A new cryptand, bis(1,3,5-phenylene)tri(1,4,7,10-tetraoxadecyl) (3a), has been synthesized in good yield from bis(5-hydroxy-1,3-phenylene)-26-crown-8 (2a) and tri(ethylene glycol) ditosylate using pseudo-high dilution conditions. 3a forms a strong 1:1 complex with paraquat (1) in acetone solution with a high apparent association constant, 1.4 x 10(4) M-1. A stoichiometry of 1:1 was also observed by mass spectrometry in the gaseous state. However, in the solid state, as determined by X-ray crystallography, the two complexes of 3a and the previously reported homologous cryptand, bis(1,3,5-phenylene)tri(1,4,7,10,13-pentaoxatridecyl) (3b), with paraquat (1) have 2:1 stoichiometry. A unique feature of these trimolecular pseuclorotaxane-like complexes is that the guest occupies parts of the cavities of two cryptand molecules. For the first time it was found that in cryptand-based complexes, different stoichiometries are possible for the same host-guest pair.