Association constants for the interaction of almost insoluble substrates with triphenylene ketal-based receptors in toluene have been determined by means of an extraction method employing the corresponding radio-labelled substrates. Flexible and more polar receptors tend to aggregate and exhibit inferior extraction qualities. Binding constants in toluene were found to be in the range 10(5)-10(7) m(-1), which is significantly higher than in dichloromethane. X-ray analyses indicate the direct participation of a water molecule in the binding process, which may account for the surprisingly small effect of moisture in the solvent on the stability of the complexes.