Under conditions of slow intermolecular hydroxyl proton exchange 6JpOH,F < 0, 5JtransOH,F > 0, 5JcisOH,F < 0, 4JoOH,F < 0 in fluorophenol derivatives. 5JmOH,F is remarkably insensitive to intrinsic substituent effects, yields accurate values of conformational populations of m-fluorophenol derivatives and can be used to demonstrate a buttressing effect on the strength of the relatively weak [Formula: see text] hydrogen bond. 4JoOH,F displays a stereospecific dependence opposite to that of other couplings from a side-chain proton to a ring fluorine nucleus, is apparently very sensitive to the distance between proton and fluorine nucleus and is cited as an example of a negative through-space coupling mechanism. Approximate molecular orbital calculations give some support to the last suggestion.