Competing interactions in hierarchical porphyrin self-assembly introduce robustness in pathway complexity

Mathijs F.J. Mabesoone, Albert J. Markvoort, Motonori Banno, Tomoko Yamaguchi, Floris Helmich, Yuki Naito, Eiji Yashima, Anja R.A. Palmans, E.W. Meijer

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19 Citations (Scopus)

Abstract

Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways. This behavior is illustrated with the supramolecular polymerization of a porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It is found that the monomers aggregate via an isodesmic mechanism in weakly coupled J-type aggregates at intermediate solvent quality and temperature, followed by nucleated H-aggregates at lower solvent qualities and temperatures. At further increased thermodynamic driving forces, such as high concentration and low temperature, the H-aggregates can form hierarchical superhelices. Our mathematical models show that, contrary to a single-pathway polymerization, the existence of the isodesmic aggregation pathway buffers the free monomer pool and renders the nucleation of the H-aggregates insensitive to concentration changes in the limit of high concentrations. We also show that, at a given temperature or solvent quality, the thermodynamically stable aggregate morphology can be selected by controlling the remaining free external parameter. As a result, the judicious application of pathway complexity allows us to synthesize a diverse set of materials from only a single monomer. We envision that the engineering of competing pathways can increase the robustness in a wide variety of supramolecular polymer materials and lead to increasingly versatile applications.

LanguageEnglish
Pages7810-7819
Number of pages10
JournalJournal of the American Chemical Society
Volume140
Issue number25
DOIs
StatePublished - 27 Jun 2018

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Porphyrins
Self assembly
Temperature
Polymerization
Monomers
Polymers
Agglomeration
Thermodynamics
Buffers
Theoretical Models
Nucleation
Switches
Mathematical models
Chemical analysis

Cite this

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title = "Competing interactions in hierarchical porphyrin self-assembly introduce robustness in pathway complexity",
abstract = "Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways. This behavior is illustrated with the supramolecular polymerization of a porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It is found that the monomers aggregate via an isodesmic mechanism in weakly coupled J-type aggregates at intermediate solvent quality and temperature, followed by nucleated H-aggregates at lower solvent qualities and temperatures. At further increased thermodynamic driving forces, such as high concentration and low temperature, the H-aggregates can form hierarchical superhelices. Our mathematical models show that, contrary to a single-pathway polymerization, the existence of the isodesmic aggregation pathway buffers the free monomer pool and renders the nucleation of the H-aggregates insensitive to concentration changes in the limit of high concentrations. We also show that, at a given temperature or solvent quality, the thermodynamically stable aggregate morphology can be selected by controlling the remaining free external parameter. As a result, the judicious application of pathway complexity allows us to synthesize a diverse set of materials from only a single monomer. We envision that the engineering of competing pathways can increase the robustness in a wide variety of supramolecular polymer materials and lead to increasingly versatile applications.",
author = "Mabesoone, {Mathijs F.J.} and Markvoort, {Albert J.} and Motonori Banno and Tomoko Yamaguchi and Floris Helmich and Yuki Naito and Eiji Yashima and Palmans, {Anja R.A.} and E.W. Meijer",
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Competing interactions in hierarchical porphyrin self-assembly introduce robustness in pathway complexity. / Mabesoone, Mathijs F.J.; Markvoort, Albert J.; Banno, Motonori; Yamaguchi, Tomoko; Helmich, Floris; Naito, Yuki; Yashima, Eiji; Palmans, Anja R.A.; Meijer, E.W.

In: Journal of the American Chemical Society, Vol. 140, No. 25, 27.06.2018, p. 7810-7819.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Competing interactions in hierarchical porphyrin self-assembly introduce robustness in pathway complexity

AU - Mabesoone,Mathijs F.J.

AU - Markvoort,Albert J.

AU - Banno,Motonori

AU - Yamaguchi,Tomoko

AU - Helmich,Floris

AU - Naito,Yuki

AU - Yashima,Eiji

AU - Palmans,Anja R.A.

AU - Meijer,E.W.

PY - 2018/6/27

Y1 - 2018/6/27

N2 - Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways. This behavior is illustrated with the supramolecular polymerization of a porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It is found that the monomers aggregate via an isodesmic mechanism in weakly coupled J-type aggregates at intermediate solvent quality and temperature, followed by nucleated H-aggregates at lower solvent qualities and temperatures. At further increased thermodynamic driving forces, such as high concentration and low temperature, the H-aggregates can form hierarchical superhelices. Our mathematical models show that, contrary to a single-pathway polymerization, the existence of the isodesmic aggregation pathway buffers the free monomer pool and renders the nucleation of the H-aggregates insensitive to concentration changes in the limit of high concentrations. We also show that, at a given temperature or solvent quality, the thermodynamically stable aggregate morphology can be selected by controlling the remaining free external parameter. As a result, the judicious application of pathway complexity allows us to synthesize a diverse set of materials from only a single monomer. We envision that the engineering of competing pathways can increase the robustness in a wide variety of supramolecular polymer materials and lead to increasingly versatile applications.

AB - Pathway complexity in supramolecular polymerization has recently sparked interest as a method to generate complex material behavior. The response of these systems relies on the existence of a metastable, kinetically trapped state. In this work, we show that strong switch-like behavior in supramolecular polymers can also be achieved through the introduction of competing aggregation pathways. This behavior is illustrated with the supramolecular polymerization of a porphyrin-based monomer at various concentrations, solvent compositions, and temperatures. It is found that the monomers aggregate via an isodesmic mechanism in weakly coupled J-type aggregates at intermediate solvent quality and temperature, followed by nucleated H-aggregates at lower solvent qualities and temperatures. At further increased thermodynamic driving forces, such as high concentration and low temperature, the H-aggregates can form hierarchical superhelices. Our mathematical models show that, contrary to a single-pathway polymerization, the existence of the isodesmic aggregation pathway buffers the free monomer pool and renders the nucleation of the H-aggregates insensitive to concentration changes in the limit of high concentrations. We also show that, at a given temperature or solvent quality, the thermodynamically stable aggregate morphology can be selected by controlling the remaining free external parameter. As a result, the judicious application of pathway complexity allows us to synthesize a diverse set of materials from only a single monomer. We envision that the engineering of competing pathways can increase the robustness in a wide variety of supramolecular polymer materials and lead to increasingly versatile applications.

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T2 - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

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