Emergent Self-Assembly of a Multicomponent Capsule via Iodine Capture

Described here is a three-component self-assembly system that displays emergent behavior that differs from that of its constituents. The system comprises an all-hydrocarbon octaaryl macrocycle cyclo[8]­(1,3-(4,6-dimethyl)­benzene (D 4d -CDMB-8), corannulene (Cora), and I2. No appreciable interaction is seen between any pair of these three-components, either in cyclohexane or under various crystallization conditions. On the other hand, when all three-components are mixed in cyclohexane and allowed to undergo crystallization, a supramolecular iodine-containing capsule, ((D 4d -CDMB-8)3 ⊃(Cora)2)⊃I2, is obtained. This all-hydrocarbon capsule consists of three D 4d -CDMB-8 and two Cora subunits and contains a centrally bound I2 molecule as inferred from single-crystal and powder X-ray diffraction studies as well as solid-state 13C NMR and Raman spectroscopy. These analyses were complemented by solution-phase 1H NMR and UV–vis spectroscopic studies. No evidence of I2 escape from the capsule is seen, even at high temperatures (e.g., up to 418 K). The bound I2 is likewise protected from reaction with alkali or standard reductants in aqueous solution (e.g., saturated NaOH­(aq) or aqueous Na2S2O3). It was also found that a mixed powder containing D 4d -CDMB-8 and Cora in a 3:2 molar ratio could capture saturated I2 vapor or iodine from aqueous sources (e.g., 1.0 mM I2 in NaCl (35 wt %) or I2 + NaI­(aq) (1.0 mM each)). The present system displays structural and functional features that go beyond what would be expected on the basis of a simple sum-of-the-components analysis. As such, it illustrates a new approach to creating self-assembled ensembles with emergent features.