Photoinduced and dark complexation of unsaturated viologen analogues containing two ammonium tails with cucurbit[8]uril

Abstract

Complex formation between cucurbit[8]uril (CB[8]) and unsaturated viologen analogues 1a,b bearing two ammoniopropyl substituents was studied using 1H NMR spectroscopy and X-ray diffraction. The complex stability constants were measured by 1H NMR titration. CB[8] was found to encapsulate 1,2-di(4-pyridyl)ethylene derivative (E)-1a in water/acetonitrile solution to form only inclusion complex of 1 : 1 composition. The high stability of CB[8]·1a (lg K1:1 ≥ 5) is apparently due to the possibility of hydrogen bond formation between two NH3+ groups of 1a and the OC fragments of both portals of CB[8]. Contrarily, the derivative of 1,2-di(4-quinolyl)ethylene (E)-1b gave three types of inclusion complexes upon mixing with CB[8]. The stability of the 1 : 1 complex (lg K1:1 = 4.6) is decreased compared to (E)-1a, suggesting a poorer fit with respect to the bulky (E)-1b in the cavity of CB[8] for the simultaneous hydrogen bonding of the both ammonium groups. This is the driving force for the formation of an unusual 2 : 1 complex, {CB[8]}2·(E)-1b. The expanded π-system of (E)-1b allows also two tetracationic molecules of the acceptor to form a 1 : 2 complex owing to stacking interactions. Crystallization of a 1b/CB[8] mixture under irradiation resulted in an inclusion complex of the Z-isomer of 1b. The supramolecular complex is formed because the shape of (Z)-1b fits well to the host cavity and the ammonium groups form a system of hydrogen bonds with oxygen atoms of both portals of CB[8]. The features of crystalline complexes CB[8]·(Z)-1b and CB[8]·HClO4 are discussed.