Influence of Amide Connectivity on the Hydrogen‐Bond‐Directed Self‐Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self‐assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n =2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self‐assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units ( C ‐centered/carboxamide vs. N ‐centered/anilide). This subtle change results in a ≈30‐fold increase in the elongation constant for the [2.2]pCp ‐4,7,12,15‐tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp ‐4,7,12,15‐tetracarboxamide ( [2.2]pCpTA ), and a ≈300‐fold increase in the elongation constant for the [3.3]pCp ‐5,8,14,17‐tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp ‐5,8,14,17‐tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution‐phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X‐ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π‐surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H‐bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).