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]aneN4 (L1), [12]aneN3O (L2), or [14]aneN4 (L3) moieties appended to a tren unit, is reported. The crystal structure of the [(Na(ClO4)6)⊂L12H13]Na6Cl2(ClO4)12 compound shows the anionic cluster [Na(ClO4)6]5- assembled inside the cavity defined by two bowl-shaped polyammonium receptors, held by multiple charge−charge and hydrogen bond interactions.