Citation: Sem Bleus, Sergio Ribone, Renny Maria Losus, Liliana Dobrzańska, Luc Van Meervelt, Wim Dehaen. Imination enables efficient formation of a pillararene-inspired host with endo-cavity hydrogen-bonding capability[J]. Chinese Chemical Letters, ;2026, 37(6): 111792. doi: 10.1016/j.cclet.2025.111792 shu

Imination enables efficient formation of a pillararene-inspired host with endo-cavity hydrogen-bonding capability

a.
Sustainable Chemistry for Metals and Molecules, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
b.
Unidad de Investigación y Desarrollo en Tecnología Farmacéutica (UNITEFA, CONICET), Dpto. Ciencias Farmacéuticas, Fac. Ciencias Químicas, Universidad Nacional de Córdoba, Córdoba X5000HUA, Argentina
c.
Nicolaus Copernicus University in Toruń, Faculty of Chemistry, Gagarina 7, Toruń 87-100, Poland
d.
Biomolecular Architecture, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium

wim.dehaen@kuleuven.be

Received Date: 29 April 2025
Revised Date: 18 August 2025
Accepted Date: 4 September 2025
Available Online: 5 September 2025

Figures(6)

The efficient design of novel macrocycles with enhanced properties over their parent scaffold represents a major challenge in supramolecular chemistry. Here, we exemplify imination as a purification-free method to develop novel pillar[n]arene-like macrocycles with partial-belt nitrogen functionalization. Compared to similarly sized pillar[n]arene-inspired arenes, the strategy provides an increased scalability and an up to 16-fold improvement in macrocyclization yield. X-ray crystallography and theoretical calculations reveal a similar electron density and cavity size as pillar[5]arene. The altered geometry and enhanced flexibility, however, permit complexing di-, tri- and tetrasubstituted cyanobenzenes, generating guest complementarity to all-carbon pillar[n]arenes. The suitable positioning of hydrogen bond acceptors facilitates binding based on endo-cavity hydrogen bonding, a feature largely unreported in peralkylated pillar[n]arenes. Reduction straightforwardly afforded a polyamine macrocycle of modified geometry.
- Supramolecular chemistry,
- Host-guest,
- Macrocycle,
- Pillararene,
- Dynamic combinatorial chemistry
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