Two shape-persistent arylene ethynylene macrocycles have been designed and synthesized as scaffolds to bind the nonpolar molecule 1,4-diiodobutadiyne. Binding via halogen bonding interactions between the pyridine moieties of the macrocycle and 1,4-diiodobutadiyne is predicted by density functional theory calculations and has been demonstrated in solution by C NMR titrations. The binding constant for the macrocycle-monomer complex ( = 10.5 L mol) is much larger than for other comparable halogen bonds, strongly supporting cooperative binding of both ends of the diyne. These results demonstrate a fully inserted geometry of 1,4-diiodobutadiyne in the complex.
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