Programmable Supramolecular Polymerizations

Abstract

Living large: Rational design of self-assembly pathways has been demonstrated in supramolecular polymers. By controlling the concentration of an aggregation-competent monomer through intramolecular interactions, living supramolecular polymerization conditions were achieved. This universal approach can be used to obtain aggregates of well-defined length and narrow dispersity, and allows access to new supramolecular polymer architectures.

Controlling supramolecular polymerization through multicomponent self‐assembly

“…36 De Greef, Meijer and coworkers lead the pioneering work in the thermodynamic and kinetic elucidation of small molecule based self-assembly pathways in supramolecular polymers. 33,424,427 A nucleus that has a higher free energy compared to the monomeric species and the significant energy barrier for selfassembly result in characteristic lag phases in the polymerization kinetics, in full agreement with protein aggregation systems. [428][429][430][431][432][433][434] Detailed studies have highlighted the presence of these lag phases, as well as the presence of competing offpathway aggregates, which can act as traps for free monomer and are thereby able to buffer the assembly dynamics.…”

“…10,[420][421][422] Alternatively, the manipulation of self-assembly pathways was very recently achieved via the rational design of selfassembling small molecular weight building blocks by three different groups. [423][424][425] Sugiyasu, Takeuchi and coworkers have been able to show that seed-induced growth in combination with a competing off-pathway aggregation leads to a "living" supramolecular polymerization of a Zn(II)-porphyrin dye ZnP4 in apolar methylcyclohexan (MCH). 36,426 The competing off-pathway porphyrin J-aggregates with a nanoparticle morphology are formed through isodesmic growth, and act as a kinetic trap that consumes monomers from solution (Fig.…”

Steric ploy for alternating donor–acceptor co-assembly and cooperative supramolecular polymerization

“…14 We have already shown (Fig. 2c) that the temperature for the onset of homo-polymerization of NDI-2-EH ( T A ∼ 343 K) or DAN-4 ( T D ∼ 333 K) is significantly less compared to that for an alternating D–A stack ( T DA > 353 K).…”

Unravelling the Pathway Complexity in Conformationally Flexible N‐Centered Triarylamine Trisamides

“…Pathway complexity—the different reaction pathways and intermediates that can occur in a self‐assembling system—has recently been disclosed in several systems and the importance of controlling complex kinetic processes is a fundamental next step to take . The ability to access different assembled states and the quantification of the energetic barriers of a complex supramolecular landscape creates opportunities to realize living supramolecular polymerizations . Initially the strategy used to control the assembled architectures was the isolation of a kinetically trapped state and its seeding with a thermodynamically stable aggregate seed .…”