The seeming lack of CF HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solutionElectronic supplementary information (ESI) available: FB synthesis procedure. FE, FP and FB conformer geometrical representations, energies and QTAIM molecular graphs. Infrared and 1H and 19F NMR spectra for FE, FP and FB. See DOI: 10.1039/c4cp02463j

No CF HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk solvation effects, even in nonpolar media, such as CCl 4 , cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit. According to ab initio and DFT computations the global minima of 3-fluoropropanol and 4-fluorobutanol are stabilised by intramolecular CF HO hydrogen bonds. Entropy and bulk solvation effects, however, are indicated to diminish the population of these global minima, apparently below the detection limit.