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Cooperative Supramolecular Polymerization: Comparison of Different Models Applied on the Self-Assembly of Bis(merocyanine) Dyes

Authors

  • Dr. Gustavo Fernández,

    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
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  • Dr. Matthias Stolte,

    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
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  • Dr. Vladimir Stepanenko,

    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
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  • Prof. Dr. Frank Würthner

    Corresponding author
    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
    • Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
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Abstract

Three new molecular building blocks 1 ac for supramolecular polymerization are described that feature two dipolar merocyanine dyes tethered by p-xylylene spacers. Concentration- and temperature-dependent UV/Vis spectroscopy in chloroform combined with dynamic light scattering, capillary viscosimetry and atomic force microscopy investigations were applied to elucidate the mechanistic features of the self-assembly of these strongly dipolar dyes. Our detailed studies reveal that the self-assembly is very pronounced for bis(merocyanines) 1 a,b bearing linear alkyl chains, but completely absent for bis(merocyanine) 1 c bearing sterically more bulky ethylhexyl substituents. Both temperature- and concentration-dependent UV/Vis data provide unambiguous evidence for a cooperative self-assembly process for bis(merocyanines) 1 a,b, which was analyzed in detail by the Meijer–Schenning–Van-der-Schoot model (applicable to temperature-dependent data) and by the Goldstein–Stryer model (applicable to concentration-dependent data). By combining both methods all parameters of interest to understand the self-assembly process could be derived, including in particular the nucleus size (8–10 monomeric units), the cooperativity factor (ca. 0.006), and the nucleation and elongation constants of about 103 and 106M−1 in chloroform at room temperature, respectively.

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