat amorphous and crystalline phases, at 50 and 190 K, respectively, were investigated by infrared spectroscopy and DFT(B3LYP)/6-311++G(d,p) calculations. The systematic theoretical analysis of the 5CSA conformational landscape showed that the compound exhibits four different conformers, which were structurally characterized in detail. In the as-deposited low-temperature matrices of 5CSA, only the most stable conformer, the intramolecularly hydrogen-bonded form I, was found. The same was observed in the case of the investigated low-temperature amorphous and crystalline phases of 5CSA. Conformer I was successfully converted into a higher-energy conformer(II), where both aldehyde and hydroxyl groups are rotated by 180° relative to their position in the initial conformer, through narrowband ultraviolet (UV) (λ = 308 nm) in situ irradiation of the as-deposited N2 matrix of 5CSA. The infrared spectra of both matrix-isolated conformers, as well as those of the neat amorphous and crystalline phases of 5CSA, were assigned and interpreted in comparative terms, allowing us to elucidate structurally and vibrationally relevant effects of the main intra- and intermolecular interactions operating in the different studied phases. Very interestingly, the observed UV-induced I → II rotamerization was found to take place in an exclusive basis, with no other photochemical processes being observed to occur upon UV irradiation, under the experimental conditions used in the present investigation.