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ChemComm
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DOI: 10.1039/C7CC00554G
COMMUNICATION
Journal Name
J. Am. Chem. Soc., 2009, 131, 11106.
2R-cNDI, with the latter showing about 30% reduced uptake.
This suggests that aggregation of the encapsulated dyes
proceed fairly independently (Fig. 3b), resulting in a perfect
self-sorting in the aggregate state.19 We speculate that the
observed self-sorting is an outcome of a fast encapsulation
followed by an equally fast H-aggregation kinetics discussed
earlier, which precludes the formation of any mixed aggregate.
To conclude, we have demonstrated that spatial
confinement offers a rapid and efficient strategy for molecular
aggregation, particularly when intermolecular non-covalent
interactions are too weak to accomplish the same. Local
concentration and the entropy of the confined molecules are
significantly different from those in solution, making it possible
to realize unique geometries through different self-assembly
pathways. Micellar core provides a significant degree of
thermal stability/insulation to the encapsulated aggregates.
Finally, fast aggregation kinetics allows a perfect self-sorting of
aggregates.
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The authors gratefully acknowledge IISER Kolkata and
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Notes and references
† London dispersion forces between the hydrocarbon side-chains
are much shorter-range interactions (1/r6) than pi-stacking (1/r5)
and are therefore, less likely to play a dominant role in the initial
stages of self-assembly, when molecules are isolated and far
from each other.
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‡ A coexistence of two kinds of aggregates within the tiny core of
the micelle is likely to favour an efficient transfer of
photoexcitation energy from the reorganized J- to H-aggregates,
thus explaining a lack of PL from the former.
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