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 solvent-dependent equilibrium between the hexamer and an unprecedented pentameric [N⋯I⁺⋯N] halogen-bonded 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.

中文翻译：

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大型[N⋯I+⋯N]卤素键合超分子胶囊中令人惊讶的溶剂诱导结构重排：离子淌度-质谱研究†‡

配位卤素键最近在超分子胶囊的组装中引起了人们的兴趣。^{离子淌度-质谱法和理论计算现在揭示了二聚体和六聚体 [N⋯I +} ⋯N] 卤素键合胶囊的明确气相结构，其中反离子作为客体位于其空腔内。当溶剂从氯仿变为二氯甲烷时，大六聚胶囊的溶液反应性显示了六聚体和前所未有的五聚[N⋯I ⁺ ⋯N]卤键胶囊之间存在有趣的溶剂依赖性平衡。空配体的固有灵活性使这种新颖的结构能够采用伪三角双锥几何形状，沿边缘有九个 [N⋯I ^{+ ⋯N] 键和两个未复合的吡啶结合位点。}