Trianglamines—Readily Prepared, Conformationally Flexible Inclusion‐Forming Chiral Hexamines

Abstract Trianglamines, macrocyclic heteraphanes, were readily synthesised through a [3+3] cyclocondensation of ( R , R )‐1,2‐diaminocyclohexane with terephthalaldehyde, followed by NaBH 4 reduction and N‐alkylation. The macrocyclic ring shows a remarkable ability to change its conformation, as a consequence of rotation about the CN bonds or nitrogen inversion due to protonation or N‐alkylation, as revealed by circular dichroism spectra, computational modelling and X‐ray diffraction analysis. The flexible natures of the trianglamine macrocycles allow ready accommodation of a variety of guest molecules to form crystalline inclusion complexes of highly diversified interpenetrating structures.