title: "Helter-skelter-like" perylene polyisocyanopeptides.
abstract: Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well-defined 4(1) 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 4(1) 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.
authors.affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 Ed Nijmegen, The Netherlands.
authors.forename: Erik
authors.initials: E
authors.lastname: Schwartz
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Palermo
authors.forename: Chris E
authors.initials: CE
authors.lastname: Finlayson
authors.forename: Ya-Shih
authors.initials: YS
authors.lastname: Huang
authors.forename: Matthijs B J
authors.initials: MB
authors.lastname: Otten
authors.forename: Andrea
authors.initials: A
authors.lastname: Liscio
authors.forename: Sara
authors.initials: S
authors.lastname: Trapani
authors.forename: Irene
authors.initials: I
authors.lastname: González-Valls
authors.forename: Patrick
authors.initials: P
authors.lastname: Brocorens
authors.forename: Jeroen J L M
authors.initials: JJ
authors.lastname: Cornelissen
authors.forename: Kalina
authors.initials: K
authors.lastname: Peneva
authors.forename: Klaus
authors.initials: K
authors.lastname: Müllen
authors.forename: Frank C
authors.initials: FC
authors.lastname: Spano
authors.forename: Arkady
authors.initials: A
authors.lastname: Yartsev
authors.forename: Sebastian
authors.initials: S
authors.lastname: Westenhoff
authors.forename: Richard H
authors.initials: RH
authors.lastname: Friend
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.forename: Roeland J M
authors.initials: RJ
authors.lastname: Nolte
authors.forename: Paolo
authors.initials: P
authors.lastname: Samorì
authors.forename: Alan E
authors.initials: AE
authors.lastname: Rowan
mesh_terms: D004563:Electrochemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D010569:Perylene / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D011140:Polyurethanes / Q000737:chemistry*; D013050:Spectrometry, Fluorescence
chemical_list: D010455:Peptides; D011108:Polymers; D011140:Polyurethanes; D010569:Perylene