Synthesis of New Tren-Based Tris-Macrocycles. Anion Cluster Assembling Inside the Cavity Generated by a Bowl-Shaped Receptor

The synthesis of three new tris-macrocycles, containing three [12]aneN<sub>4</sub> (<b>L1</b>), [12]aneN<sub>3</sub>O (<b>L2</b>), or [14]aneN<sub>4</sub> (<b>L3</b>) moieties appended to a tren unit, is reported. The crystal structure of the [(Na(ClO<sub>4</sub>)<sub>6</sub>)⊂<b>L1</b><sub>2</sub>H<sub>13</sub>]Na<sub>6</sub>Cl<sub>2</sub>(ClO<sub>4</sub>)<sub>12</sub> compound shows the anionic cluster [Na(ClO<sub>4</sub>)<sub>6</sub>]<sup>5-</sup> assembled inside the cavity defined by two bowl-shaped polyammonium receptors, held by multiple charge−charge and hydrogen bond interactions.