title: Diversification of self-organized architectures in supramolecular dye assemblies.
abstract: Upon complexation with bismelamine receptors (BMn) featuring different alkyl linker lengths (number of methylene groups (n) = 5-12), a barbituric acid merocyanine dye (1) can be loaded into diverse self-organized superstructures through multiple hydrogen-bonding interactions. UV/vis, dynamic light scattering, and NMR studies in cyclohexane demonstrate that the diversification of the primarily formed hydrogen-bonded species in solution occurs by varying the linker length of BMn. Hierarchical organization of the hydrogen-bonded species is achieved by slow evaporation of the solvent (forming solvent-free films), and the resulting superstructures are evaluated by polarized optical microscopy, X-ray diffraction, SEM, and AFM techniques. The formation of columnar structures with and without two-dimensional ordering are revealed for shorter (n = 5-7) and longer (n = 11, 12) linker bis(melamines), respectively. On the contrary, in the cases of n = 8-10, the formation of lamellar structures is unveiled. Several assemblies (n = 5, 7, 11) indicate the formation of a liquid crystalline mesophase in POM and DSC analyses. Hierarchical organization is also achieved in solution by prolonged aging, affording phase-separated crystalline nanofibers (n = 5, 7) and soft nanofibrils agglomerating into wormlike objects (n = 8), gel-forming continuous globular networks (n = 10), and nanofibers (n = 11, 12). These superstructural and morphological diversifications are an outcome of the variation in the primarily formed hydrogen-bonded supramolecular architectures. Using this strategy, diverse self-assembled materials will be obtained from a single dye component.
authors.affiliation: Department of Applied Chemistry and Biotechnology, Faculty of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan. yagai@faculty.chiba-u.jp
authors.forename: Shiki
authors.initials: S
authors.lastname: Yagai
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Kinoshita
authors.forename: Masatsugu
authors.initials: M
authors.lastname: Higashi
authors.forename: Keiki
authors.initials: K
authors.lastname: Kishikawa
authors.forename: Takashi
authors.initials: T
authors.lastname: Nakanishi
authors.forename: Takashi
authors.initials: T
authors.lastname: Karatsu
authors.forename: Akihide
authors.initials: A
authors.lastname: Kitamura