We report how two flexible diphenylacetylene (DPA) derivatives distort to accommodate both cationic and anionic partners in the binary X(±)·DPA series with X = TMA(+) (tetramethylammonium), Na(+), Cl(-), Br(-), and I(-). This is accomplished through theoretical analysis of X(±)·DPA·2D2 vibrational spectra, acquired by predissociation of the weakly bound D2 adducts formed in a 10 K ion trap. DPA binds the weakly coordinating TMA(+) ion with an arrangement similar to that of the neutral compound, whereas the smaller Na(+) ion breaks all intramolecular H-bonds yielding a structure akin to the transition state for interconversion of the two conformations in neutral DPA. Halides coordinate to the urea NH donors in a bidentate H-bonded configuration analogous to the single intramolecular H-bonded motif identified at high chloride concentrations in solution. Three positions of the "switch" are thus identified in the intrinsic ion accommodation profile that differ by the number of intramolecular H-bonds (0, 1, or 2) at play.