Arylene–hexaynylene and –octaynylene macrocycles: extending the polyyne chains drives self-association by enhanced dispersion force (In memory of François Diederich.)(Electronic supplementary information (ESI) available: Synthetic procedures and characterization data of all new compounds as well as additional physicochemical and theoretical data. See DOI: 10.1039/d0cc07540j)

Tetraalkoxyphenanthrylene–hexaynylene and –octaynylene macrocycles, which represent the first examples of isolable arylene–alkynylene macrocycles (AAMs) that contain polyyne chains longer than tetrayne, were synthesized and their self-association behavior was examined. Extending the polyyne chain from diyne to tetrayne, hexayne, and octayne exponentially increased the self-association constant of the macrocycles.