Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Vantomme, Ghislaine; Huurne, Gijs M. ter; Kulkarni, Chidambar; Eikelder, Huub M. M. ten; Markvoort, Albert J.; Palmans, Anja R. A.; Meijer, E. W.

doi:10.1021/jacs.9b09443

Cited by 60 publications

(62 citation statements)

References 51 publications

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“…These results point to either an absence of interactions between a‐BTA polymers and S ‐nMe‐BTA (self‐sorting) or to a chain‐capper role of S ‐nMe‐BTA for a‐BTA stacks . This is in contrast to two other scenarios: 1) an increase in T e is expected if S ‐nMe‐BTA intercalates into a‐BTA stacks because the total concentration of BTAs present in supramolecular polymers increases, or 2) a decrease of T e is expected when S ‐nMe‐BTA interacts with a‐BTA monomers by forming short stable side species in a competitive pathway, which effectively decreases the concentration of BTAs present in the supramolecular polymers . For the analysis of HC‐BTA , UV/CD spectroscopy could not be performed for a‐BTA / HC‐BTA solutions in toluene because of the overlap between the solvent absorption and the maximum absorption of BTA monomers.…”

Section: Resultsmentioning

confidence: 90%

“…To further understand the interactions between the different additives and a‐BTA , the weight‐average length of the supramolecular polymers as a function of the addition of S ‐nMe‐BTA and HC‐BTA was measured by static light scattering (SLS) experiments (Figure and Figure S6). The scattering curves were fitted to a cylinder model with a fixed radius of 6 nm (radius obtained from SAXS measurements) . Upon addition of S ‐3Me‐BTA to a‐BTA , the changes in a‐BTA polymer length are negligible.…”

Section: Resultsmentioning

confidence: 99%

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Controlling the Length of Cooperative Supramolecular Polymers with Chain Cappers

Huurne

Chidchob

Long

et al. 2020

Chemistry A European J

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The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain capperso fs upramolecular polymers and feature one face as reactive as the BTAd iscotic to interact strongly with the polymere nd, whereas the other face is nonreactive and therefore impedes further polymerization. Such ad esign requires fine tuning of the conformational preorganization of the amides and the steric hindrance of the motif. The chain capperss tudied are monotopic derivatives of BTA, modified by partial N-methylation of the amides or by positioning of ab ulky cyclotriveratrylene cage on one face of the BTAu nit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterizationmethods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Controlling the Length of Cooperative Supramolecular Polymers with Chain Cappers

Huurne

Chidchob

Long

et al. 2020

Chemistry A European J

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“…Whereas chain-cappers for the isodesmic supramolecular polymers are easy to design, for highly cooperative and ordered polymers it is still a mystery. [100] Dynamics of the exchange of monomers from one polymer to the other is probably one of the most fascinating elements of ordered filaments in solution. This exchange can occur at the end of the chain or just by an escape from within the chain followed by an intercalation to enter another chain.…”

Section: Perspective On Some Of the Major Challengesmentioning

confidence: 99%

“…Concepts to arrive at block copolymers under thermodynamic and kinetic controls are just emerging, but lack clear generality at present. Whereas chain‐cappers for the isodesmic supramolecular polymers are easy to design, for highly cooperative and ordered polymers it is still a mystery . Dynamics of the exchange of monomers from one polymer to the other is probably one of the most fascinating elements of ordered filaments in solution.…”

