Consequences of hidden kinetic pathways on supramolecular polymerization

Abstract

<p>We show that hidden kinetic states have a dramatic impact on the thermodynamics of supramolecular polymerization, enabling new aggregation pathways with potentially new functionalities.</p>

Tuning energy landscapes and metal–metal interactions in supramolecular polymers regulated by coordination geometry

“…These findings can be attributed to stretching of the phenyl rings as well as the ethynylene units. 75–77 …”

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

“…Very recently, the group of Fernández showed that quenching of a supramolecular system with bad solvents may lead to the formation of kinetic traps that cannot be accessed through thermal quenching. 141 Thus, although the dependency of the Gibbs free energy of a polymer on solvent quality is analogous to the temperature dependency (see eq 1 ), these results show that kinetic trapping via solvent or thermal quenching can be different.…”

The Competitive Aggregation Pathway of an Asymmetric Chiral Oligo(p‐phenyleneethynylene) Towards the Formation of Individual P and M Supramolecular Helical Polymers

“…The NÀH, C=O and amide II stretching bands obtained for Agg I and Agg II -n N-H = 3302 cm À1 , n C=O = 1670 cm À1 , n amide II = 1522 cm À1 -indicate the presence of an H-bond pattern that stabilizes both aggregates, which is not observed for the monomeric form of (S)-1 -n N-H = 3375 cm À1 , n C=O = 1690 cm À1 , n amide II = 1518 cm À1 -(Figure S4a). [15] NMR also confirmed the presence of aggregates. Comparison of the 1 H-NMR spectra obtained in DCM-d 2 and different mixtures of MCH-d 14 / DCM-d 2 shows an upfield shift for all the proton signals of (S)-1, denoting the aggregation of this compound and the high anisotropic effects of the OPE and MPA units (Figure S4b, c).…”

“…The CD trace obtained for a freshly prepared Agg I sample becomes null with time accompanied with a reduction in UV/Vis spectroscopy, indicating that the aggregates are not dispersed in the solvent mixture. [15] Next, the aggregation of (S)-1 was studied in detail by a combination of CD, UV/Vis, 1 H-NMR, ATR-FTIR and microscopy studies.…”