Counterintuitive consequences of competitive pathways in supramolecular polymerizations

Mathijs F J Mabesoone,E W Meijer

doi:10.1002/pola.29456

Mathijs F J Mabesoone, E W Meijer

Open Access

https://doi.org/10.1002/pola.29456

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Abstract

Competition between supramolecular polymers for the same monomers can lead to strong responses in these systems. Using numerical simulations, we show that the sharpness and asymmetry of the transition from one thermodynamically stable polymer to another upon changing temperature is determined by the most unstable rather than the most stable supramolecular polymer. The width and asymmetry of the transitions are shown to depend on the relative and absolute nucleation penalties of the competing supramolecular polymerizations.

Highlights

The performance of molecular and polymeric materials in various applications, such as optoelectronics, is highly dependent on the defined morphology and order in these materials.[1,2] In supramolecular polymeric systems, high degrees of helical order are typically achieved in strongly cooperative polymerizations.[3]
Control over the kinetic stability has paved the way of living supramolecular polymers[5,6,7,8] and the synthesis of kinetically controlled supramolecular block copolymers.[9,10]
Many of these studies are inspired by the seminal science of Kris Matyjaszewski on covalent macromolecules, where kinetic information is combined with the synthesis of novel architectures