Designing structural motifs for clickamers: exploiting the 1,2,3-triazole moiety to generate conformationally restricted molecular architectures |
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Authors: | Zornik Denise Meudtner Robert M El Malah Tamer Thiele Christina M Hecht Stefan |
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Institution: | 1. Department of Chemistry, Humboldt‐Universit?t zu Berlin, Brook‐Taylor‐Strasse 2, 12489 Berlin (Germany), Fax: (+49)?30‐2093‐6940;2. Clemens Sch?pf Institut für Organische Chemie, Technische Universit?t Darmstadt, Petersenstrasse 22, 64287 Darmstadt (Germany) |
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Abstract: | Noncovalent interactions, especially hydrogen-bonding interactions as well as electrostatic forces, confined within one macromolecule are the key to designing foldamers that adopt well-defined conformations in solution. In the context of significant recent activities in the area of triazole-connected foldamers, so-called clickamers, we present a fundamental study that compares various model compounds that bear adjacent N-, O-, or F-heteroatom substituents. The interplay of attractive and repulsive interactions leads to rotational constraints around the single bonds attached to both the 1- and 4-positions of the 1,2,3-triazole moiety and should therefore be able to induce well-defined conformational preferences in higher oligomers and polymers, that is, foldamers. Various compounds were synthesized and characterized with regard to their preferred conformations in all three aggregation states--that is, in the gas phase, in solution as well as in the solid state--by employing DFT calculations, NMR spectroscopic experiments, and X-ray crystallography, respectively. On the basis of the thus-obtained general understanding of the conformational behavior of the individual connection motifs, heterostructures were prepared from different motifs without affecting their distinct folding characteristics. Therefore, this work provides a kind of foldamer construction kit, which should enable the design of various clickamers with specific shape and incorporated functionality. |
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Keywords: | click chemistry conformation analysis foldamers supramolecular chemistry triazoles |
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