Synthesis and Preferred All‐ syn Conformation of C 3 ‐Symmetrical N ‐(Hetero)arylmethyl Triindoles

A new series of C 3 ‐symmetrical N ‐(hetero)arylmethyl triindoles has been synthesized in a straightforward procedure. The structure and conformation in the solid state have been determined for three derivatives ( 3 , 4 , and 6 ) by X‐ray crystallographic analysis. In all three cases, the molecules adopt a tripodal conformation with all of the flexible arms directed towards the same side, thereby delimiting an inner cavity. Compound 6 crystallizes and forms C 3 ‐symmetric dimeric cagelike complexes. Guest molecules of chloroform and water are confined within the resulting cavities with stabilization by different intermolecular interactions; this highlights the potential of these compounds in the construction of supramolecular systems. A computational analysis has been performed to predict the most stable conformers. As a general trend, a preference for a conformation with all branches directed to the same side has been predicted. Comparison between theoretical and experimental results indicates that the computational level selected for the present study, B3LYP/6‐31G*, is able to reproduce both the minimum energy conformations and the rotation barriers about the NCH 2 bond.