Structurally-variable, rigid and optically-active D2 and D3 macrocycles possessing recognition properties towards C60

Abstract

The reactivity of aromatic dicarboxylic acids, in combination with an axially-chiral, suitable dibenzylic alcohol, derived from BINOL, has been exploited in one-pot esterification reactions for the direct formation of several rigid, homochiral macrocycles. Cyclic adducts possessing, respectively, average molecular D(2) and D(3) symmetries, have been characterized in pure forms, with isolated yields and selectivities which are substantially different from those rising from purely statistical arguments. NMR and CD spectroscopies detect the structural and shape variability in the scaffolds, reflected both in terms of large changes in chemical shifts of selected proton resonances, and in terms of the variation of the CD signature related to the dihedral angle defined by the binaphthyl units embedded in the rigid cyclic skeleton. The crystal structure of two homochiral D(2) macrocycles show the formation of ordered nanostructures in the solid state, with the naphthyl rings of the binaphthyl units packing intermolecularly in an eclipsed-like conformation to yield nonhelical tubular arrangements. The larger D(3) cyclic adducts are able to afford stable complexes with C(60) in toluene solution, with comparable binding strengths, yet whose stoichiometries are dependent on small variations in the spacing units and therefore in the shapes of the internal cavities of the cyclic structures.