Self‐Assembly of a Highly Organized,Hexameric Supramolecular Architecture: Formation,Structure and Properties |
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Authors: | Dr Gaël Schaeffer Dr Olaf Fuhr Prof Dieter Fenske Prof Jean‐Marie Lehn |
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Institution: | 1. Laboratoire de Chimie Supramoléculaire, ISIS, Université de Strasbourg, 8 Allée Gaspard Monde, 67000 Strasbourg (France), Fax: (+33)?368‐855‐140;2. Institut für Nanotechnologie und Karlsruhe Nano Micro Facility (KNMF), Karlsruher Institut für Technologie (KIT), Hermann‐von‐Helmholtz‐Platz 1, 76344 Eggenstein‐Leopoldshafen (Germany);3. Lehn‐Institute for Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat‐Sen University, Guangzhou (P. R. China);4. Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstra?e 15, 76131 Karlsruhe (Germany) |
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Abstract: | Two derivatives, 3 L and 9 L , of a ditopic, multiply hydrogen‐bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self‐assembly into a complex supramolecular species. The solid‐state molecular structure of 3 L , determined by single‐crystal X‐ray crystallography, revealed that it forms a highly organized hexameric entity 3 L 6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen‐bonding interactions. The complicated 1H NMR spectra observed in o‐dichlorobenzene (o‐DCB) for 3 L and 9 L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen‐bond‐disrupting solvent, such as DMSO, the 1H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature‐dependent 1H NMR studies in o‐DCB showed that the L 6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. |
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Keywords: | hydrogen bonds noncovalent interactions self‐assembly structure elucidation supramolecular chemistry |
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