“Helter-Skelter-Like” Perylene Polyisocyanopeptides

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Schwartz, Erik and Palermo, Vincenzo and Finlayson, Chris E. and Huang, Ya-Shih and Otten, Matthijs B.J. and Liscio, Andrea and Trapani, Sara and Gonzalez-Valls, Irene and Brocorens, Patrick and Cornelissen, Jeroen J.L.M. and Peneva, Kalina and Mullen, Klaus and Spano, Frank C. and Yartsev, Arkady and Westenhoff, Sebastian and Friend, Richard H. and Beljonne, David and Nolte, Roeland J.M. and Samori, Paolo and Rowan, Alan E. (2009) “Helter-Skelter-Like” Perylene Polyisocyanopeptides. Chemistry: a European Journal, 15 (11). pp. 2536-2547. ISSN 0947-6539

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Abstract: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
Item Type:Article
Copyright:© 2009 WILEY-VCH Verlag GmbH
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Science and Technology (TNW)
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Link to this item:http://purl.utwente.nl/publications/77785
Official URL:http://dx.doi.org/10.1002/chem.200801746
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Metis ID: 263213