Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 42, Pages 14851-14861Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502434
Keywords
dipolar interaction; dyes/pigments; excitonic coupling; foldamers; self-assembly
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We have synthesized a large series of bis(merocyanine) dyes with varying spacer unit and investigated in detail their self-organization behavior by concentration-as well as solvent-dependent UV/Vis spectroscopy. Our in-depth studies have shown that the self-organization of the present bis(merocyanine) dyes is subtly influenced by the nature of the spacer unit. The utilization of rigid spacers results in the formation of self-associated bimolecular complexes with high binding strength, while flexible spacers drive the respective bichromophoric dyes to intramolecular folding. Our thorough investigations on the impact of alkyl spacer chain length on the folding tendency of the present series of bis(merocyanine) dyes revealed a biphasic behavior, that is, a steep increase of the folding tendency for the dyes containing C4 to C7 chains and then a gentle decrease for dyes with longer alkyl spacer chains as evidenced by free energy (Delta G) values for the folding of these dyes. Furthermore, analyses of aggregates' optical properties based on exciton theory as well as quantum chemical calculations suggest a bimolecular aggregate structure for the dye possessing a rigid spacer and a rotationally twisted pleated structure for the bis(merocyanine) dyes having spacer units with less than seven carbon atoms, while the application of longer alkyl chain linkers (>= C7) provides enough flexibility to orient the chromophores in electrostatically most favored antiparallel fashion.
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