Surprising solvent-induced structural rearrangements in large [N⋯I+⋯N] halogen-bonded supramolecular capsules : an ion mobility-mass spectrometry study

Coordinative halogen bonds have recently gained interest for the assembly of supramolecular capsules. Ion mobility-mass spectrometry and theoretical calculations now reveal the well-defined gas-phase structures of dimeric and hexameric [N/I +/N] halogen-bonded capsules with counterions located inside their cavities as guests. The solution reactivity of the large hexameric capsule shows the intriguing solventdependent equilibrium between the hexamer and an unprecedented pentameric [N/I +/N] halogenbonded capsule, when the solvent is changed from chloroform to dichloromethane. The intrinsic flexibility of the cavitands enables this novel structure to adopt a pseudo-trigonal bipyramidal geometry with nine [N/I +/N] bonds along the edges and two pyridine binding sites uncomplexed.