[en] The chiroptical properties of multi-chromophoric systems are governed by the intermolecular arrangement of the monomeric units. We report on a computational and experimental study of the linear optical properties and supramolecular structure of a rhodamine heterodimer assembled on a DNA scaffold. The experimental absorption and circular dichroism (CD) profiles confirm the dimer formation. Computationally, starting from low-cost DFT/TDDFT simulations of the bare dimer we attribute the measured -/+ CD sign sequence of the S1/S2 bands to a specific chiral conformation of the heterodimer. In the monomers, as typical for rhodamine dyes, the electric transition dipole of the lowest π-π* transition is parallel to the long axis of the xanthene planes. We show that in the heterodimer the sign sequence of the two CD bands is related to the orientation of these long axes. To account explicitly for environment effects, we use molecular dynamics (MD) simulations for characterizing the supramolecular structure of the two optical isomers tethered on DNA. Average absorption and CD-profiles were modeled using ab initio TDDFT calculations at the geometries sampled along a few nanosecond MD run. The absorption profiles computed for both optical isomers are in good agreement with the experimental absorption spectrum and do not allow one to discriminate between them. The computed averaged CD profiles provide the orientation of monomers in the enantiomer that is dominant under the experimental conditions.
Disciplines :
Chemistry
Author, co-author :
Rukin, P. S.; Theoretical Physical Chemistry, University of Liege, Liege, B4000, Belgium
Komarova, K. G.; Theoretical Physical Chemistry, University of Liege, Liege, B4000, Belgium
Fresch, B.; Department of Chemical Sciences, University of Padova, via Marzolo 1, Padova, 35131, Italy
Collini, E.; Department of Chemical Sciences, University of Padova, via Marzolo 1, Padova, 35131, Italy
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Language :
English
Title :
Chirality of a rhodamine heterodimer linked to a DNA scaffold: an experimental and computational study
Publication date :
2020
Journal title :
Physical Chemistry Chemical Physics
ISSN :
1463-9076
eISSN :
1463-9084
Publisher :
NLM (Medline)
Volume :
22
Issue :
14
Pages :
7516-7523
Peer reviewed :
Peer reviewed
Tags :
CÉCI : Consortium des Équipements de Calcul Intensif
Funders :
DG RDT - European Commission. Directorate-General. Research and Innovation FNR - Fonds National de la Recherche
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