An Inhospitable Cryptand: The Importance of Conformational Freedom in Host‐Guest Complexation

Abstract

Two new cryptands were synthesized from bis(5‐bromomethyl‐1,3‐phenylene)‐32‐crown‐10 (4). The third arms, containing 19 or 21 atoms, were installed via Williamson ether syntheses with bisphenols containing 2,6‐disubstituted pyridines. 2,6‐Diaminopyridine was converted into the bis(p‐hydroxybenzoyl) derivative 3 for the first cryptand (5) and 2,6‐dicarboxypyridine was converted into the bis(p‐hydroxybenzylamide) 9 for the second cryptand (10). Cryptand 5 did not complex viologen derivatives 11–13 to an extent detectable by 1H NMR. We attribute the lack of complexation between viologen derivatives and 5 to its lack of conformational flexibility that prevents π‐stacking, a necessary component for complexation of viologens. In contrast longer and more flexible cryptand 10 did complex dimethyl paraquat (11) with Ka = 1.6 (±0.2) × 103 m–1 in acetone at 23 °C, probably by π‐stacking with the p‐oxybenzyl moieties of the host, made available by its enhanced flexibility.