Solvent dependent pathway complexity and seeded supramolecular polymerization

Abstract

cNDI-1 exhibits an off-pathway aggregate in cyclic hydrocarbon (MCH) but produces a helical supramolecular polymer in linear alkane (decane) by well-defined J-aggregation. Effective solvent-assisted nucleation in linear alkanes due to shape matching with the peripheral alkyl chains of a monomer is responsible for the pathway complexity. Seed, produced by sonication induced fragmentation of the fibers in decane, could initiate supramolecular polymerization of the off-pathway aggregate in MCH generating controllable helical nanostructures. The chiral seed of cNDI-1 was also successfully employed for the synthesis of a helical supramolecular polymer from the off-pathway aggregate of achiral cNDI-2.

Living supramolecular polymerization based on reversible deactivation of a monomer by using a ‘dummy’ monomer

“…In the last decade, mechanistic insights into supramolecular polymerization have been signicantly enriched, 1,[4][5][6][7][8][9][10][11] and have recently led to the development of living supramolecular polymerization (LSP). [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] It is intriguing that both LRP and LSP rely on reversible and dynamic equilibrium coupled with the polymerization pathway. So far, the formation of metastable aggregates (Fig.…”

“…So far, the formation of metastable aggregates (Fig. 1b) [12][13][14][15][16][17] and intramonomer hydrogen bonds (Fig. 1c), [18][19][20][21][22][23] and photoisomerization ( Fig.…”

Composition‐dependent crystallization behavior of copolyperoxides from methyl methacrylate and 4‐vinylbenzyl stearate

“…Note that the dilute CPVBM3 and CPVBM4 samples were drop casted onto mica followed by spin coating to prepare the homogenous surface, and these samples were not annealed thermally at above their melting temperature to avoid cleavage of thermally labile peroxy links in the main chain of the copolyperoxides. Formation of a layered fibrillar structure was witnessed with the average thickness of ~8.90 and ~8.46 nm for the CPVBM3 and CPVBM4, respectively. Interestingly, the average height of the monolayer for the CPVBM3 nicely matched with the d ‐spacing value as estimated from SAXS analysis (8.44 nm) .…”

Trismaleimide Dendrimers: Helix‐to‐Superhelix Supramolecular Transition Accompanied by White‐Light Emission

“…Ghosh et al. reported the formation pathways of helical supramolecular polymers from naphthalenediimides substituted with long soft chains . In G 1.5 a , 12 long alkyl chains surrounding a dendrimer rigid core release the stress from dendrimer cores packing together, which favors the formation of energy‐minimized and optimized supramolecular superstructures.…”