The novel title macrocycles, based on methylene-bridged 1,5-naphthalene units, have been obtained by template effect in a thermodynamically controlled synthesis. In details, the prism[5]arene 1 or the prism[6]arene 3 was selectively taken away from the equilibrium mixture by using the complemen-tary ammonium-templating agent. When only the solvent 1,2-DCE was used, then the 1,4-confused derivative 2 was ob-tained. The prism[5]arene here described shows a deep π-electron rich aromatic cavity thanks to which exhibits a great affinity for the quaternary ammonium guests, originat-ing from favorable cation··· π and +NC−H··· π interactions. This recognition motif is the basis of the templated synthesis of the prism[n]arenes here reported.

When a 1,3-dipolar cycloaddition between nitrones and α,β-unsaturated aldehydes catalyzed by L-proline derivatives takes place inside the hexameric resorcin[4]arene capsule the products are obtained in higher yields and selectivity, with respect to the reaction in bulk solution. The 4-formyl regioisomers were obtained preferentially, with an excellent preference for the endo-diastereoisomers and with moderate to good enantioselectivities. An extended in silico study was conducted to rationalize the observed outcome and to investigate the equilibria between the reagents outside and inside the capsule.

The composition of dynamic covalent imine libraries adapts to the presence of the hexameric resorcinarene capsule. In the presence of the self-assembled capsule a kinetic and thermodynamic modulation of the imine constituents of the DCLs was observed, which was induced by an unusual predatory action of the capsule on specific imine constituents. More complex 2x2 DCLs also adapt to the presence of the hexameric capsule showing a thermodynamic and kinetic mod-ulation of the constituents induced by the predatory action of the capsule. By cross-referencing experimental data, a good selectivity (up to 66 %) for one constituent can be induced in a 2x2 DCL