Dissipative Formation of Covalent Basket Cages.

Liyana Gunawardana, Vageesha W.; Finnegan, Tyler J.; Ward, Carson E.; Moore, Curtis E.; Badjić, Jovica D.

Living systems use chemical fuels to transiently assemble functional structures. As a step toward constructing abiotic mimics of such structures, we herein describe dissipative formation of covalent basket cage CBC 5 by reversible imine condensation of cup‐shaped aldehyde 2 (i.e. basket) with trivalent aromatic amine 4. This nanosized [4 4] cage (V=5 nm3, Mw=6150 Da) has shape of a truncated tetrahedron with four baskets at its vertices and four aromatic amines forming the faces. Importantly, tris‐aldehyde basket 2 and aliphatic tris‐amine 7 undergo condensation to give small [1 1] cage 6. The imine metathesis of 6 and aromatic tris‐amine 4 into CBC 5 was optimized to bias the equilibrium favouring 6. Addition of tribromoacetic acid (TBA) as a chemical fuel perturbs this equilibrium to result in the transient formation of CBC 5, with subsequent consumption of TBA via decarboxylation driving the system back to the starting state.

CHEMICAL systems; BASKETS; AROMATIC amines; DECARBOXYLATION; CONDENSATION

Angewandte Chemie, 2022, Vol 134, Issue 33, p1

0044-8249

Academic Journal

10.1002/ange.202207418