"Helter-skelter-like" perylene polyisocyanopeptides.
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.
Schwartz
Erik
E
Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 Ed Nijmegen, The Netherlands.
Palermo
Vincenzo
V
Finlayson
Chris E
CE
Huang
Ya-Shih
YS
Otten
Matthijs B J
MB
Liscio
Andrea
A
Trapani
Sara
S
González-Valls
Irene
I
Brocorens
Patrick
P
Cornelissen
Jeroen J L M
JJ
Peneva
Kalina
K
Müllen
Klaus
K
Spano
Frank C
FC
Yartsev
Arkady
A
Westenhoff
Sebastian
S
Friend
Richard H
RH
Beljonne
David
D
Nolte
Roeland J M
RJ
Samorì
Paolo
P
Rowan
Alan E
AE
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
D010455:Peptides; D011108:Polymers; D011140:Polyurethanes; D010569:Perylene