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Noncovalent interactions between several protonated amines and an original ditopic receptor, nor-seco-cucurbit[10]uril, are investigated by combining mass spectrometry-based methods and computational chemistry. Electrospray ionization is used to transfer the intact supramolecular assemblies from their acidic solution to the gas phase, provided fine-tuning of the source parameters is achieved. Ternary complexes, associating two guest molecules and one host cavity, are observed systematically in the mass spectrometry analyses and the quasi-exclusive occurrence of these 2:1associations reveals the allosteric nature of the complexation reaction. It is demonstrated that the binary 1:1complex ions that are detected arise from collision-induced dissociation processes undergone by the ternary complex ions inside the ion source. Based on ion mobility experiments supported by theoretical calculations, the inclusion nature of the gas-phase ternary complexes is clearly evidenced independent of the size of the probed guest molecule and the charge state of the complex ions. The allosteric nature of the complexation reactions is dictated by size criteria. This is demonstrated on the basis of mass spectrometry experiments by analyzing solutions containing ligands of different sizes in competition for inclusion within the guest cavity. Computational chemistry is also used to characterize the three-dimensional structures of the complexes.