'Helter-Skelter-Like' Perylene Polyisocyanopeptides
| Autor: | Schwartz, E., Schwartz, Erik, Palermo, Vincenzo, Finlayson, Chris E., Huang, Ya-Shih, Otten, Matthijs B.J., Liscio, Andrea, Trapani, Sara, Gonzalez-Valls, Irene, Brocorens, Patrick, Cornelissen, Jeroen Johannes Lambertus Maria, Peneva, Kalina, Mullen, Klaus, Spano, Frank C., Yartsev, Arkady, Westenhoff, Sebastian, Friend, Richard H., Beljonne, David, Nolte, Roeland J.M., Samori, Paolo, Rowan, Alan E. |
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| Přispěvatelé: | Biomolecular Nanotechnology, Faculty of Science and Technology |
| Rok vydání: | 2009 |
| Předmět: |
Models
Molecular Polymers Stereochemistry Polyurethanes polyisocyanides Supramolecular chemistry METIS-263213 Catalysis Molecular dynamics chemistry.chemical_compound Electrochemistry Molecule electron transport Perylene Molecular Structure Hydrogen bond Molecular Materials Organic Chemistry IR-77785 General Chemistry Chromophore Spectrometry Fluorescence chemistry Chemical physics Helix Peptides perylene diimides Physical Organic Chemistry Cotton effect |
| Zdroj: | Chemistry : a European Journal, 15, 2536-2547 Chemistry : a European journal, 15(11), 2536-2547. Wiley-VCH Verlag Chemistry : a European Journal, 15, 11, pp. 2536-2547 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.200801746 |
| Popis: | Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well-defined 41 helix in which the perylene molecules (see figure) form four “helter-skelter-like” overlapping pathways along which excitons and electrons can rapidly migrate. We report on a combined experimental and computational investigation on the synthesis and thorough characterization of the structure of perylene-functionalized polyisocyanides. Spectroscopic analyses and extensive molecular dynamics studies revealed a well defined 41 helix in which the perylene molecules form four “helter skelter-like” overlapping pathways along which excitons and electrons can rapidly migrate. The well-defined polymer scaffold stabilized by hydrogen bonding, to which the chromophores are attached, accounts for the precise architectural definition, and molecular stiffness observed for these molecules. Molecular-dynamics studies showed that the chirality present in these polymers is expressed in the formation of stable right-handed helices. The formation of chiral supramolecular structures is further supported by the measured and calculated bisignated Cotton effect. The structural definition of the chromophores aligned in one direction along the backbone is highlighted by the extremely efficient exciton migration rates and charge densities measured with Transient Absorption Spectroscopy |
| Databáze: | OpenAIRE |
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