Host-Guest Complexes of C-Ethyl-2-methylresorcinarene and Aromatic N,N′-Dioxides

The C‐ethyl‐2‐methylresorcinarene (1) forms 1:1 in‐cavity complexes with aromatic N,N′‐dioxides, only if each of the aromatic rings has an N−O group. The structurally different C‐shaped 2,2′‐bipyridine N,N′‐dioxide (2,2′‐BiPyNO) and the linear rod‐shaped 4,4′‐bipyridine N,N′‐dioxide (4,4′‐BiPyNO) both form 1:1 in‐cavity complexes with the host resorcinarene in C4v crown and C2v conformations, respectively. In the solid state, the host–guest interactions between the 1,3‐bis(4‐pyridyl)propane N,N′‐dioxide (BiPyPNO) and the host 1 stabilize the unfavorable anti‐gauche conformation. Contrary to the N,N′‐dioxide guests, the mono‐N‐oxide guest, 4‐phenylpyridine N‐oxide (4PhPyNO), does not form an in‐cavity complex in the solid state. The host–guest complexation and the relative guest affinities were studied through 1H NMR competition experiments in methanol. Single‐crystal X‐ray crystallography of the 1:1 complexes supports the proposed solution‐state structures, also revealing strong hydrogen bonds between the host and the guests, not observed in solution owing to hydrogen/deuterium (H/D) exchange processes in methanol.