Theoretical study of the cooperativity in substituted dimethyl ethers complexed with two water molecules. Red or blue shifts of the ν(CH) vibrations?

► Cooperativity in fluorinated -water systems has been analyzed for the first time. ► Highly fluorinated ethers show blue shift of CH bond with one water but red shifts with two water molecules. ► The relative magnitude of intra- and intermolecular hyperconjugations is found to determine the shift. ► Nice charge reciprocal effect is observed between the two water molecules.