Effect of Substituents on the Molecular Shapes of π-Basic Macrotricyclic Receptors

2010

Molecular recognition between receptor and substrate is optimized when these compounds show complementary shapes, sizes, and interacting moieties. A family of C3v-symmetric macrotricycles 1–4 is presented that incorporate resorcinol- and mesitylene-derived “walls” and “cap”, respectively. These compounds feature, in principle, a tetrahedral π-basic cavity. This paper reports the effect of substituents in the “walls” and the “cap” on the shapes of the macrotricycles in solution (1H NMR), the solid state (X-ray diffraction), and gas phase (calculations). Substitution of the lower position of the “walls” by Br (in 3) or MeS (in 4) has the same effect as ethyl substitution of the “cap” (in 2), …