Section: Perspective On Some Of the Major Challengesmentioning

confidence: 99%

Supramolecular Polymers – we've Come Full Circle

Aida

Meijer

2020

Israel Journal of Chemistry

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161

142

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Since the first polymers were discovered, scientists have debated their structures. Before Hermann Staudinger published the brilliant concept of macromolecules, polymer properties were generally believed to be based on the colloidal aggregation of small particles or molecules. From 1920 onwards, polymers and macromolecules are synonymous with each other; i. e. materials made by many covalent bonds connecting monomers in 2 or 3 dimensions. Although supramolecular interactions between macromolecular chains are evidently important, e. g. in nylons, it was unheard of to proposing polymeric materials based on the interaction of small molecules. Breakthroughs in supramolecular chemistry, however, showed that polymer materials can be made by small molecules using strong directional secondary interactions; the field of supramolecular polymers emerged. In a way, we have come full circle. In this essay we give a personal story about the birth of supramolecular polymers, with special emphasis on their structures, way of formation, and the dynamic nature of their bonding. The adaptivity of supramolecular polymers has become a major asset for novel applications, e. g. in the direction for the sustainable use of polymers, but also in biomedicine and electronics as well as self‐healing materials. The lessons learned in the past years include aspects that forecast a bright future for the use of supramolecular interactions in polymer materials in general and for supramolecular polymers in particular. In order to give full tribute to Staudinger in the year celebrating 100 years of macromolecules, we will show that many of the concepts of macromolecular polymers apply to supramolecular polymers, with only one important difference with fascinating consequences: the dynamic nature of the bonds that form polymer chains.

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“…We most recently applied these scripts to delineate the copolymerization of chiral and achiral analogues of BTA and thio-BTA in modified types of sergeant-and-soldiers and majority-rules experiments 56 as well as to investigate the effect of competitive sequestration, chain capping, and intercalation on supramolecular polymer lengths. 57 Moreover, these scripts also allow other interested researchers to apply mass-balance models to rationalize their current and future supramolecular (co)polymerization systems. We envision that this will help to unravel a wealth of other phenomena in supramolecular (co)polymerizations in the future.…”

Section: Resultsmentioning

confidence: 99%

Mass-Balance Models for Scrutinizing Supramolecular (Co)polymerizations in Thermodynamic Equilibrium

Eikelder

Markvoort

2019

Acc. Chem. Res.

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ConspectusRecent years have witnessed increasing attention on supramolecular polymerization, i.e., the formation of one-dimensional aggregates in which the monomeric units bind together via reversible and usually highly directional non-covalent interactions. Because of the presence of these reversible interactions, such as hydrogen bonding, π–π interactions, or metal coordination, supramolecular polymers exhibit numerous desirable properties ranging from high thermoresponsiveness to self-healing and great capacity for processability and recycling. These properties relate to intriguing experimentally observed nonlinear effects such as the monomer-dependent presence of a critical temperature for aggregation and a solvent- and temperature-tunable aggregate morphology. For coassemblies this is complemented with monomer-ratio- and monomer-compatibility-dependent internal order as well as majority-rules-type chiral amplification. However, the dynamic nature of the (co)polymers and the intricate interplay of many interactions make these effects difficult to rationalize without theoretical models.This Account presents recent advances in the development and use of equilibrium models for supramolecular copolymerization based on mass balances, mainly developed by our group. The basic idea of these models is that we describe a supramolecular (co)polymerization by a set of independent equilibrium reactions, like monomer associations and dissociations, and that in thermodynamic equilibrium the concentrations of the reactants and products in each reaction are coupled via the equilibrium constant of that reaction. Recursion then allows the concentration of each possible aggregate to be written as a function of the free monomer concentrations. Because a monomer should be present either as a free monomer or in one of the aggregates, a set of n equations can be formed with the n free monomer concentrations as the only unknowns. This set of mass-balance equations can then be solved numerically, yielding the free monomer concentrations, from which the complete system can be reconstituted.By a step-by-step extension of the model for the aggregation of a single monomer type to include the formation of multiple aggregate types and the coassembly of multiple monomer types, we can capture increasingly complex supramolecular (co)polymerizations. In each step we illustrate how the extended model explains in detail another of the experimentally observed nonlinear effects, with the common denominator that small differences in association energies are intricately amplified at the supramolecular level. We finally arrive at our latest and most general approach to modeling (cooperative) supramolecular (co)polymerization, which encompasses all of our earlier models and shows great promise to help rationalize also future systems featuring ever-increasing complexity.

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Tuning the Length of Cooperative Supramolecular Polymers under Thermodynamic Control

Cited by 60 publications

References 51 publications

Controlling the Length of Cooperative Supramolecular Polymers with Chain Cappers

Controlling the Length of Cooperative Supramolecular Polymers with Chain Cappers

Supramolecular Polymers – we've Come Full Circle

Mass-Balance Models for Scrutinizing Supramolecular (Co)polymerizations in Thermodynamic Equilibrium

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