Hierarchical Chiral Expression from the Nano- to Mesoscale in Synthetic Supramolecular Helical Fibers of a Nonamphiphilic C3-Symmetrical π-Functional Molecule
| Autor: | Narcis Avarvari, John D. Wallis, François Riobé, Mathieu Linares, Flavia Piron, David B. Amabilino, Josep Puigmartí-Luis, Ion Danila, Hans Ågren, David Beljonne |
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| Přispěvatelé: | MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institute of Biological Chemistry, Washington State University (WSU), Department of Science and Technology [Linköping], Linköping University (LIU), Theoretical Chemistry, Royal Institute of Technology [Stockholm] (KTH ), Laboratory for Chemistry of Novel Materials, Université de Mons (UMons), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2011 |
| Předmět: |
Circular dichroism
010405 organic chemistry Chemistry Supramolecular chemistry General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography Molecular dynamics chemistry.chemical_compound Colloid and Surface Chemistry Enantiopure drug Helix Molecule Enantiomer Tetrathiafulvalene |
| Zdroj: | Journal of the American Chemical Society Journal of the American Chemical Society, American Chemical Society, 2011, 133 (21), pp.8344-8353. ⟨10.1021/ja202211k⟩ Journal of the American Chemical Society, 2011, 133 (21), pp.8344-8353. ⟨10.1021/ja202211k⟩ |
| ISSN: | 0002-7863 1520-5126 |
| DOI: | 10.1021/ja202211k⟩ |
| Popis: | International audience; The controlled preparation of chiral structures is a contemporary challenge for supramolecular science because of the interesting properties that can arise from the resulting materials, and here we show that a synthetic nonamphiphilic C3 compound containing π-functional tetrathiafulvalene units can form this kind of object. We describe the synthesis, characterization, and self-assembly properties in solution and in the solid state of the enantiopure materials. Circular dichroism (CD) measurements show optical activity resulting from the presence of twisted stacks of preferential helicity and also reveal the critical importance of fiber nucleation in their formation. Molecular mechanics (MM) and molecular dynamics (MD) simulations combined with CD theoretical calculations demonstrate that the (S) enantiomer provides the (M) helix, which is more stable than the (P) helix for this enantiomer. This relationship is for the first time established in this family of C3 symmetric compounds. In addition, we show that introduction of the “wrong” enantiomer in a stack decreases the helical reversal barrier in a nonlinear manner, which very probably accounts for the absence of a “majority rules” effect. Mesoscopic chiral fibers, which show inverted helicity, i.e. (P) for the (S) enantiomer and (M) for the (R) one, have been obtained upon reprecipitation from dioxane and analyzed by optical and electronic microscopy. The fibers obtained with the racemic mixture present, as a remarkable feature, opposite homochiral domains within the same fiber, separated by points of helical reversal. Their formation can be explained through an “oscillating” crystallization mechanism. Although C3 symmetric disk-shaped molecules containing a central benzene core substituted in the 1,3,5 positions with 3,3′-diamido-2,2′-bipyridine based wedges have shown peculiar self-assembly properties for amphiphilic derivatives, the present result shows the benefits of reducing the nonfunctional part of the molecule, in our case with short chiral isopentyl chains. The research reported herein represents an important step toward the preparation of functional mesostructures with controlled helical architectures. |
| Databáze: | OpenAIRE |
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