Probing Orientation-Specific Charge-Dipole Interactions between Hexafluoroisopropanol and Halides: A Joint...

The interactions between hexafluoroisopropanol (HFIP) and halogen anions X^- (F^-, Cl^-, Br^-, and I^-) have been investigated using negative ion photoelectron (NIPE) spectroscopy and ab initio calculations. The measured NIPE spectrum of each [HFIP·X]^- (X = Cl, Br, and I) complex shows a pattern identical to the corresponding X^- by shifting to the high electron binding energy side, indicative of the formation of the [HFIP···X^-] structure in which X^- interacts with HFIP via charge-dipole interactions. However, the spectrum of [HFIP·F]^- appears completely different from that of F^- and is more similar to the spectrum of the deprotonated HFIP anion (HFIP_-H). The geometry and electron density calculations indicate that a neutral HF molecule is formed upon HFIP interacting with F^- via proton transfer, rendering a stable structure of [HFIP_-H···HF]^-. Two conformers of [HFIP_-H·HF]^- with HFIP being in synperiplanar and antiperiplanar configurations, respectively, are observed, providing direct experimental evidences to show the distinctly different and orientation-specific interactions between HFIP and halide anions.