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Ion Pair Binding in the Solid-State with Ditopic Crown Ether Uranyl Salophen Receptors.

Two ditopic uranyl salophen receptors with benzo-15-crown-5 and benzo-18-crown-6 units (R(1) and R(2), respectively) have been synthesized from commercially available starting materials. Comprehensive studies on the solid-state ion pair complexation with various alkali and ammonium halides have been conducted. From the 19 obtained solid-state structures (6 structures with R(1), 13 structures with R(2)), three general interaction motifs I-III have been observed. Interaction motif I has a separated ion pair with the cation coordinated to the crown ether unit, and the anion or oxygen containing solvent molecule coordinated to the uranyl center. The interaction motif II manifests a polymeric structure with a contact ion pair between the uranyl-coordinated anion and cation coordinated in the crown ether in the adjacent receptor. Interaction motif III consists of a more general stacked packing structure of the receptors with or without ion pairs. From the obtained solid-state structures, the complex R(2)·NaI shows an interesting formation of infinite coordination polymeric structure where the crown ether complexed sodium cations and the O═U═O units of the adjacent receptors form a nearly linear 1-D chains. In the course of this work also the first solid-state structure of uranyl salophen acetate complex was obtained (R(2)·KAcO).