Hierarchical Self-Organization of Chiral Columns from Chiral Supramolecular Spheres
| العنوان: | Hierarchical Self-Organization of Chiral Columns from Chiral Supramolecular Spheres |
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| المؤلفون: | Xiangbing Zeng, Virgil Percec, Goran Ungar, Mihai Peterca, Mohammad R. Imam, Paul A. Heiney, Daniela A. Wilson, Dipankar Sahoo, Benjamin E. Partridge |
| المصدر: | Journal of the American Chemical Society, 140, 13478-13487 Journal of the American Chemical Society, 140, 41, pp. 13478-13487 |
| سنة النشر: | 2018 |
| مصطلحات موضوعية: | Systems Chemistry, Supramolecular chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Bio-Organic Chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Tetragonal crystal system, Colloid and Surface Chemistry, Monomer, Polymerization, chemistry, Phase (matter), Intermediate state, Molecule, 0210 nano-technology, Chirality (chemistry) |
| الوصف: | The supramolecular column is an archetypal architecture in the field of periodic liquid crystalline and crystalline arrays. Columns are generated via self-assembly, coassembly, and polymerization of monomers containing molecules shaped as discs, tapered, twin- and Janus-tapered, crowns, hat-shaped crowns, and fragments thereof. These supramolecular columns can be helical and therefore exhibit chirality. In contrast, spheres represent a fundamentally distinct architecture, generated from conical and crown-like molecules, which self-organize into body-centered cubic, Pm3̅ n cubic (also known as Frank-Kasper A15), and tetragonal (also known as Frank-Kasper σ) phases. Supramolecular spherical aggregates are not known to further assemble into a columnar architecture, except as an intermediate state between a columnar periodic array and a cubic phase. In the present work, a chiral dendronized cyclotetraveratrylene (CTTV) derivative is demonstrated to self-organize into a supramolecular column unexpectedly constructed from supramolecular spheres, with no subsequent transition to a cubic phase. Structural and retrostructural analysis using a combination of differential scanning calorimetry, X-ray diffraction (XRD), molecular modeling, and simulation of XRD patterns reveals that this CTTV derivative, which is functionalized with eight chiral first-generation minidendrons, self-organizes via a column-from-spheres model. The transition from column to column-from-spheres was monitored by circular dichroism spectroscopy, which demonstrated that both the supramolecular column and supramolecular spheres are chiral. This column-from-spheres model, which unites two fundamentally distinct self-assembled architectures, provides a new mechanism to self-organize supramolecular columnar architectures. |
| وصف الملف: | application/pdf |
| تدمد: | 0002-7863 |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::26f32de9c3910b6a32c1debb4d9db700Test https://hdl.handle.net/2066/197359Test |
| حقوق: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....26f32de9c3910b6a32c1debb4d9db700 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 00027863 |
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