Diels–Alder/Retro-Diels–Alder Reactions as Fold Altering Chemical Stimuli to Control the Self-Assembly of Aromatic Oligoamides
(2026) Journal of the American chemical society — Vol. 148, n° 5, p. 4989-4998 (2026)
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- Authors
Singleton, Michael L. 
- Abstract
- Self-assembly of aromatic oligoamides into multi- 5 helical structures is a powerful strategy for developing complex and 6 functional molecular architectures. As the hybridization process is 7 directed by the folded state of the oligomers, inducing changes in 8 the folding can be used to control the self-assembly. As one 9 approach for this, Diels−Alder reactions on diazaanthracene 10 monomers allow site-specific modification of aromatic oligoamides. 11 The reaction leads to a bend in the monomer that, in turn, distorts 12 the structure of the oligomer. Herein, we show that this strategy 13 can be used to control the self-assembly of the oligomers. Using 14 reversible Diels−Alder reactions allows switching between distinct 15 folded states with different self-assembly preferences. This strategy can be applied during oligomer synthesis to prevent self-assembly 16 or postsynthetically to disassemble multihelical structures. In complex systems containing multiple oligomers, we show that the 17 modification can further be used to direct social versus narcissistic self-sorting, allowing for the switch between homomeric and 18 heteromeric double helical assemblies.
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Citations
Smal, L., Kerff, F., Robeyns, K., & Singleton, M. L. (2026). Diels–Alder/Retro-Diels–Alder Reactions as Fold Altering Chemical Stimuli to Control the Self-Assembly of Aromatic Oligoamides. Journal of the American chemical society, 148(5), 4989-4998. https://doi.org/10.1021/jacs.5c14812 (Original work published 2026)