Journal
SMALL
Volume 14, Issue 3, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.201702437
Keywords
kinetics; living supramolecular polymerization; pathway complexity; seeded supramolecular polymerization; self-assembly
Categories
Funding
- MINECO of Spain [CTQ2014-53046-P]
- Comunidad de Madrid (NanoBIOSOMA) [S2013/MIT-2807]
- MINECO
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Herein, the synthesis and self-assembling features of N-heterotriangulenes 1-3 decorated in their periphery with 3,4,5-trialkoxy-N-(alkoxy)benzamide moieties that enable kinetic control of the supramolecular polymerization process are described. The selection of an appropriate solvent results in a tunable energy landscape in which the relative energy of the different monomeric or aggregated species can be regulated. Thus, in a methylcyclohexane/toluene (MCH/Tol) mixture, intramolecular hydrogen-bonding interactions in the peripheral side units favor the formation of metastable inactivated monomers that evolve with time at precise conditions of concentration and temperature. A pathway complexity in the supramolecular polymerization of 1-3 cannot be determined in MCH/Tol mixtures but, importantly, this situation changes by using CCl4. In this solvent, the off-pathway product is a face-to-face H-type aggregate and the on-pathway product is the slipped face-to-face J-type aggregate. The autocatalytic transformation of the metastable monomeric units, as well as the two competing off- and on-pathway aggregates allow the realization of seeded and living supramolecular polymerizations. Interestingly, the presence of chiral, branched side chains in chiral (S)-2 noticeably retards the kinetics of the investigated transformations. This work brings to light the relevance of controlling the pathway complexity in self-assembling units and opens new avenues for the investigation of complex and functional supramolecular structures.
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