Twisted Baskets

A preparative procedure for obtaining a pair of twisted molecular baskets, each comprising a chiral framework with either right ((P)-1(syn)) or left ((M)-1(syn)) sense of twist and six ester groups at the rim has been developed and optimized. The racemic (P/M)-1(syn) can be obtained in three synthetic steps from accessible starting materials. The resolution of (P/M)-1(syn) is accomplished by its transesterification with (1R,2S,5R)-(-)-menthol in the presence of a Ti-IV catalyst to give diastereomeric 8(P) and 8(M). It was found that dendritic-like cavitands 8(P) and 8(M), in CD2Cl2, undergo self-inclusion ((HNMR)-H-1 spectroscopy) with a menthol moiety occupying the cavity of each host. Importantly, the degree of inclusion of the menthol group was ((HNMR)-H-1 spectroscopy) found to be greater in the case of 8(P) than 8(M). Accordingly, it is suggested that different folding characteristic of 8(P) and 8(M) ought to affect the physicochemical characteristics of the hosts to permit their effective separation by column chromatography. The absolute configuration of 8(P)/8(M), encompassing right- and left-handed cups, was determined with the exciton chirality method and also verified in silico (DFT: B3LYP/TZVP). Finally, the twisted baskets are strongly fluorescent due to three naphthalene chromophores, having a high fluorescence quantum yield within the rigid framework of 8(P)/8(M).