Competing
Interactions in Hierarchical Porphyrin Self-Assembly
Introduce Robustness in Pathway Complexity
Version 2 2018-06-18, 19:04
Version 1 2018-06-18, 19:02
Posted on 2018-06-18 - 19:04
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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Mabesoone, Mathijs
F. J.; Markvoort, Albert J.; Banno, Motonori; Yamaguchi, Tomoko; Helmich, Floris; Naito, Yuki; et al. (2018). Competing
Interactions in Hierarchical Porphyrin Self-Assembly
Introduce Robustness in Pathway Complexity. ACS Publications. Collection. https://doi.org/10.1021/jacs.8b02388
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AUTHORS (9)
MM
Mathijs
F. J. Mabesoone
AM
Albert J. Markvoort
MB
Motonori Banno
TY
Tomoko Yamaguchi
FH
Floris Helmich
YN
Yuki Naito
EY
Eiji Yashima
AR
Anja R. A. Palmans
EM
E. W. Meijer
KEYWORDS
porphyrin-based monomermonomer poolJ-type aggregatessingle-pathway polymerizationisodesmic aggregation pathway buffersapplicationconcentration changespathway complexitymodels showPathway Complexity Pathway complexityswitch-like behaviormaterial behaviorH-aggregateisodesmic mechanismHierarchical Porphyrin Self-Assemblyaggregation pathways