Crystal Structures and Redox Responses Coupled with Ion Recognition of p-Benzoquinone- and Hydroquinone-Fused [18]crown-6

The crystal structures and redox properties of p‐benzoquinone (BQ)‐fused [18]crown‐6 1 and bis‐BQ‐fused [18]crown‐6 2 were examined. The anion radicals of these BQ molecules were stabilized by addition of metal ions, through effective electrostatic interactions between the negatively charged BQ moiety and positively charged ion‐capturing [18]crown‐6 unit. The electrostatic interactions and solvation energy played important roles in determining the magnitudes of anodic redox shifts in the reduction potentials. Regular π‐stacking of BQ units and regular arrays of [18]crown‐6 units were observed in crystal 2, in which one‐dimensional π‐electron columns were separated by ionic channels. The hydroquinone‐fused [18]crown‐6 molecule 3 and a new BQ‐ and phenol‐fused [18]crown‐6 derivative 4 were obtained as single crystals. The molecular conformations of [18]crown‐6 in crystal 3 and hydrated crystal 3⋅H2O were different from each other. Like jewels in a crown: Crystal structures of p‐benzoquinone (BQ)‐ and hydroquinone‐fused [18]crown‐6 derivatives were investigated. The redox properties of BQ‐fused [18]crown‐6 derivatives, coupled with ion capturing, were dominated by electrostatic interactions and the solvation energy.