The nature of improper, blue-shifting hydrogen bonding verified experimentally.

In the infrared spectra of solutions in liquid argon of dimethyl ether ((CH(3))(2)O) and fluoroform (HCF(3)), bands due to a 1:1 complex between these monomers have been observed. The C-H stretch of the HCF(3) moiety in the complex appears 17.7 cm(-1) above that in the monomer, and its intensity decreases by a factor of 11(2). These characteristics situate the interaction between the monomers in the realm of improper, blue-shifting hydrogen bonding. The complexation shifts the C-F stretches downward by some 9 cm(-1), while the C-H stretches in (CH(3))(2)O are shifted upward by 9-15 cm(-1), and the C-O stretches are shifted downward by 5 cm(-1). These shifts are in very good agreement with those calculated by means of correlated ab initio methods, and this validates a two-step mechanism for improper, blue-shifting hydrogen bonding. In the first step, the electron density is transferred from the oxygen lone electron pairs of the proton acceptor ((CH(3))(2)O) to fluorine lone electron pairs of the proton donor (CHF(3)) which yields elongation of all CF bonds. Elongation of CF bonds is followed (in the second step) by structural reorganization of the CHF(3) moiety, which leads to the contraction of the CH bond. It is thus clearly demonstrated that not only the spectral manifestation of H-bonding and improper H-bonding but also their nature differ.