One‐Step Construction of the Shape Persistent, Chiral But Symmetrical Polyimine Macrocycles

Abstract

A unique combination of structural flexibility, shape persistency and functionality, makes macrocycles and molecular cages as essential molecular entities that have displayed applications that go beyond chemistry. Among macrocycles, the selectively obtained symmetrical (poly)cyclic polyimines have shown great utility in the design of molecules varied in shape and properties. The reversible and thermodynamically controlled cycloimination reaction is governed by configurational and conformational constraints imposed on the intermediate products, ensures a sufficiently high level of preorganization. The high geometrical control over the macrocycle structure has profound effect on their assembly mode. In this Account, we were interested in showing how the structure of small building blocks affects the structure of macrocyclic product and further, how influenced the association mode of the given macromolecule. The latter is of primarily importance in supramolecular and in material chemistry.

The Chemistry of Porous Organic Molecular Materials

“…Heterochiral pairing between chiral POCs is a useful and somewhat generalizable route to modulate the pore structure and material form of POC materials, [16,17,21,27,28,[304][305][306] and similar chiral recognition behavior has been reported for imine macrocycles, prepared using chiral vicinal diamines. [307,308] For POCs, our group applied this chiral recognition strategy to create crystalline solids with 1D porous nanotube structures by cocrystallizing racemic mixtures of tubular POCs that had two linearly arranged cage windows. [27] For these 1D porous nanotube structures, CSP calculations provided a valuable in silico screening method that was used to evaluate the crystal packing preferences of the tubular POCs.…”

Imine polymers containing chiral nanohoops in the backbone obtained through [2 + 2] cyclocondensation

“…The cyclocondensation reaction is favourized by structure of the amine and aldehyde partners. (1R,2R)‐ trans ‐1,2‐Diaminocyclohexane ( 2 ) has a limited flexibility due to the rigidity of cyclohexane skeleton and the 1,2‐amine functions occupy equatorial positions and forms an 60 o quasi valence angle projected in the plane of molecule while dialdehyde 1 has the angle between OHCC 6 H 4 NC 6 H 4 CHO bonds close to 120° . Therefore, free‐strain macrocycles with rhomboidal shape are obtained as main product by [2 + 2] cyclocondensation.…”

A novel Schiff base macrocycle based on 1,1′‐binaphthyl for fluorescence recognition

“…Shape‐persistent macrocycles have been a hot subject for applications in the field of nanoscience. [ 1,2 ] Organic chiral macrocycles have been studied for their applications in molecular recognition, supramolecular architectures, and use as an asymmetric catalyst. [ 3,4 ] The incorporation of chiral building blocks into macrocyclic systems can lead to the formation of chiral macrocycle architectures, which continue to emerge as fluorescence sensors, and as chiral ligands for various asymmetric catalytic reactions.…”