Supramolecular Conformational Control of Aliphatic Oligoketones by Rotaxane Formation

Conformational control of aliphatic oligoketones bearing two 1,3-diketone subunits is achieved by molecular recognition with pillar[5]arene. Pillar[S]arene binds to aliphatic ketones, with association constants K of similar to 10 M-1, to form pseudorotaxanes. The pseudorotaxanes are locked by BF, complexation at the 1,3-diketone sites through quasi-solid-state reactions. X-ray crystallography reveals linear conformations for the axis molecules. The effect of supramolecular conformational restriction is evaluated using an alkyl-linked dyad chromophore system that shows solvatochromism upon intramolecular aggregation.