Issue 34, 2017

Coherent electronic and nuclear dynamics in a rhodamine heterodimer–DNA supramolecular complex

Abstract

Elucidating the role of quantum coherences in energy migration within biological and artificial multichromophoric antenna systems is the subject of an intense debate. It is also a practical matter because of the decisive implications for understanding the biological processes and engineering artificial materials for solar energy harvesting. A supramolecular rhodamine heterodimer on a DNA scaffold was suitably engineered to mimic the basic donor–acceptor unit of light-harvesting antennas. Ultrafast 2D electronic spectroscopic measurements allowed identifying clear features attributable to a coherent superposition of dimer electronic and vibrational states contributing to the coherent electronic charge beating between the donor and the acceptor. The frequency of electronic charge beating is found to be 970 cm−1 (34 fs) and can be observed for 150 fs. Through the support of high level ab initio TD-DFT computations of the entire dimer, we established that the vibrational modes preferentially optically accessed do not drive subsequent coupling between the electronic states on the 600 fs of the experiment. It was thereby possible to characterize the time scales of the early time femtosecond dynamics of the electronic coherence built by the optical excitation in a large rigid supramolecular system at a room temperature in solution.

Graphical abstract: Coherent electronic and nuclear dynamics in a rhodamine heterodimer–DNA supramolecular complex

Supplementary files

Article information

Article type
Paper
Submitted
01 Mar 2017
Accepted
11 Jul 2017
First published
17 Aug 2017
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2017,19, 23043-23051

Coherent electronic and nuclear dynamics in a rhodamine heterodimer–DNA supramolecular complex

M. Cipolloni, B. Fresch, I. Occhiuto, P. Rukin, K. G. Komarova, A. Cecconello, I. Willner, R. D. Levine, F. Remacle and E. Collini, Phys. Chem. Chem. Phys., 2017, 19, 23043 DOI: 10.1039/C7CP01334E

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