“Helter‐Skelter‐Like” Perylene Polyisocyanopeptides
- 23 February 2009
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 15 (11), 2536-2547
- https://doi.org/10.1002/chem.200801746
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.Keywords
This publication has 73 references indexed in Scilit:
- Acid‐Initiated Stereospecific Polymerization of IsocyanopeptidesAngewandte Chemie, 2005
- Investigation of Perylene Photonic Wires by Combined Single-Molecule Fluorescence and Atomic Force MicroscopyAngewandte Chemie, 2004
- Investigation of Perylene Photonic Wires by Combined Single-Molecule Fluorescence and Atomic Force MicroscopyAngewandte Chemie-International Edition, 2004
- Helical Polymer-Anchored Porphyrin NanorodsChemistry – A European Journal, 2003
- Vesicles and Polymerized Vesicles from Thiophene‐Containing Rod–Coil Block CopolymersAngewandte Chemie-International Edition, 2003
- Self-Organizing Liquid Crystal Perylene Diimide Thin Films: Spectroscopy, Crystallinity, and Molecular OrientationThe Journal of Physical Chemistry B, 2002
- Origin of the stabilization energy of perylene excimer as studied by fluorescence and near-IR transient absorption spectroscopyJournal of Photochemistry and Photobiology A: Chemistry, 2001
- Supramolecular Second-Order Nonlinearity of Polymers with Orientationally Correlated ChromophoresScience, 1995
- Screw sense selective polymerization of achiral isocyanides catalyzed by optically active nickel(II) complexesJournal of the American Chemical Society, 1988
- Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes. 3. Singlet and triplet excited-state properties of the bis(2,5-di-tert-butylphenyl)imide derivativeThe Journal of Physical Chemistry, 1987