Living Supramolecular Polymerisation of Perylene Diimide Amphiphiles by Seeded Growth under Kinetic Control

Abstract

The controlled solution self-assembly of an amphiphilic perylene diimide (PDI), with a hydrophobic perylene core and hydrophilic imide substituents with polydisperse oligo(ethylene glycol) (OEG) tethers is presented. It was possible, by a seeded-growth mechanism, to form colloidally stable, one-dimensional fibres with controllable lengths (from 400 to 1700 nm) and low dispersities (1.19-1.29) via a living supramolecular polymerisation process. Under the solvent conditions used, it was found that molecularly dissolved material (unimer) was present in samples of the fibre-like supramolecular assemblies. The free unimer may be present in a conformationally derived kinetically trapped state and/or may represent a more soluble PDI fraction with longer hydrophilic tethers. Significantly, it was also possible to form segmented supramolecular block copolymers by the addition of PDI unimer to chemically distinct PDI seeds, yielding fibres with controlled lengths. These results represent a significant advance in the ability to form PDI-based supramolecular polymers with precisely controlled lengths and architectures.

How to Determine the Role of an Additive on the Length of Supramolecular Polymers?

“…Moreover, by controlling the seed-to-monomer ratio, control over the polymer length has been achieved. The use of small seeds to synthesize supramolecular polymers of controlled length has since been shown in several other systems, such as zinc-chlorins, 29 perylenes, [30][31][32][33][34][35] pyrenes, 36 naphthalenes, 37 carbonyl-bridged triarylamine trisamides, 38 and peptide amphiphiles. 39 Recently, the groups of Che and Zhao expanded the use of seeded polymerization to generate also two-dimensional aggregates of controlled surface area.…”

Living supramolecular polymerization of fluorinated cyclohexanes

“…Many recent examples of LSP are based on a similar use of offpathway aggregates 14 , which can be self-assembled from diverse building blocks such as rylene dyes [15][16][17][18][19][20][21] , (aza)-BODIPY dyes 22,23 , N-heteroangulenes 24 and amphiphilic Pt II complexes 25 . Further examples make use of the counter-anion modulated aggregation of Pt II and Pd II pincer-type complexes 26 , the coupling of SP with a chemical fuel or light [27][28][29][30] , the trapping of an active monomer using "dummy" monomers incapable of 1D supramolecular polymerization 31 and the amplification of macrocycles from dynamic combinatorial libraries 32 .…”

Circularly Polarized Luminescence from Chiral Supramolecular Polymer and Seeding Effect

“…Although sonication fragmented the long polymers to shorter objects, UV/Vis and CD spectra of the sonicated sample (Figure S13) were almost identical to those of the parent polymer, confirming that sonication did not destroy the internal order of the aggregate and thus the possibility of using it as seed became feasible. Seeded supramolecular polymerization was then attempted by following a recently reported method . A monomeric solution of NDI‐1 in THF (100 μL, 3×10 −3 m ) was injected into the NDI‐2 seed solution in decane (900 μL, 5×10 −6 m ) so that NDI‐2 seed /NDI‐1 mono =1:67 in decane/THF (9:1) solvent mixture.…”