An Experimental Study on the Effect of Substituents on Aromatic-Aromatic Interactions in Dithia[3,3]-metaparacyclophanes

Simple model systems based on the 2,11-dithia[3,3]-metaparacyclophane skeleton were synthesized to study the effects of substituents on the intramolecular aromaticaromatic interactions between benzene rings. X-ray crystallography established that, in their more stable conformations, these metaparacyclophanes featured partially overlapping aromatic rings (interplanar distances of about 3.5 angstrom), with the planes of the aromatic systems arranged in a slightly tilted disposition (interplanar angles in the range 519 degrees). Calculations showed that these derivatives underwent topomerization by flipping of the meta-substituted ring over the para-substituted one, a process in which the two rings adopted a continuum of edge-to-face dispositions, including an orthogonal one, which were less stable than the starting face-to-face arrangement. The energy barriers to the isomerization process were experimentally determined by variable-temperature NMR spectroscopy, by using an internal temperature standard to assess even minor differences in energy (relative experimental error: (+/- 0.1 kJ?mol-1). The variation in the barriers as a function of the different substituents on the interacting ring was small and apparently unrelated to the effect of the substituents on the polarity of the p-systems. An explanation based on the charge-penetration effect seemed more-suitable to rationalize the observed trends in the barriers.