Co-conformational isomerism in a neutral ion-paired supramolecular system

Article abstract of DOI:10.1002/chem.201203483

Two different counter-ion-free host-guest complexes have been prepared and isolated. These compounds were formed from two equally and opposite doubly-charged species, the viologen guests 1 a²⁺ and 1 b ²⁺ and the anti-disulfodibenzo[24]crown-8 [DSDB24C8]^2- host, which gave rise to the 1:1 neutral complexes [1 a×DSDB24C8] and [1 b×DSDB24C8]. These species are held together by hydrogen bonding and π stacking, as well as strong electrostatic interactions. The investigation of these neutral ion-paired supramolecular systems in solution and in the solid state allowed us to establish their co-conformational preferences. Compound [1 a×DSDB24C8], with small methyl groups as substituents on the viologen unit, may adopt three different geometries, 1) an exo nonthreaded, 2) a partially threaded, and 3) a threaded arrangement, depending on the relative spatial orientation between the host and guest: The partially-threaded structure is preferred in solution and in the solid state. The presence of bulky tert-butylbenzyl groups in the viologen moiety in compound [1 b×DSDB24C8] restricts the possible geometrical arrangements to one: The exo nonthreaded arrangement. This structure was confirmed in the solid state by X-ray crystallography. The stability of the neutral complexes in solution was determined by UV/Vis spectrophotometry. The stoichiometry of the complexes was established by continuous variation experiments, and ove Copyright